Polymer, composition, cement admixture, and hydraulic composition

Abstract

The polymer contains a structural unit (a) represented by general formula (I) or (II), and a structural unit (b) represented by general formula (III). (Symbols in the formulae are as defined in the description.)

Description

Polymer, composition, cement admixture and hydraulic composition

[0001] The present invention relates to polymers, compositions, cement admixtures and hydraulic compositions.

[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, with water. Generally, hydraulic compositions begin to harden from the time they are mixed and prepared, and therefore tend to lose fluidity over time. Therefore, when a hydraulic composition prepared in a manufacturing plant or the like is transported to a construction site and poured, hardening progresses, resulting in a decrease in fluidity and a significant decrease in workability.

[0003] In order to solve the above problems, it is effective to suppress the increase in viscosity over time. One method for doing so is to increase the water / cement ratio, but this method has problems such as separation of aggregates and cements in the hydraulic composition, and a decrease in the strength of the set product of the hydraulic composition due to evaporation of water during setting of the hydraulic composition. Furthermore, with the above method, it is difficult to sufficiently suppress the increase in viscosity over time, i.e., to sufficiently suppress the decrease in fluidity over time.

[0004] In light of this background, various additives for hydraulic compositions have been proposed. For example, Patent Document 1 proposes a copolymer for cement admixtures obtained by polymerizing a specific unsaturated polyalkylene glycol ether monomer and an unsaturated monocarboxylic acid monomer, each having a limited chain length, under specific conditions. It is described that the copolymer exhibits excellent dispersibility even in a high water reduction range where the water / cement ratio is low. Patent Document 2 also proposes a concrete admixture containing (a) a copolymer of a specific alkenyl ether and maleic acid or a salt thereof, and (b) a copolymer obtained by polymerizing a monomer mixture containing (a) a specific monomer such as a (meth)acrylic acid ester of methoxypolyethylene glycol and (b) a specific monomer such as (meth)acrylic acid. It is described that the concrete admixture can impart stable fluidity to concrete.

[0005] Japanese Patent Application Laid-Open No. 2001-220417 Japanese Patent Application Laid-Open No. 2001-172068

[0006] If the decrease in fluidity of a hydraulic composition over time could be suppressed without increasing the water / cement ratio, workability during application would be improved and a decrease in strength of the set hydraulic composition could also be suppressed. However, the techniques described in Patent Documents 1 and 2 were not able to sufficiently suppress the decrease in fluidity over time. Therefore, an object of the present invention is to provide a polymer, a composition, and a cement admixture that can suppress the decrease in fluidity over time. Another object of the present invention is to provide a hydraulic composition in which the decrease in fluidity over time is suppressed.

[0007] As a result of investigations conducted by the inventors to solve the above problems, they found that a polymer having a specific structure can suppress the decrease in fluidity of a hydraulic composition over time, and thus completed the present invention.

[0008] That is, the present invention provides the following items [1] to

[13] : [1] A polymer comprising a structural unit (a) represented by the following general formula (I) or (II) and a structural unit (b) represented by the following general formula (III): (In general formulas (I) and (II), R １ and R２ 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. ３ 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 0 or 1, and m and n each independently represent an integer of 5 to 100. * represents a bond. (In general formula (III), R ２１ , R ２２ , and R ２３ each independently represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an alkyloxy group having 1 to 6 carbon atoms, an alkenyl group having 2 to 6 carbon atoms, an alkenyloxy group having 2 to 6 carbon atoms, an aralkyl group having 7 to 12 carbon atoms, an aralkyloxy group having 7 to 12 carbon atoms, an aryl group having 6 to 12 carbon atoms, an aryloxy group having 6 to 12 carbon atoms, a carboxy group, or an alkanoyloxy group having 2 to 6 carbon atoms linked together. X represents a carboxylate group, a phosphonate group, a sulfonate group, or a silicate group. M represents a hydrogen atom, an alkali metal atom, or ammonium. * represents a bond.) [2] In the general formula (I), R３ represents a hydrogen atom, R ４ , R ５ , R ６ , R ７ , R ８ , R ９ , R １０ , and R １１ [3] In the general formula (II), R ３ , R ４ , R ５ , R ６ , and R ７ [4] The polymer according to the above [1] or [2], wherein R ４ , R ５ , R ６ , and R ７ represents a hydrogen atom, and o and p are 0. [5] The polymer according to any one of the above [1] to [3], wherein in at least one selected from the group consisting of general formulas (I) and (II), R Ａ and R Ｂ each independently represent an ethylene group, a propylene group, or a butylene group. [6] The polymer according to any one of [1] to [5] above, wherein in at least one selected from the group consisting of general formulas (I) and (II), m and n each independently represent an integer of 10 to 50. [7] A composition comprising the polymer according to any one of [1] to [6] above and a polymer (A) represented by at least one selected from the group consisting of general formulas (IV) and (V) below: (In general formula (IV), R ３１ and R ３２ 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. ３３ represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or an alkanoyloxy group having 2 to 6 carbon atoms. ３４ , R ３５ , R ３６ , R ３７ , R ３８ , R３９ , R ４０ , and R ４１ R each independently represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms. ３４ , R ３５ , R ３６ , R ３７ , R ３８ , R ３９ , R ４０ , and R ４１ may be bonded to each other to form a ring structure. Ｃ and R Ｄ each independently represents an alkylene group having 2 to 6 carbon atoms. Ｃ O- may be the same or different from each other. Ｄ O- may be the same or different. q and r each independently represent 0 or 1, and s and t each independently represent an integer of 5 to 100.) [8] The composition according to the above [7], wherein the mass ratio of the polymer (A) to the polymer (polymer (A) / polymer) is 0.02 to 99.00. [9] The composition according to the above [7] or [8], wherein the mass ratio of the polymer (A) to the polymer (polymer (A) / polymer) is 0.02 to 20.00.

[10] A cement admixture comprising the polymer according to any of the above [1] to [6].

[11] A cement admixture comprising the composition according to any of the above [7] to [9].

[12] A hydraulic composition comprising the polymer according to any of the above [1] to [6].

[13] A hydraulic composition comprising the composition according to any of the above [7] to [9].

[0009] According to the present invention, it is possible to provide a polymer, a composition, and a cement admixture that can suppress the fluidity of a hydraulic composition from decreasing over time. It is also possible to provide a hydraulic composition in which the fluidity decrease over time is suppressed.

[0010] First, the definitions of the notations used in this specification are shown below. "(Meth)acrylic" is a general term for acrylic and methacrylic. Similarly, "(meth)acrylate" is a general term for acrylate and methacrylate, and "(meth)allyl" is a general term for allyl and methallyl. Furthermore, "acid (salt)" is a general term for acids and their acid salts. The weight average molecular weight in this specification is the weight average molecular weight calculated in terms of standard polystyrene as determined by gel permeation chromatography (GPC). Detailed measurement methods can be performed according to the methods described in the Examples.

[0011] [Polymer] The polymer according to the embodiment of the present invention contains a structural unit (a) represented by the following general formula (I) or (II) and a structural unit (b) represented by the following general formula (III).

[0012]

[0013]

[0014] It is believed that the polymer according to the embodiment of the present invention, containing the structural unit (a), exhibits excellent dispersing properties, and as a result, can suppress a decrease in the fluidity of the hydraulic composition over time. Although the detailed mechanism is unclear, it is believed to be as follows: The structural unit (a) has a polyfunctional alkylene glycol chain as a side chain. The polyfunctional alkylene glycol chain has an extremely bulky structure, which suppresses rapid adsorption of the polymer to cement and cement hydrate. As a result, there remains polymer that has not adsorbed to cement and cement hydrate even over time, and adsorption of the polymer to cement and cement hydrate progresses over time, which is believed to suppress a decrease in the fluidity of the hydraulic composition over time.

[0015] Furthermore, when the polymer contains the structural unit (b), the dispersibility of cement and cement hydrate immediately after the production of the hydraulic composition is improved.

[0016] <Structural Unit (a)> The structural unit (a) is represented by the above general formula (I). In general formula (I), R １ and R ２each independently represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or an alkanoyl group having 2 to 6 carbon atoms.

[0017] R １ and R ２ Examples of the alkyl group having 1 to 6 carbon atoms represented by include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, an n-pentyl group, an isopentyl group, a neopentyl group, an n-hexyl group, a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, and a cyclohexyl group.

[0018] R １ and R ２ Examples of the alkanoyl group having 2 to 6 carbon atoms represented by the formula (I) include an acetyl group, a propionyl group, a butyryl group, an isobutyryl group, a pentanoyl group, an isopentanoyl group, a pivaloyl group, a hexanoyl group, a cyclopropylacetyl group, a cyclobutaneacetyl group, and a cyclopentaneacetyl group.

[0019] 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.

[0020] R ３ represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or an alkanoyloxy group having 2 to 6 carbon atoms.

[0021] R ３ The alkyl group having 1 to 6 carbon atoms represented by is the same as the above-mentioned R １ and R ２ The same groups as those exemplified as the "alkyl group having 1 to 6 carbon atoms" represented by the formula: can be exemplified.

[0022] R ３ Examples of the alkanoyloxy group having 2 to 6 carbon atoms represented by the formula (I) include an acetyloxy group, a propionyloxy group, a butyryloxy group, an isobutyryloxy group, a pentanoyloxy group, an isopentanoyloxy group, a pivaloxy group, a cyclopropylacetyloxy group, a cyclobutaneacetyloxy group, and a cyclopentaneacetyloxy group.

[0023] From the viewpoint of the polymerizability of the monomer, R ３ 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.

[0024] 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.

[0025] R ４ , R ５ , R ６ , R ７ , R ８ , R ９ , R １０ , and R １１ The alkyl group having 1 to 6 carbon atoms represented by is the same as the above-mentioned R １ and R ２ The same groups as those exemplified as the "alkyl group having 1 to 6 carbon atoms" represented by the formula: can be exemplified.

[0026] From the viewpoint of ease of production and polymerizability of the monomer, R ４ , R ５ , R ６ , R ７ , R ８ , R ９ , R １０ , and R １１ is preferably a hydrogen atom or a methyl group, and more preferably a hydrogen atom.

[0027] 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. ４ , R ５ , R ６ , R ７ , R ８ , R９ , R １０ , and R １１ Examples 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.

[0028] 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, a butylene group, an isobutylene group, a pentylene group, an isopentylene group, a hexylene group, and a cyclohexylene group.

[0029] From the viewpoint of availability and polymerizability, in at least one selected from the group consisting of general formulas (I) and (II), R Ａ and R Ｂ is preferably an ethylene group, a propylene group, or a butylene group, more preferably an ethylene group or a propylene group, and even more preferably an ethylene group.

[0030] A plurality of oxyalkylene-R Ａ From the viewpoint of ease of production, a plurality of oxyalkylene-R Ａ It is preferable that the O- are the same as each other. Ｂ From the viewpoint of ease of production, a plurality of oxyalkylene-R Ｂ It is preferred that the O- are the same as each other.

[0031] o and p each independently represent 0 or 1, and m and n each independently represent an integer of 5 to 100. * represents a bond.

[0032] From the viewpoint of polymerizability, o and p are preferably 0 in at least one selected from the group consisting of general formulas (I) and (II). From the viewpoint of polymerizability, m and n are preferably integers of 10 to 50, more preferably integers of 10 to 40, and even more preferably integers of 15 to 30 in at least one selected from the group consisting of general formulas (I) and (II).

[0033] In one embodiment of the present invention, in order to suppress a decrease in fluidity of the hydraulic composition over time, ３ 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. From the viewpoint of suppressing a decrease in fluidity of the hydraulic composition over time, in general formula (II), R ３ , R ４ , R ５ , R ６ , and R ７ In another embodiment of the present invention, from the viewpoint of improving the fluidity of the hydraulic composition and suppressing a decrease in fluidity over time, it is preferable that R 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 represents a methyl group, R ５ , R ６ , and R ７ represents a hydrogen atom, and o and p are preferably 0.

[0034] From the viewpoint of imparting adsorption properties to cement, the content of structural unit (a) in the polymer is preferably 1 to 50 mol %, more preferably 2 to 45 mol %, and even more preferably 5 to 40 mol %, relative to all structural units constituting the polymer. The content of each structural unit in the polymer in this specification is a value calculated from a 1H-NMR spectrum, and can be calculated by comparing the integral value of the spectrum derived from structural unit (a) appearing around 4.0 to 4.5 ppm with the integral value of the spectrum derived from structural unit (b) appearing around 1.5 to 2.5 ppm. Details of the measurement method can follow the method described in the Examples.

[0035] <Structural Unit (b)> The structural unit (b) is represented by the above general formula (III). In general formula (III), R ２１ , R ２２ , and R ２３ each independently represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an alkyloxy group having 1 to 6 carbon atoms, an alkenyl group having 2 to 6 carbon atoms, an alkenyloxy group having 2 to 6 carbon atoms, an aralkyl group having 7 to 12 carbon atoms, an aralkyloxy group having 7 to 12 carbon atoms, an aryl group having 6 to 12 carbon atoms, an aryloxy group having 6 to 12 carbon atoms, a carboxy group, or an alkanoyloxy group having 2 to 6 carbon atoms linked together.

[0036] R ２１ , R ２２ , and R ２３ The alkyl group having 1 to 6 carbon atoms represented by is the same as the above-mentioned R １ and R ２ The same groups as those exemplified as the "alkyl group having 1 to 6 carbon atoms" represented by the formula: can be exemplified.

[0037] R ２１ , R ２２ , and R ２３ Examples of the alkyloxy group having 1 to 6 carbon atoms represented by include an ethoxy group, a propoxy group, a butoxy group, an isobutyloxy group, a pentyloxy group, an isopentyloxy group, a hexyloxy group, and a cyclohexyloxy group.

[0038] R ２１ , R ２２ , and R ２３Examples of the alkenyl group having 2 to 6 carbon atoms represented by include a vinyl group, an allyl group, a propenyl group, an isopropenyl group, a butenyl group, an isobutenyl group, a pentenyl group, a hexenyl group, an iso-3-hexenyl group, and a cyclohexenyl group.

[0039] R ２１ , R ２２ , and R ２３ Examples of the alkenyloxy group having 2 to 6 carbon atoms represented by include an ethenyloxy group, a propenyloxy group, a butenyloxy group, an isobutenyloxy group, a pentenyloxy group, an isopentenyloxy group, a hexenyloxy group, and a cyclohexenyloxy group.

[0040] R ２１ , R ２２ , and R ２３ Examples of the aralkyl group having 7 to 12 carbon atoms represented by include a methylphenyl group, an ethylphenyl group, a propylphenyl group, an isopropylphenyl group, a butylphenyl group, an isobutylphenyl group, a pentylphenyl group, an isopentylphenyl group, a hexylphenyl group, an isohexylphenyl group, and a cyclohexylphenyl group.

[0041] R ２１ , R ２２ , and R ２３ Examples of the aralkyloxy group having 7 to 12 carbon atoms represented by the formula (I) include a benzyloxy group, a methylphenylmethoxy group, a dimethylphenylmethoxy group, a trimethylphenylmethoxy group, a tetramethylphenylmethoxy group, a pentamethylphenylmethoxy group, an ethylphenylmethoxy group, a propylphenylmethoxy group, a butylphenylmethoxy group, and a naphthylmethoxy group.

[0042] R ２１ , R ２２ , and R ２３ Examples of the aryl group having 6 to 12 carbon atoms represented by include a phenyl group, a tolyl group, a xylyl group, and a naphthyl group.

[0043] R ２１ , R ２２ , and R ２３Examples of the aryloxy group having 6 to 12 carbon atoms represented by include a phenoxy group, a methylphenoxy group, a dimethylphenoxy group, and a naphthoxy group.

[0044] R ２１ , R ２２ , and R ２３ The alkanoyloxy group having 2 to 6 carbon atoms represented by the above-mentioned R ３ The same groups as those exemplified as the "alkanoyloxy group having 2 to 6 carbon atoms" represented by the formula: can be exemplified.

[0045] From the viewpoint of availability and the number of acid groups per unit mass, R ２１ , R ２２ , and R ２３ is preferably a hydrogen atom or a methyl group, more preferably a hydrogen atom.

[0046] X represents a carboxylate group, a phosphonate group, a sulfonate group, or a silicate group. From the viewpoints of availability and handling, X is preferably a carboxylate group.

[0047] M represents a hydrogen atom, an alkali metal atom, or ammonium. From the viewpoint of the stability of the polymer, M is preferably an alkali metal atom or ammonium, more preferably an alkali metal atom, and even more preferably sodium.

[0048] * represents a bond.

[0049] The structural unit (b) represented by general formula (III) is preferably a structure derived from a polymerizable monomer having a polymerizable unsaturated group and an acid group in one molecule. Examples of polymerizable monomers having a polymerizable unsaturated group and an acid group in one molecule include (meth)acrylic acid (salt), crotonic acid (salt), isocrotonic acid (salt), senecioic acid (salt), and oleic acid (salt). From the viewpoints of polymerizability and availability, the structural unit (b) is preferably a structure derived from (meth)acrylic acid (salt).

[0050] From the viewpoint of imparting adsorbability to cement, the content of the structural unit (b) in the polymer is preferably 20 to 90 mol %, more preferably 30 to 80 mol %, and even more preferably 35 to 70 mol %, based on all structural units constituting the polymer.

[0051] <Other Structural Units> The polymer may contain other structural units in addition to the structural unit (a) and the structural unit (b). When the polymer contains other structural units, the content of the other structural units in the polymer is preferably more than 0 mol and not more than 20 mol%, more preferably more than 0 mol and not more than 10 mol%, and even more preferably more than 0 mol and not more than 5 mol%, based on the total structural units constituting the polymer.

[0052] <Weight-Average Molecular Weight of Polymer> The weight-average molecular weight of the polymer is preferably 5,000 to 100,000, more preferably 8,000 to 50,000, and even more preferably 10,000 to 30,000, from the viewpoints of improving the fluidity of the hydraulic composition and suppressing a decrease in fluidity over time.

[0053] <Method for Producing Polymer> The method for producing the polymer of the present invention is not particularly limited as long as the effects of the present invention can be obtained. The polymer can be produced, for example, by polymerizing a solution containing an unsaturated polyalkylene glycol monomer and a polymerizable monomer having a polymerizable unsaturated group and an acid group in one molecule using a polymerization initiator. A solution containing further components other than those mentioned above may also be used as long as the effects of the present invention are not impaired.

[0054] The unsaturated polyalkylene glycol monomer used in the production of the polymer includes a polymer (A) represented by the general formula (III) described below.

[0055] Examples of the polymerizable monomer having a polymerizable unsaturated group and an acid group in one molecule, which is used for producing the polymer, include the polymerizable monomer having a polymerizable unsaturated group and an acid group in one molecule described in the above <Structural Unit (b)>.

[0056] Examples of the polymerization method include known methods such as solution polymerization and bulk polymerization. Among these, solution polymerization is preferred. Examples of the solvent used in solution polymerization include water, alcohol 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. The solvents may be used alone or in combination of two or more.

[0057] The polymerization initiator may be a thermally decomposable polymerization initiator, a redox polymerization initiator, or the like. Examples of thermally decomposable polymerization initiators include persulfates such as ammonium persulfate and potassium persulfate, peroxides such as hydrogen peroxide and peracetic acid, and azo compounds such as 2,2'-azobisisobutyronitrile (AIBN). Examples of redox polymerization initiators include hydrogen peroxide and L-ascorbic acid. These polymerization initiators may be used alone or in combination of two or more.

[0058] When carrying out the polymerization, a chain transfer agent may be used as necessary. Examples of the chain transfer agent include 2-mercaptoethanol, 3-mercaptopropionic acid, n-octanethiol, phosphorous acid (salt), and sulfurous acid (salt). The chain transfer agents may be used alone or in combination of two or more.

[0059] The reaction conditions for polymerization can be appropriately selected depending on the monomers, polymerization method, solvent, polymerization initiator, etc. The reaction temperature is preferably 0° C. or higher, more preferably 30° C. or higher, and is preferably 150° C. or lower, more preferably 120° C. or lower.

[0060] The concentration of each component during polymerization can be appropriately selected depending on the monomer, polymerization method, solvent, polymerization initiator, etc. used, but it is preferable to adjust each component so that the solid content concentration after completion of polymerization is 2% by mass or more, more preferably 5% by mass or more. If the solid content concentration after completion of polymerization is 2% by mass or more, the amount added to the hydraulic composition can be reduced, which is economically advantageous. The solid content concentration here refers to the mass ratio of non-volatile content to the total, calculated using an infrared moisture meter, etc.

[0061] The polymer may be stored in the solution used in polymerization in the same state after polymerization. However, when storing the polymer in the solution used in polymerization, it is preferable to adjust the pH of the solution used in polymerization to 5 or more and store the polymer in the solution, from the viewpoint of avoiding deterioration of handleability due to gelation of the solution, etc. The pH can be adjusted using inorganic salts such as hydroxides and carbonates of alkali metals, alkaline substances such as ammonia and organic amines, etc. The pH adjusters may be used alone or in combination of two or more. Furthermore, the polymer stored in the solution used in polymerization in the same state after polymerization may be used together with the solution as a component of the composition and cement admixture. Alternatively, the polymer used in polymerization and stored in a solution adjusted to a pH of 5 or more may be used together with the solution as a component of the composition and cement admixture. Alternatively, the solution used in polymerization may be removed and the polymer may be used as a component of the composition and cement admixture.

[0062] [Composition] The composition according to an embodiment of the present invention contains the above-described polymer and a polymer (A) represented by at least one selected from the group consisting of the following general formulae (IV) and (V).

[0063]

[0064] The composition containing the polymer according to the embodiment of the present invention can suppress the decrease in fluidity of the hydraulic composition over time. Furthermore, the composition containing the polymer (A) improves the dispersibility of cement and cement hydrate immediately after the production of the hydraulic composition, and also improves the dispersibility over time. As a result, the fluidity of the hydraulic composition immediately after production is improved, and the decrease in fluidity over time can be further suppressed.

[0065] From the viewpoint of further suppressing the decrease in fluidity of the hydraulic composition over time, the mass ratio of the polymer (A) to the polymer (polymer (A) / polymer) is preferably 0.02 to 99.00, more preferably 0.02 to 50.00, even more preferably 0.02 to 20.00, and still more preferably 0.02 to 15.0.

[0066] From the viewpoint of further suppressing a decrease in fluidity over time, the content of the polymer in the composition is preferably 2 to 99% by mass, more preferably 2 to 97% by mass, and even more preferably 2 to 95% by mass.

[0067] <Polymer (A)> The polymer (A) is represented by at least one selected from the group consisting of the general formulas (IV) and (V). In the general formula (IV), R ３１ and R ３２ 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.

[0068] From the viewpoint of ease of manufacturing, R ３１ and R ３２ 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.

[0069] R ３３ represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or an alkanoyloxy group having 2 to 6 carbon atoms. ３３ 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.

[0070] R ３４ , R ３５ , R ３６ , R ３７ , R ３８ , R ３９ , R ４０ , and R ４１ 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 ３４ , R ３５, R ３６ , R ３７ , R ３８ , R ３９ , R ４０ , and R ４１ are each independently preferably a hydrogen atom or a methyl group, and more preferably a hydrogen atom.

[0071] R ３４ , R ３５ , R ３６ , R ３７ , R ３８ , R ３９ , R ４０ , and R ４１ may be bonded to each other to form a ring structure. ３４ , R ３５ , R ３６ , R ３７ , R ３８ , R ３９ , R ４０ , and R ４１ Examples 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.

[0072] R Ｃ and R Ｄ R each independently represents an alkylene group having 2 to 6 carbon atoms. Ｃ and R Ｄ The alkylene group having 2 to 6 carbon atoms represented by is the same as the above-mentioned R Ａ and R Ｂ The same groups as those exemplified as the "alkylene group having 2 to 6 carbon atoms" represented by the formula: can be exemplified.

[0073] From the viewpoint of availability and reactivity, R Ｃ and R Ｄ is preferably an ethylene group, a propylene group, or a butylene group, more preferably an ethylene group or a propylene group, and even more preferably an ethylene group.

[0074] A plurality of oxyalkylene-R Ｃ O- may be the same or different from each other. ＤO- may be the same or different.

[0075] q and r each independently represent 0 or 1, and s and t each independently represent an integer of 5 to 100.

[0076] From the viewpoint of polymerizability, q and r are preferably 0. From the viewpoint of further improving the fluidity of the hydraulic composition and further suppressing a decrease in fluidity over time, q and r are preferably the same number. From the viewpoint of polymerizability, s and t are preferably integers of 10 to 50, more preferably integers of 10 to 40, and even more preferably integers of 15 to 30.

[0077] In one embodiment of the present invention, R ３３ is a hydrogen atom, and R ３４ , R ３５ , R ３６ , R ３７ , R ３８ , R ３９ , R ４０ , and R ４１ are each independently a hydrogen atom or a methyl group. ３４ , R ３５ , R ３６ , and R ３７ is preferably a hydrogen atom, and q and r are preferably 0.

[0078] From the viewpoint of further suppressing the decrease in fluidity over time and from the viewpoint of the strength of the cured product of the hydraulic composition, the content of the polymer (A) in the composition is preferably 1 to 98 mass%, more preferably 1 to 96 mass%, and even more preferably 1 to 94 mass%.

[0079] <Weight Average Molecular Weight of Polymer (A)> The weight average molecular weight of the polymer (A) is preferably 300 to 15,000, more preferably 500 to 10,000, and even more preferably 800 to 5,000, from the viewpoints of improving the fluidity of the hydraulic composition and suppressing a decrease in fluidity over time.

[0080] <Other Components> The 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 hardening retarder, a hardening accelerator, a material separation reducer, a hydraulic powder, a non-hydraulic powder, an aggregate, water, 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, or the like.

[0081] <Solids Content of Composition> The solids content of the composition is preferably 0.5 to 80 mass %, more preferably 1 to 50 mass %, and even more preferably 3 to 40 mass %, from the viewpoint of efficiently achieving the effects of the present invention.

[0082] [Cement admixture] The polymer and composition according to the embodiment of the present invention can be suitably used as components of a cement admixture. In one aspect of the present invention, the cement admixture according to the embodiment of the present invention comprises the polymer according to the embodiment of the present invention. In another aspect of the present invention, the cement admixture according to the embodiment of the present invention comprises the composition according to the embodiment of the present invention. The cement admixture according to the embodiment of the present invention can suppress a decrease in fluidity of a hydraulic composition over time.

[0083] The cement admixture may contain components other than the polymer and composition of the present invention, as long as the effects of the present invention are not impaired. Examples of such 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.

[0084] Examples of the defoaming agent include oxyalkylene-based defoaming agents, silicone-based defoaming agents, and aliphatic amine-based defoaming agents. Preferred oxyalkylene-based defoaming agents are polyoxyalkylene glycol alkyl ethers, preferred silicone-based defoaming agents are dimethylpolysiloxane, and preferred aliphatic amine-based defoaming agents are alkyldimethylamines and their salts. One or more types of defoaming agents may be used in combination.

[0085] 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.

[0086] 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.

[0087] 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.

[0088] 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.

[0089] 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.

[0090] 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.

[0091] 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.

[0092] 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.

[0093] 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.

[0094] The content of the polymer in the cement admixture can be adjusted appropriately depending on the purpose. From the viewpoint of imparting fluidity, the content of the polymer in the cement admixture is 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.

[0095] The content of the composition in the cement admixture can be adjusted appropriately depending on the purpose. From the viewpoint of imparting fluidity, the content of the composition in the cement admixture is preferably 5% by mass or more, more preferably 8% by mass or more, even more preferably 10% by mass or more, and may be 100% by mass.

[0096] From the viewpoint of efficiently obtaining the effects of the present invention, the solid content concentration of the cement admixture is preferably 5 to 100 mass %, more preferably 8 to 100 mass %, and even more preferably 10 to 100 mass %.

[0097] [Hydraulic Composition] In one aspect of the present invention, the hydraulic composition according to the embodiment of the present invention comprises the polymer according to the embodiment of the present invention. In another aspect of the present invention, the hydraulic composition according to the embodiment of the present invention comprises the composition according to the embodiment of the present invention. The hydraulic composition according to the embodiment of the present invention is one in which the decrease in fluidity over time is suppressed.

[0098] The hydraulic composition refers to a cement paste, a mortar composition, a concrete composition, etc. The hydraulic composition according to the embodiment of the present invention may be an unhardened product before hardening, a partially hardened semi-hardened product, or a hardened product. The hydraulic composition contains a solidifying agent such as cement, aggregates such as sand, gravel, and stone, water, etc., and may optionally contain 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 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, ether solvents such as tetrahydrofuran, etc.

[0099] The contents of the polymer and composition in the hydraulic composition can be adjusted appropriately depending on the purpose. The content of the 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 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%.

[0100] In addition to cement admixtures, the polymers and compositions of the present invention can be used in a wide range of applications, such as aqueous slurry dispersants for inorganic pigments, scale inhibitors, detergent builders, deinking agents for recycled waste paper, chelating agents, dispersants for various dyes, pesticide dispersants, cotton scouring and cleaning agents, coal dispersants, thickeners, flocculants, and non-aqueous applications, and can exhibit excellent performance.

[0101] 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.

[0102] [Measurement and Evaluation Methods] Various physical properties were measured or evaluated by the following methods.

[0103] <Weight-average molecular weight> The weight-average molecular weight of the polymers obtained in the following examples and comparative examples was measured by gel permeation chromatography (GPC) under the following conditions and calculated in terms of standard polystyrene. Apparatus: "HLC-8320GPC" manufactured by Tosoh Corporation Eluent: tetrahydrofuran Column: two "TSKgel SuperMultiporeHZ-M" (inner diameter 4.6 mm, effective length 15 cm) and two "SuperH-RC" (inner diameter 4.6 mm, effective length 15 cm) manufactured by Tosoh Corporation connected in series Column temperature: 40°C Detector: RI Flow rate: 0.35 mL / min

[0104] <Content of Each Component in the Composition> The content of each component (polymer (1), polymer (2), polymer (1'), polymer (3), polymer (4), polymer (A-1), polymer (A'-1), and polymer (A''-1)) in the compositions obtained in the following examples and comparative examples was measured by liquid chromatography under the following conditions and calculated by quantitative analysis. Apparatus: Liquid Chromatography Prominence Series, manufactured by Shimadzu Corporation Eluent: acetonitrile / distilled water / phosphoric acid = 1000 / 1000 / 1 (v / v / w) Column: "TSKgel ODS-80Ts (inner diameter 4.6 mm, effective length 150 cm)" and "TSKgel Amide-80 (inner diameter 4.6 mm, effective length 150 cm)" manufactured by Tosoh Corporation connected in series Column temperature: 40°C Detector: RI Flow rate: 0.50 mL / min

[0105] <Mini-slump test (fluidity evaluation)> In order to evaluate the fluidity of the cement paste to which the compositions (X-1) to (X-10) and (Y-1) to (Y-4) obtained in the examples and comparative examples were added, a mini-slump test was carried out by the following method. Distilled water was added to each of the compositions (X-1) to (X-4) so ​​that the concentration of polymer (1) in the composition was 10% by mass; each of the compositions (X-5) and (X-6) so that the concentration of polymer (2) in the composition was 10% by mass; each of the compositions (X-7) and (X-8) so that the concentration of polymer (3) in the composition was 10% by mass; each of the compositions (X-9) and (X-10) so that the concentration of polymer (4) in the composition was 10% by mass; each of the compositions (Y-1) and (Y-2) so that the concentration of polymer (1') in the composition was 10% by mass; each of the compositions Y-3 so that the concentration of polymer (A-1) in the composition was 10% by mass; and each of the compositions Y-4 so that the concentration of polymer (A'-1) in the composition was 10% by mass, to obtain aqueous compositions. 0.77 g of the resulting aqueous composition solution, 37.73 g of distilled water, and 110 g of ordinary Portland cement (manufactured by Taiheiyo Cement Corporation) were mixed using a mixer to produce a cement paste. The cement paste was poured into a mini-slump cone described in Reference 1 on a stainless steel plate. The mini-slump cone was then pulled out under the conditions described in Reference 1 immediately after the cement paste injection (0 min) and 90 minutes after the cement paste injection (90 min). The length and width of the cement paste were measured, and the average value was taken as the slump flow value. A higher slump flow value indicates higher fluidity. The obtained slump flow value was used to calculate the slump flow retention rate according to the following formula: Slump flow retention rate = [(slump flow value 90 minutes after the cement paste injection (90 min)) / (slump flow value immediately after the cement paste injection (0 min))] × 100 (%). A higher slump flow retention rate indicates more suppressed fluidity degradation over time. Furthermore, a sample that satisfied all of the following criteria A to C was evaluated as G (Good), and a sample that did not satisfy at least one of the following criteria A to C was evaluated as B (Bad).A: Slump flow value immediately after cement paste injection (0 min) is 8 cm or more. B: Slump flow value 90 minutes after cement paste injection (90 min) is 6 cm or more. C: Slump flow maintenance rate is 70% or more.

[0106] Reference 1: Cement. Concrete. and Aggregates. CCAGDP, Vol. 2, No. 2, Winter 1980, pp95-102.

[0107] [Production Example 1] 2-hydroxymethyl-3-propen-1-ol and ethylene oxide were reacted by a known method to obtain polymer (A), which is represented by the following formula (A-1). The weight average molecular weight of the obtained polymer (A-1) was 1,900.

[0108]

[0109] [Production Example 2] 2-Isopropylidene-1,3-propanediol and ethylene oxide were reacted by a known method to obtain polymer (A"-1) represented by the following formula. The weight average molecular weight of polymer (A"-1) was 2,320.

[0110] [Example 1] A reactor equipped with a stirrer, thermometer, and dropping funnel was charged with 52.00 g (28.10 mmol) of polymer (A-1) and 72.00 g of distilled water. Subsequently, under a nitrogen stream, the internal temperature was raised to 60 ° C. with stirring, and 0.15 ml of a 30% by mass aqueous hydrogen peroxide solution (1.46 mmol, manufactured by FUJIFILM Wako Pure Chemical Industries, Ltd.) was added. An aqueous solution of 7.90 g of acrylic acid (109.63 mmol, manufactured by FUJIFILM Wako Pure Chemical Industries, Ltd.) dissolved in 12.00 g of distilled water, and an aqueous solution of 150 mg of L-ascorbic acid (0.85 mmol, manufactured by FUJIFILM Wako Pure Chemical Industries, Ltd.) dissolved in 12.00 g of distilled water were each added dropwise over 2 hours, and then the mixture was allowed to react at 60 ° C. for 1 hour. The resulting reaction mixture was cooled and neutralized to pH 7 with sodium hydroxide, yielding 641.75 g of composition (X-1). Composition (X-1) contained 64.175 g of polymer (1) as the polymer of the present invention (the content in composition (X-1) was 10% by mass), and 1.28 g of polymer (A-1) as the polymer (A). The mass ratio of polymer (A) to polymer (polymer (A) / polymer) was 0.02 (77.00 parts by mass of polymer (1) to 1.54 parts by mass of polymer (A-1)). The weight-average molecular weight of polymer (1) was 12,500. A mini-slump test was conducted using the resulting composition (X-1). The results are shown in Table 1.

[0111] Example 2 Composition (X-1) was obtained in the same manner as in Example 1, and 32.73 g of polymer (A-1) was added to composition (X-1) to obtain composition (X-2) having a mass ratio of polymer (A) to polymer (polymer (A) / polymer) of 0.53 (77.00 parts by mass of polymer (1) to 40.96 parts by mass of polymer (A-1)). A mini-slump test was carried out using the obtained composition (X-2). The results are shown in Table 1.

[0112] Example 3 Composition (X-1) was obtained in the same manner as in Example 1, and 96.91 g of polymer (A-1) was added to composition (X-1) to obtain composition (X-3) having a mass ratio of polymer (A) to polymer (polymer (A) / polymer) of 1.53 (77.00 parts by mass of polymer (1) to 117.96 parts by mass of polymer (A-1)). A mini-slump test was carried out using the obtained composition (X-3). The results are shown in Table 1.

[0113] Example 4 Composition (X-1) was obtained in the same manner as in Example 1, and 674.48 g of polymer (A-1) was added to composition (X-1) to obtain composition (X-4) having a mass ratio of polymer (A) to polymer (polymer (A) / polymer) of 10.53 (77.00 parts by mass of polymer (1) to 810.96 parts by mass of polymer (A-1)). A mini-slump test was carried out using the obtained composition (X-4). The results are shown in Table 1.

[0114] Example 5 A reactor equipped with a stirrer, thermometer, and dropping funnel was charged with 87.68 g (47.39 mmol) of polymer (A-1) and 52.59 g of distilled water. Subsequently, under a nitrogen stream, the internal temperature was raised to 60 ° C with stirring, and 0.44 mL (3.88 mmol) of a 30% by mass aqueous hydrogen peroxide solution was added. An aqueous solution prepared by dissolving 20.50 g (284.49 mmol) of acrylic acid in 30.69 g of distilled water and an aqueous solution prepared by dissolving 750 mg (4.26 mmol) of L-ascorbic acid in 17.74 g of distilled water were each added dropwise over 2 hours, followed by a reaction at 60 ° C for 1 hour. The resulting reaction mixture was cooled and neutralized to pH 7 using sodium hydroxide, yielding 708.71 g of composition (X-5). Composition (X-5) contained 70.871 g of polymer (2) as the polymer of the present invention (the content in composition (X-5) was 10% by mass), and 10.63 g of polymer (A-1) as the polymer (A). The mass ratio of polymer (A) to polymer (polymer (A)) (polymer (A) / polymer) was 0.15 (77.00 parts by mass of polymer (2) to 11.40 parts by mass of polymer (A-1)). The weight average molecular weight of polymer (2) was 22,300. A mini-slump test was carried out using the obtained composition (X-5). The results are shown in Table 1.

[0115] Example 6 Composition (X-5) was obtained in the same manner as in Example 5, and 27.64 g of polymer (A-1) was added to composition (X-5) to obtain composition (X-6) having a mass ratio of polymer (A) to polymer (polymer (A) / polymer) of 0.54 (77.00 parts by mass of polymer (2) to 41.58 parts by mass of polymer (A-1)). A mini-slump test was carried out using the obtained composition (X-6). The results are shown in Table 1.

[0116] Example 7 A reactor equipped with a stirrer, thermometer, and dropping funnel was charged with 19.06 g (8.22 mmol) of polymer (A''-1) and 72.12 g of distilled water. Subsequently, under a nitrogen stream, the internal temperature was raised to 60°C with stirring, and 0.33 mL (2.72 mmol) of a 30% by mass aqueous hydrogen peroxide solution was added. An aqueous solution prepared by dissolving 6.32 g (87.64 mmol) of acrylic acid in 47.08 g of distilled water and an aqueous solution prepared by dissolving 120 mg (0.67 mmol) of L-ascorbic acid in 37.05 g of distilled water were each added dropwise over 4.5 hours, followed by a reaction at 60°C for 1 hour. The resulting reaction mixture was cooled and neutralized to pH 7 using sodium hydroxide, yielding 286.24 g of composition (X-5). Composition (X-7) contained 28.62 g of polymer (3) as the polymer of the present invention (the content in composition (X-7) was 10% by mass), and 13.96 g of polymer (A"-1) as the polymer (A). The mass ratio of polymer (A) to polymer (polymer (A) (polymer (A) / polymer) was 0.49 (77.00 parts by mass of polymer (3) to 37.58 parts by mass of polymer (A"-1)). The weight average molecular weight of polymer (3) was 19,600. A mini-slump test was carried out using the obtained composition (X-7). The results are shown in Table 1.

[0117] Example 8 Composition (X-7) was obtained in the same manner as in Example 7, and 67.82 g of polymer (A"-1) was added to composition (X-7) to obtain composition (X-8) having a mass ratio of polymer (A) to polymer (polymer (A) / polymer) of 2.37 (77.00 parts by mass of polymer (3) to 182.49 parts by mass of polymer (A"-1)). A mini-slump test was carried out using the obtained composition (X-8). The results are shown in Table 1.

[0118] Example 9 A reactor equipped with a stirrer, thermometer, and dropping funnel was charged with 19.19 g (8.28 mmol) of polymer (A''-1) and 51.82 g of distilled water. Subsequently, under a nitrogen stream, the internal temperature was raised to 60°C with stirring, and 0.33 mL (2.72 mmol) of a 30% by mass aqueous hydrogen peroxide solution was added. An aqueous solution prepared by dissolving 3.16 g (43.85 mmol) of acrylic acid in 23.02 g of distilled water and an aqueous solution prepared by dissolving 58.4 mg (0.33 mmol) of L-ascorbic acid in 18.13 g of distilled water were each added dropwise over 4.5 hours, followed by a reaction at 60°C for 1 hour. The resulting reaction mixture was cooled and neutralized to pH 7 using sodium hydroxide, yielding 176.69 g of composition (X-9). Composition (X-9) contained 17.6 g of polymer (4) as the polymer of the present invention (the content in composition (X-9) was 10% by mass), and 13.96 g of polymer (A"-1) as the polymer (A). The mass ratio of polymer (A) to polymer (polymer (A) (polymer (A) / polymer) was 0.79 (77.00 parts by mass of polymer (4) to 61.06 parts by mass of polymer (A"-1)). The weight average molecular weight of polymer (4) was 29,900. A mini-slump test was carried out using the obtained composition (X-9). The results are shown in Table 1.

[0119] Example 10 Composition (X-9) was obtained in the same manner as in Example 9, and 42.59 g of polymer (A"-1) was added to composition (X-9) to obtain composition (X-10) having a mass ratio of polymer (A) to polymer (polymer (A) / polymer) of 2.42 (77.00 parts by mass of polymer (2) to 186.34 parts by mass of polymer (A"-1)). A mini-slump test was carried out using the obtained composition (X-10). The results are shown in Table 1.

[0120] Comparative Example 1 A reactor equipped with a stirrer, thermometer, and dropping funnel was charged with 70.01 g (30.78 mmol) of polymer (A'-1) represented by the following formula (A'-1), 175.20 g of distilled water, and 0.47 g (4.44 mmol, manufactured by FUJIFILM Wako Pure Chemical Industries, Ltd.). Subsequently, the internal temperature was raised to 65°C with stirring under a nitrogen stream, and 0.60 g (5.29 mmol) of a 30% by mass aqueous hydrogen peroxide solution was added. An aqueous solution prepared by dissolving 13.31 g (184.71 mmol) of acrylic acid in 81.66 g of distilled water and an aqueous solution prepared by dissolving 92 mg (5.23 mmol) of L-ascorbic acid in 46.71 g of distilled water were each added dropwise over 6 hours, followed by reaction at 65°C for 1 hour. The resulting reaction mixture was cooled and neutralized to pH 7 using sodium hydroxide, yielding 916.79 g of composition (Y-1). Composition (Y-1) contained 91.679 g of polymer (1') (the content in composition (Y-1) was 10% by mass) and 0.917 g of polymer (A'-1). The mass ratio of polymer (A'-1) to polymer (1') (polymer (A'-1) / polymer (1')) was 0.01 (77.00 parts by mass of polymer (1') to 0.85 parts by mass of polymer (A'-1)). The weight average molecular weight of polymer (1') was 38,000. A mini-slump test was carried out using the resulting composition (Y-1). The results are shown in Table 1.

[0121]

[0122] Comparative Example 2 Composition (Y-1) was obtained in the same manner as in Comparative Example 1, and 35.75 g of polymer (A'-1) was added to composition (Y-1) to obtain composition (Y-2) in which the mass ratio of polymer (A'-1) to polymer (1') (polymer (A'-1) / polymer (1')) was 0.40 (77.00 parts by mass of polymer (1') to 30.08 parts by mass of polymer (A'-1)). A mini-slump test was carried out using the obtained composition (Y-2). The results are shown in Table 1.

[0123] Comparative Example 3 7.7 g of polymer (A-1) and 69.3 g of distilled water as a solvent were mixed to obtain composition (Y-3). A mini-slump test was carried out using the obtained composition (Y-3). The results are shown in Table 1.

[0124] Comparative Example 4 7.7 g of polymer (A'-1) and 69.3 g of distilled water as a solvent were mixed to obtain composition (Y-4). A mini-slump test was carried out using the obtained composition (Y-4). The results are shown in Table 1.

[0125]

[0126] It can be seen from Table 1 that the polymer and composition of the present invention suppress a decrease in fluidity over time. Therefore, the polymer and composition of the present invention can be suitably used in cement admixtures and hydraulic compositions.

Claims

1. A polymer comprising a structural unit (a) represented by the following general formula (I) or (II) and a structural unit (b) represented by the following general formula (III): (In the general formulas (I) and (II), 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. ３ 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 0 or 1, and m and n each independently represent an integer of 5 to 100. * represents a bond. (In general formula (III), R ２１ , R ２２ , and R ２３ each independently represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an alkyloxy group having 1 to 6 carbon atoms, an alkenyl group having 2 to 6 carbon atoms, an alkenyloxy group having 2 to 6 carbon atoms, an aralkyl group having 7 to 12 carbon atoms, an aralkyloxy group having 7 to 12 carbon atoms, an aryl group having 6 to 12 carbon atoms, an aryloxy group having 6 to 12 carbon atoms, a carboxy group, or an alkanoyloxy group having 2 to 6 carbon atoms linked together. X represents a carboxylate group, a phosphonate group, a sulfonate group, or a silicate group. M represents a hydrogen atom, an alkali metal atom, or ammonium. * represents a bond.

2. In the above general formula (I), R ３ represents a hydrogen atom, R ４ , R ５ , R ６ , R ７ , R ８ , R ９ , R １０ , and R １１ Each of independently represents a hydrogen atom or a methyl group.

3. In the general formula (II), R ３ , R ４ , R ５ , R ６ , and R ７ Each of independently represents a hydrogen atom or a methyl group.

4. In at least one selected from the group consisting of the general formulas (I) and (II), R ４ , R ５ , R ６ , and R ７ The polymer according to claim 1 , wherein represents a hydrogen atom, and o and p are 0.

5. In at least one selected from the group consisting of the general formulas (I) and (II), R Ａ and R Ｂ Each independently represents an ethylene group, a propylene group, or a butylene group.

6. The polymer according to claim 1, wherein in at least one selected from the group consisting of general formulas (I) and (II), m and n each independently represent an integer of 10 to 50.

7. A composition comprising the polymer according to any one of claims 1 to 6 and a polymer (A) represented by at least one selected from the group consisting of the following general formulas (IV) and (V): In the general formulas (IV) and (V), R ３１ and R ３２ 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. ３３ represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or an alkanoyloxy group having 2 to 6 carbon atoms. ３４ , R ３５ , R ３６ , R ３７ , R ３８ , R ３９ , R ４０ , and R ４１ R each independently represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms. ３４ , R ３５ , R ３６ , R ３７ , R ３８ , R ３９ , R ４０ , and R ４１ may be bonded to each other to form a ring structure. Ｃ and R Ｄ each independently represents an alkylene group having 2 to 6 carbon atoms. Ｃ O- may be the same or different. Ｄ O- may be the same or different. q and r each independently represent 0 or 1, and s and t each independently represent an integer of 5 to 100.

8. The composition according to claim 7, wherein the mass ratio of the polymer (A) to the polymer (polymer (A) / polymer) is 0.02 to 99.

00.

9. The composition according to claim 7, wherein the mass ratio of the polymer (A) to the polymer (polymer (A) / polymer) is 0.02 to 20.

00.

10. A cement admixture comprising the polymer according to any one of claims 1 to 6.

11. A cement admixture comprising the composition of claim 7.

12. A hydraulic composition comprising the polymer according to any one of claims 1 to 6.

13. A hydraulic composition comprising the composition of claim 7.

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