JP5936504B2 - Polycarboxylic acid copolymer and use thereof - Google Patents

Description

The present invention relates to a polycarboxylic acid copolymer and its use. More specifically, the present invention relates to a polycarboxylic acid copolymer having a repeating unit formed by an unsaturated carboxylic acid monomer, and a dispersant, a cement admixture and a cement composition using the same.

A polycarboxylic acid polymer is a polymer having a repeating unit formed by an unsaturated carboxylic acid monomer, and can exhibit dispersion performance due to this structure. In addition, it is widely used as a soft segment for various uses such as adhesives and sealants, softening ingredients, and detergent builder. Recently, the use of cement admixtures added to cement compositions such as cement paste with water added to cement, mortar with fine aggregate mixed with cement paste, and concrete with coarse aggregate mixed with mortar has been studied. ing. The cement admixture is usually used as a water reducing agent, etc., and aims to exert the effect of improving the strength and durability of the cured product by increasing the fluidity of the cement composition to reduce the water content of the cement composition. It is used as

As such a cement admixture, in recent years, in addition to water reduction performance (dispersion performance) with respect to a cement composition, a cement admixture that can improve hardening delay and develop strength early is desired. For example, a secondary concrete product (precast) is made by pouring concrete into a formwork at a factory and then transporting it to the site for assembly. However, this will improve productivity, increase work efficiency, and save labor. Therefore, it is required to be able to remove the mold from the mold at an early stage. Also, in the field of ready-mixed concrete, if the concrete hardens quickly after being placed, it is possible to quickly move on to the next step. Therefore, it is desired to develop a cement admixture that develops strength at an early stage.

Regarding conventional polycarboxylic acid polymers, for example, Patent Documents 1 and 2 include a structural unit derived from an unsaturated polyether monomer having a branched (poly) alkylene glycol chain, and an unsaturated carboxylic acid monomer. A polycarboxylic acid-based dispersant containing a structural unit is disclosed. Patent Document 3 discloses a copolymer of a polyoxyethylene ether having a branched (poly) alkylene glycol chain and an unsaturated carboxylic acid.

Chinese Patent Application No. 102060465 Specification Chinese Patent Application No. 102030496 Chinese Patent Application No. 102140167

As described above, various polycarboxylic acid polymers have been studied, and Patent Documents 1 to 3 disclose polycarboxylic acid polymers having a branched (poly) alkylene glycol chain in the side chain. However, these copolymers have the same or lower dispersibility than the polycarboxylic acid polymer having a linear (poly) alkylene glycol chain in the side chain, and no improvement in early strength is seen. It was. From such a point of view, there has been room for ingenuity to make it possible to exhibit excellent early strength development and dispersibility and to be useful for various uses such as a dispersant and a cement admixture.

The present invention has been made in view of the above situation, and is excellent in various performances, in particular, early strength development and dispersibility, and useful for various uses such as dispersants and cement admixtures. An object of the present invention is to provide a dispersant and a cement admixture containing the polycarboxylic acid copolymer, and a cement composition.

The inventors of the present invention have made various studies on polycarboxylic acid-based polymers. When the polymer has a branched polyalkylene glycol chain (branched polyalkylene glycol chain) in the side chain, It is thought that the main chain can be shortened while maintaining the performance, that is, the hydration area can be increased by reducing the adsorption area (polymer coating area) to the inorganic or organic matter, thereby suppressing the setting delay Therefore, we thought that an early improvement in strength could be expected. However, the polycarboxylic acid polymers disclosed in Patent Documents 1 to 3 are less than or equal to a polymer having a linear polyalkylene glycol chain in the side chain, and an improvement in early strength is seen. I found nothing. Therefore, as a monomer component for forming a polymer, a monomer having a structure in which an unsaturated bond (carbon-carbon double bond) and a branched polyalkylene glycol chain are bonded via another polyalkylene glycol chain. And the use of an unsaturated carboxylic acid monomer, it has been found that the resulting polymer is remarkably excellent in both dispersibility (also referred to as water reduction or fluidity) and early strength development. This is because the polymer main chain formed from the unsaturated bond and the polymer side chain formed from the branched polyalkylene glycol chain due to the presence of the intervening polyalkylene glycol chain (length) Therefore, the main chain can be shortened and the side chain can be made more bulky, that is, the adsorption area (polymer coating area) on the inorganic or organic matter can be reduced and the hydration area can be increased. It is speculated that this is possible. In addition, a polymer using a monomer having a structure in which the number of branched polyalkylene glycol chains (the number of branches) is 3 or more and an unsaturated carboxylic acid monomer, or a polyalkylene glycol chain and (poly) glycidol It has been found that even a polymer using a monomer having a group and an unsaturated carboxylic acid monomer can exhibit excellent dispersibility and early strength development.

Furthermore, the present inventors have found that these polycarboxylic acid copolymers are novel polymers that have never existed, and are extremely useful for various applications such as dispersants and cement admixtures. In particular, if such a polycarboxylic acid copolymer is used as a cement admixture, the blending amount can be significantly reduced when preparing a cement composition, and at the same time, sufficient strength can be developed. Therefore, the present inventors have found that the present invention is extremely useful in the field of civil engineering / construction handling concrete, etc., and have conceived that the above-mentioned problems can be solved brilliantly, thereby achieving the present invention.

That is, the present invention is a monomer comprising an unsaturated polyalkylene glycol monomer represented by the following general formula (1) and an unsaturated carboxylic acid monomer represented by the following general formula (4). It is a polycarboxylic acid copolymer obtained by polymerizing components.

(.Y ^wherein, R 1, ^{R 2} and ^{R 3} are the same or different, .A ¹ O represents a hydrogen atom or a methyl group, the same or different and each represents an oxyalkylene group having 2 to 18 carbon atoms ¹ represents a residue of a compound having two or more active groups, Z represents the same or different and represents — (A ² O) _n —R ⁴ , A ² O represents the same or different and represents the number of carbon atoms Represents an oxyalkylene group having 2 to 18. R ⁴ is the same or different and represents a hydrogen atom or a hydrocarbon group having 1 to 30 carbon atoms, n is an average addition of an oxyalkylene group represented by A ² O The number of moles is the same or different and is a number of 2 to 300. p is 0, 1 or 2. q is 0 or 1. t is an oxyalkylene represented by A ¹ O. represents an average addition mole number of groups, .m ¹ is a number from 1 to 300 is an integer of 2 or more der Is the number of the maximum number is determined depending an active group represented by Y ¹ in the active groups of the compound having two or more.)

（式中、Ｒ^５、Ｒ^６及びＲ^７は、同一又は異なって、水素原子、メチル基又は−（ＣＨ_２）_ｙＣＯＯＭ^２を表す。なお、−（ＣＨ_２）_ｙＣＯＯＭ^２を表す場合、−ＣＯＯＭ^１又は他の−（ＣＨ_２）_ｙＣＯＯＭ^２と無水物を形成していてもよく、この場合は、これらの基のＭ^１及びＭ^２は存在しない。ｙは、０、１又は２である。Ｍ^１及びＭ^２は、同一又は異なって、水素原子、アルカリ金属原子、アルカリ土類金属原子、アンモニウム基、アルキルアンモニウム基又は置換アルキルアンモニウム基を表す。）

(In the formula, R ⁵ , R ⁶ and R ⁷ are the same or different and each represents a hydrogen atom, a methyl group or — (CH ₂ ) _y COOM ^2. Note that when — (CH ₂ ) _y COOM ² is represented, -COOM ¹ or other-(CH ₂ ) _y COOM ² may form an anhydride, in which case M ¹ and M ² of these groups are absent, y is 0, 1 or 2 M ¹ and M ² are the same or different and each represents a hydrogen atom, an alkali metal atom, an alkaline earth metal atom, an ammonium group, an alkylammonium group, or a substituted alkylammonium group.

The present invention also includes a monomer comprising an unsaturated polyalkylene glycol monomer represented by the following general formula (2) and an unsaturated carboxylic acid monomer represented by the general formula (4). It is also a polycarboxylic acid copolymer obtained by polymerizing components.

(Wherein R ¹ , R ² and R ³ are the same or different and each represents a hydrogen atom or a methyl group. X represents — (A ¹ O) _t —, and A ¹ O represents the same or different. Represents an oxyalkylene group having 2 to 18 carbon atoms, t represents an average addition mole number of the oxyalkylene group represented by A ¹ O, and is a number of 1 to 300. Y ² represents an active group 3 .Z representing the residue of a compound having more than five, identical or ^different, - .p representing the (a _{2 O)} n -R ⁴ is .q is 0, 1 or 2, is 0 or 1 U is 0 or 1. m ² is an integer of 3 or more, and the maximum number is determined depending on the number of active groups of the compound having 3 or more active groups represented by Y ² . a ² O are the same or different, .R ⁴ representing an oxyalkylene group having 2 to 18 carbon atoms are the same or different, hydrogen atoms Or .n representing a hydrocarbon group having 1 to 30 carbon atoms, represents an average addition mole number of the oxyalkylene group represented by A 2 ^O, identical or different, are a number from 2 to 300.)

The present invention also provides a monomer comprising an unsaturated polyalkylene glycol monomer represented by the following general formula (3) and an unsaturated carboxylic acid monomer represented by the general formula (4). It is also a polycarboxylic acid copolymer obtained by polymerizing components.

で表される構造からなる。） ^(Wherein, R 1, ^{R 2} and ^{R 3} are the same or different, .R ⁴ represents a hydrogen atom or a methyl group are the same or different, represent a hydrogen atom or a hydrocarbon group having 1 to 30 carbon atoms A ¹ O is the same or different and represents an oxyalkylene group having 2 to 18 carbon atoms, p is 0, 1 or 2. q is 0 or 1. t is A ¹ O. The average added mole number of the oxyalkylene group represented is a number from 1 to 300. m ³ is an integer of 2 or more, and represented by Y ³ — (C ₃ H ₆ O ₂ ) _r —. The maximum number is determined depending on the number of active groups of Y ³ represents the following general formula (5).
_{- (C 3 H 6 O 2} ) r - (5)
r _represents an average addition number of moles of glyceryl group represented by _{(C 3 H 6 O 2)} , the number of 1 to 300. The glyceryl groups represented by (C ₃ H ₆ O ₂ ) are the same or different and have the following formula:

It consists of the structure represented by. )

The present invention is also a dispersant or cement admixture containing the polycarboxylic acid copolymer.
The present invention is also a cement composition comprising the above cement admixture, cement and water.
The present invention is described in detail below. A form in which two or three or more preferred forms of the present invention described below are combined is also a preferred form of the present invention.
In the present specification, (poly) glycidol means polyglycidol or glycidol, and (poly) alkylene glycol means polyalkylene glycol or alkylene glycol.

[Polycarboxylic acid copolymer]
The polycarboxylic acid copolymer of the present invention includes an unsaturated polyalkylene glycol monomer represented by the general formula (1) and an unsaturated carboxylic acid monomer represented by the general formula (4). A polycarboxylic acid copolymer (also referred to as polycarboxylic acid copolymer (1)) obtained by polymerizing a monomer component containing: an unsaturated polyalkylene glycol represented by the above general formula (2) A polycarboxylic acid copolymer (polycarboxylic acid copolymer) obtained by polymerizing a monomer component containing a monomer and an unsaturated carboxylic acid monomer represented by the general formula (4) (Also referred to as a combination (2)); a monomer comprising the unsaturated polyalkylene glycol monomer represented by the general formula (3) and the unsaturated carboxylic acid monomer represented by the general formula (4). Polycarboxylic acid copolymer (polycarboxylic acid copolymer) obtained by polymerizing monomer components Also referred to as system copolymer (3)) which is either.
Each of the monomer components may further contain other monomers as necessary. Each monomer can be used alone or in combination of two or more.

Hereinafter, the unsaturated polyalkylene glycol monomer represented by the general formula (1) is also referred to as “unsaturated polyalkylene glycol monomer (1)”, and is represented by the general formula (2). The unsaturated polyalkylene glycol monomer is also referred to as “unsaturated polyalkylene glycol monomer (2)”, and the unsaturated polyalkylene glycol monomer represented by the general formula (3) is referred to as “unsaturated”. Also referred to as “polyalkylene glycol monomer (3)”, all of these may be collectively referred to as “unsaturated polyalkylene glycol monomer”. The polycarboxylic acid copolymers (1) to (3) may be collectively referred to as “polycarboxylic acid copolymers”.

Here, the unsaturated polyalkylene glycol monomer is subjected to polymerization to give a structural unit derived from the monomer in the polycarboxylic acid copolymer. The structure which the unsaturated double bond part (C = C) in General formula (1)-(3) became a single bond (-C-C-) is meant.
The unsaturated carboxylic acid-based monomer is used for polymerization to give a structural unit derived from the monomer in the polycarboxylic acid-based copolymer. 4) The structure in which the unsaturated double bond part (C = C) in 4) becomes a single bond (-C-C-).

The polycarboxylic acid copolymer has structural units derived from the respective monomer components as described above. That is, each of the polycarboxylic acid copolymers (1) to (3) has a structural unit derived from an unsaturated polyalkylene glycol monomer and a structural unit derived from an unsaturated carboxylic acid monomer. However, these ratios (mass ratio; structural unit derived from unsaturated polyalkylene glycol monomer / structural unit derived from unsaturated carboxylic acid monomer) are, for example, 1/99 to 70/30. Is preferred. More preferably, it is 5 / 95-40 / 60.

The polycarboxylic acid-based copolymer may further have a constitutional unit derived from another monomer as required, and as a ratio thereof, for example, in each polycarboxylic acid-based copolymer, It is preferable that it is 50 mass% or less in 100 mass% of all the structural units. More preferably, it is 30 mass% or less, More preferably, it is 10 mass% or less. That is, in each of the polycarboxylic acid copolymers (1) to (3), a structural unit derived from the unsaturated polyalkylene glycol monomer and a structural unit derived from the unsaturated carboxylic acid monomer are included. The occupying ratio is preferably 50% by mass or more, more preferably 70% by mass or more, and still more preferably 90% by mass or more, in 100% by mass of all the structural units.

The weight average molecular weight (Mw) of each of the polycarboxylic acid copolymers is preferably 1000 to 500,000. By being in this range, it is possible to further enhance the dispersion performance and early strength development performance, for example, when used for dispersants and cement admixtures, it can exhibit higher dispersibility with a small addition amount. it can. More preferably, it is 5000 or more, More preferably, it is 10,000 or more, More preferably, it is 30000 or more, Especially preferably, it is 50000 or more, Most preferably, it is 80000 or more, More preferably, it is 300000 or less, More preferably, it is 200000 or less. Further, the molecular weight distribution (Mw / Mn) of the polycarboxylic acid copolymer is preferably 25 or less. More preferably, it is 20 or less, More preferably, it is 10 or less, Especially preferably, it is 7.5 or less, Most preferably, it is 5 or less, Moreover, it is preferable that it is 1 or more.
In addition, a weight average molecular weight (Mw) and molecular weight distribution (Mw / Mn) can be measured on the GPC measurement conditions mentioned later by the gel permeation chromatography (GPC) provided with the light-scattering detector, for example.

<Unsaturated polyalkylene glycol monomer (1)>
In the monomer component for obtaining the polycarboxylic acid copolymer (1) of the present invention, the unsaturated polyalkylene glycol monomer (1) is the following general formula (1):

(.Y ^wherein, R 1, ^{R 2} and ^{R 3} are the same or different, .A ¹ O represents a hydrogen atom or a methyl group, the same or different and each represents an oxyalkylene group having 2 to 18 carbon atoms ¹ represents a residue of a compound having two or more active groups, Z represents the same or different and represents — (A ² O) _n —R ⁴ , A ² O represents the same or different and represents the number of carbon atoms Represents an oxyalkylene group having 2 to 18. R ⁴ is the same or different and represents a hydrogen atom or a hydrocarbon group having 1 to 30 carbon atoms, n is an average addition of an oxyalkylene group represented by A ² O The number of moles is the same or different and is a number of 2 to 300. p is 0, 1 or 2. q is 0 or 1. t is an oxyalkylene represented by A ¹ O. represents an average addition mole number of groups, .m ¹ is a number from 1 to 300 is an integer of 2 or more der Is a compound represented by depending on the activity groups of the compound having an active group represented by Y ¹ 2 or more is a number determined maximum number.).

In the general formula (1), R ¹ , R ² and R ³ are the same or different and represent a hydrogen atom or a methyl group, and p is 0, 1 or 2. Therefore, the alkenyl group represented by (R ³ ) (R ² ) C═C (R ¹ ) — (CH ₂ ) _p — corresponds to an alkenyl group having 2 to 7 carbon atoms. Preferably, it is 3-5.
In the above general formula (1) (and the above general formulas (2) and (3)), q represents 0 or 1, but when q = 0, the single unit represented by the general formula (1) The body becomes a monomer having an ether structure (ether monomer), and when q = 1, it becomes a monomer having an ester structure (ester monomer). Among them, q = 0, that is, the unsaturated polyalkylene glycol monomer is preferably an ether monomer.

In the above general formula (1), Y ¹ represents a residue of a compound having two or more active groups. The residue of a compound having an active group means a group having a structure in which an active hydrogen constituting an active group is removed from a compound having an active group, and the active hydrogen means hydrogen to which an alkylene oxide can be added. . The compound having two or more active groups may have one residue or two or more residues.

The number of active groups (that is, the number of active hydrogens) of the compound having an active group is suitably 2 or more from the viewpoints of dispersibility and early strength development. In consideration of the polymerizability when the unsaturated polyalkylene glycol monomer (1) is used for polymerization, the number is preferably 50 or less. The number of active groups (active hydrogen number) is preferably 3 or more, more preferably 4 or more, and still more preferably 5 or more. The upper limit value is more preferably 20 or less, still more preferably 10 or less.

Specific examples of the residue of the compound having two or more active groups include, for example, a polyhydric alcohol residue having a structure in which active hydrogen is removed from the hydroxyl group of epoxy alcohol or polyhydric alcohol; A polyvalent amine residue having a structure in which active hydrogen is removed; a polyvalent imine residue having a structure in which active hydrogen is removed from an imino group of a polyvalent imine; a structure in which active hydrogen is removed from an amide group of a polyvalent amide compound A polyvalent amide residue having; Of these, polyvalent amine residues, polyvalent imine residues and polyhydric alcohol residues are preferred. That is, the residue of the compound having two or more active hydrogens is at least one polyvalent compound residue selected from the group consisting of a polyvalent amine residue, a polyvalent imine residue, and a polyhydric alcohol residue. Preferably it is. This makes it possible to obtain a polycarboxylic acid copolymer suitable for various uses such as a dispersant and a cement admixture.
The form of the compound residue having an active group may be any of a chain structure, a branched structure, and a three-dimensionally crosslinked structure, but a branched structure is preferable.

Regarding the residue of the compound having two or more active groups, the epoxy alcohol and / or the polyhydric alcohol constituting the polyhydric alcohol residue is a compound containing an average of two or more hydroxyl groups in one molecule. A compound composed of three elements of carbon, hydrogen and oxygen is preferable.
The epoxy alcohol means an alcohol having an epoxy group, and the epoxy group includes a glycidyl group (including a glycidyl ether group and a glycidyl ester group).

Specific examples of the epoxy alcohol and / or polyhydric alcohol include, for example, (poly) glycidol, (poly) glycerin, trimethylolethane, trimethylolpropane, 1,3,5-pentatriol, erythritol, pentaerythritol, di Pentaerythritol, sorbitol, sorbitan, sorbitol glycerin condensate, adonitol, arabitol, xylitol, mannitol and the like are suitable. Further, as sugars, saccharides of hexoses such as glucose, fructose, mannose, indoses, sorbose, growth, talose, tagatose, galactose, allose, psicose, altrose; arabinose, ribulose, ribose, xylose, xylulose, lyxose, etc. Saccharides of pentoses; saccharides of tetroses such as treose, erythrulose, erythrose; other saccharides such as rhamnose, cellobiose, maltose, isomaltose, trehalose, sucrose, raffinose, gentianose, melezitose; these sugar alcohols, sugar acids ( Saccharides; glucose, sugar alcohols; glucites, sugar acids; gluconic acids) and the like are also suitable. Furthermore, derivatives such as partially etherified products and partially esterified products of these exemplified compounds are also suitable. Among these, (poly) glycidol is preferable from the viewpoint of ease of reaction in the method for producing an unsaturated polyalkylene glycol monomer.
The polyhydric alcohol residue of the unsaturated polyalkylene glycol monomer (1) is formed by the epoxy alcohol and / or the polyhydric alcohol.

The polyvalent amine (polyamine) constituting the polyvalent amine residue may be a compound having an average of two or more amino groups in one molecule, such as methylamine, ethylamine, propylamine, butylamine, -Alkylamines such as ethylbutylamine, octylamine, dimethylamine, dipropylamine, dimethylethanolamine, dibutylamine, trimethylamine, triethylamine, cyclobutylamine, cyclohexylamine, laurylamine; alkyleneamines such as allylamine; fragrances such as aniline and diphenylamine Preferred are homopolymers and copolymers obtained by polymerizing one or more monoamine compounds such as nitrogen amines such as ammonia, urea and thiourea by a conventional method. Further, it may be ethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine, dipropylenetriamine, tripropylenetetramine, tetrapropylenepentamine, and the like. In addition to the primary amino group, it has a primary amino group having an active hydrogen atom or a secondary amino group (imino group). Among these, it is preferable to use a polyalkylamine. As the alkylamine constituting the polyalkylamine, an alkylamine having 8 to 18 carbon atoms such as laurylamine is preferable.
The polyvalent amine forms the polyvalent amine residue of the unsaturated polyalkylene glycol monomer (1).

The polyvalent imine (polyimine) constituting the polyvalent imine residue may be a compound having an average of two or more imino groups in one molecule, such as ethyleneimine, propyleneimine, 1,2-butylene. Homopolymers or copolymers obtained by polymerizing one or more alkylene imines having 2 to 8 carbon atoms such as imine, 2,3-butyleneimine and 1,1-dimethylethyleneimine by a conventional method Is preferred. That is, it is preferable to use polyalkyleneimine.
The polyvalent imine forms the polyvalent imine residue of the unsaturated polyalkylene glycol monomer (1).
Polyimine is three-dimensionally cross-linked by polymerization, and usually has a primary amino group having an active hydrogen atom or a secondary amino group (imino group) in addition to a tertiary amino group in the structure. .

Among the polyalkyleneimines, a polyalkyleneimine mainly composed of ethyleneimine is more preferable.
The “main body” in this case means that when the polyalkyleneimine is formed by two or more kinds of alkyleneimines, it accounts for the majority of the total number of alkyleneimines present. In the present invention, the alkyleneimine forming the polyalkyleneimine chain is mostly ethyleneimine, so that the hydrophilicity of the polyalkyleneglycol chain-containing thiol compound is improved and suitable for many applications. From the fact that the action and effect are sufficiently exhibited, by using ethyleneimine as an alkyleneimine that forms a polyalkyleneimine chain (polyalkyleneimine residue) to the extent that the above action and effect are sufficiently exhibited, It will be “occupying the majority” mentioned above. When “dominating” is expressed in terms of mol% of ethyleneimine in 100 mol% of all alkyleneimines, it is preferably 50 to 100 mol%. If it is less than 50 mol%, the hydrophilicity of the polyalkyleneimine chain may not be sufficient. More preferably, it is 60 mol% or more, More preferably, it is 70 mol% or more, Especially preferably, it is 80 mol% or more, Most preferably, it is 90 mol% or more.

The average polymerization number of alkyleneimine per one polyalkyleneimine chain is preferably 2 to 300. By setting it as such a range, it becomes possible to fully exhibit the effect resulting from the structure of the unsaturated polyalkylene glycol monomer (1). For example, when a polymer is used, It can be made suitable for applications such as cement admixture by exhibiting dispersion performance. The lower limit is more preferably 3 or more, further preferably 5 or more, and particularly preferably 10 or more. Further, the upper limit is more preferably 200 or less, still more preferably 100 or less, particularly preferably 75 or less, and most preferably 50 or less.
The average polymerization number of diethylenetriamine is 2, and the average polymerization number of triethylenetetramine is 3.

As a number average molecular weight of the said polyvalent amine and polyvalent imine, 100-50000 are preferable, More preferably, it is 200-10000, More preferably, it is 300-5000, Most preferably, it is 400-1000.

Among the residues of the compound having two or more active groups, a polyhydric alcohol residue is particularly preferable, and most preferable is a (poly) glycidol residue (also referred to as a (poly) glyceryl group) as described above. is there. In this case, Y ¹ in the general formula (1) is preferably represented by the following general formula (5).
_{- (C 3 H 6 O 2} ) r - (5)
(In the formula, r represents the average added mole number of the glyceryl group represented by (C ₃ H ₆ O ₂ ) and is a number of 1 to 300. Glyceryl represented by (C ₃ H ₆ O ₂ ) The groups are the same or different and have the following formula:

It consists of the structure represented by. )
When the unsaturated polyalkylene glycol monomer has a structure represented by the general formula (5) as Y ¹ , the effects of the present invention can be more fully exhibited.

In the above general formula (5), r is a number from 1 to 300, but when r is 300 or less, problems in production are further eliminated, and an unsaturated polyalkylene glycol monomer is more preferable. To be able to get to. From the viewpoint of production, it is preferably 2 to 200, more preferably 2 to 100, still more preferably 2 to 50, and particularly preferably 2 to 25.

In the above general formula (1), the residue (Y ¹ ) of the compound having two or more active groups is represented by m ¹ polyalkylene glycol chain-containing groups (Z; — (A ² O) _n —R ⁴ ). Will be combined. The number of polyalkylene glycol chains — (A ² O) _n — to which Y is bonded, that is, m ¹ is suitably 2 or more, but is preferably 3 or more. When the number is 3 or more, the unsaturated polyalkylene glycol monomer has a radially branched structure, that is, from the residue of a compound having two or more active groups as a starting point,-(A ² O) _The polyalkylene glycol chain represented by _n- has a structure extending radially, and by having such a structure, a dispersant and cement exhibiting extremely high dispersion performance and superior in early strength. It becomes possible to give an admixture. More preferably, it is 4 or more, More preferably, it is 5 or more. In consideration of the polymerizability when the unsaturated polyalkylene glycol monomer is used for polymerization, m ¹ is preferably 50 or less, more preferably 20 or less, still more preferably 10 or less. .

The m ¹ is preferably equal to the number of active groups in the compound having two or more active groups. That is, the unsaturated polyalkylene glycol monomer (1) is added to all active groups (more specifically, active hydrogen atoms constituting the active groups) in the compound having two or more active groups. It is preferable to have a structure in which an alkylene glycol chain — (A ² O) _n — is bonded. As a result, it is possible to provide a dispersant and a cement admixture that can exhibit further superior dispersion performance and early strength, and thus polycarboxylic acid copolymers useful for various applications can be obtained.

The polyalkylene glycol chain represented by — (A ² O) _n — may be a chain composed of one or two or more alkylene oxides having 2 to 18 carbon atoms, preferably carbon. Alkylene oxides of 2 to 8, for example, ethylene oxide, propylene oxide, butylene oxide, isobutylene oxide, 1-butene oxide, 2-butene oxide, trimethylethylene oxide, tetramethylene oxide, tetramethylethylene oxide, butadiene monooxide, octylene And oxides. In addition, aliphatic epoxides such as dipentane ethylene oxide and dihexane ethylene oxide; alicyclic epoxides such as trimethylene oxide, tetramethylene oxide, tetrahydrofuran, tetrahydropyran, and octylene oxide; aromatics such as styrene oxide and 1,1-diphenylethylene oxide Epoxides and the like can also be used.

The alkylene oxide constituting the polyalkylene glycol chain is preferably selected as appropriate according to the use required for the polycarboxylic acid copolymer of the present invention. For example, when used for producing a cement admixture component From the viewpoint of affinity with cement particles, it is preferable that the main component is a relatively short chain alkylene oxide (oxyalkylene group) having about 2 to 8 carbon atoms. More preferably, the main component is an alkylene oxide having 2 to 4 carbon atoms such as ethylene oxide, propylene oxide, butylene oxide, and still more preferably, the main component is ethylene oxide.
The “main body” as used herein means that when the polyalkylene glycol chain — (A ² O) _n — is composed of two or more types of alkylene oxides, it accounts for the majority of the total number of alkylene oxides present. Means. When expressing “dominate” in terms of mol% of ethylene oxide in 100 mol% of all alkylene oxides, 50 to 100 mol% is preferable. Thereby, the said unsaturated polyalkylene glycol-type monomer will have higher hydrophilicity. More preferably, it is 60 mol% or more, More preferably, it is 70 mol%, Especially preferably, it is 80 mol% or more, Most preferably, it is 90 mol% or more.

When the polyalkylene glycol chain is composed of two or more types of alkylene oxides, two or more types of alkylene oxides may be added in any form such as random addition, block addition, alternating addition, etc. , M (poly) alkylene glycol chains may be the same or different.

In the above polyalkylene glycol chain, for example, when a cement composition is produced by blending a polycarboxylic acid-based copolymer with a cement admixture, the viscosity and stiffness can be reduced, etc., in the chain. It is preferable to introduce an oxyalkylene group having 3 or more carbon atoms. Thereby, a certain degree of hydrophobicity is imparted to the polyalkylene glycol chain, and a slight structure (network) can be provided to the cement particles.
In this case, the content ratio of the oxyalkylene group having 3 or more carbon atoms is preferably 1 mol% or more, more preferably 100 mol% of all oxyalkylene groups (alkylene glycol units) constituting the polyalkylene glycol chain. Is 3 mol% or more, more preferably 5 mol% or more, and particularly preferably 7 mol% or more. Moreover, when the oxyalkylene group having 3 or more carbon atoms is introduced too much, the resulting monomer and the polymer using the polymer become too hydrophobic, for example, to sufficiently improve the dispersion performance of cement particles. Therefore, it is preferably 50 mol% or less, more preferably 30 mol% or less, still more preferably 20 mol% or less, and particularly preferably 10 mol% or less.

The oxyalkylene group having 3 or more carbon atoms is preferably an oxyalkylene group having 3 to 18 carbon atoms from the viewpoint of ease of introduction, affinity with cement particles, and the like. Among these, an oxyalkylene group having 3 to 8 carbon atoms is preferable, and an oxypropylene group having 3 carbon atoms and an oxybutylene group having 4 carbon atoms are more preferable.

In addition, the oxyalkylene group having 3 or more carbon atoms may be introduced in a block form or may be introduced in a random form, but (a (poly) alkylene glycol chain comprising an oxyalkylene group having 2 or more carbon atoms). )-((Poly) alkylene glycol chain comprising an oxyalkylene group having 3 or more carbon atoms)-((poly) alkylene glycol chain comprising an oxyalkylene group having 2 or more carbon atoms). preferable. Thereby, higher dispersibility can be exhibited.

The average number of repeating alkylene oxides in the polyalkylene glycol chain, that is, the average number of added moles (n) of oxyalkylene groups is suitably 2 to 300. When n is 2 or more, the unsaturated polyalkylene glycol monomer can sufficiently exhibit performance based on the polyalkylene glycol chain, and when n is 300 or less, The viscosity and reactivity of the polyalkylene glycol monomer are appropriate, which is suitable in terms of workability when handling this. The lower limit is preferably 3 or more, more preferably 5 or more, still more preferably 8 or more, particularly preferably 10 or more, and most preferably 20 or more. The upper limit is preferably 200 or less, more preferably 150 or less, and still more preferably 100 or less.
The average added mole number of the oxyalkylene group means an average value of the number of moles of alkylene oxide added in 1 mole of the branched polyalkylene glycol chain of the unsaturated polyalkylene glycol monomer. .

R ⁴ constituting the terminal group of the unsaturated polyalkylene glycol monomer, that is, the polyalkylene glycol chain-containing group (Z; — (A ¹ O) _n —R ⁴ ) is a hydrogen atom or a carbon number of 1 to 30. Represents a hydrocarbon group. From the viewpoint of improving dispersibility, it is preferable that the hydrophobicity does not become too strong. Therefore, R ⁴ is preferably a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms. More preferably, they are a hydrogen atom or a C1-C5 hydrocarbon group, More preferably, they are a hydrogen atom or a C1-C3 hydrocarbon group.
When R ⁴ represents a hydrocarbon group, it is preferably a saturated alkyl group or an unsaturated alkyl group, and may be linear, branched, or cyclic.

In the general formula (1), the branched polyalkylene glycol chain-containing group represented by —Y ¹ — (Z) _m1 is bonded to the polyalkylene glycol chain represented by — (A ¹ O) _t —. Become. In this way, the unsaturated polyalkylene glycol-based monomer has a structure in which an unsaturated bond (carbon-carbon double bond) and a branched polyalkylene glycol chain-containing group are bonded via a polyalkylene glycol chain. A sufficient hydrophilicity can be imparted to the body, and the length (interval) between the unsaturated bond and the branched polyalkylene glycol chain-containing group (—Y ^1- (Z) _m1 ) is sufficient. Therefore, the dispersibility and early strength of the polycarboxylic acid copolymer of the present invention can be remarkably improved. In addition, the polycarboxylic acid copolymer of the present invention has a molecular weight equivalent to that of the polymer, and outstanding dispersibility compared to a polymer having a linear polyalkylene glycol chain in the side chain. And early strength can be expressed.

The preferred configuration, form, and the like of the polyalkylene glycol chain represented _by- (A ¹ O) _t- are the same as those of the polyalkylene glycol chain represented by-(A ² O) _n- described above. . In addition, although t is a number of 2 to 300, from the viewpoint of improving dispersibility and early strength development performance of a polymer obtained using an unsaturated polyalkylene glycol monomer, preferably 5 to 200, More preferably, it is 10-100.

The unsaturated polyalkylene glycol monomer (1) preferably has a weight average molecular weight of 200 to 100,000. Moreover, when the polymerization reactivity at the time of superposing | polymerizing using this is considered, More preferably, it is 500-70000, More preferably, it is 1000-50000. The number average molecular weight of the unsaturated polyalkylene glycol monomer (1) is preferably 200 to 50,000. More preferably, it is 500-30000, More preferably, it is 700-20000.
The weight average molecular weight and the number average molecular weight of the unsaturated polyalkylene glycol monomer can be determined, for example, as an absolute molecular weight by gel permeation chromatography (GPC) with a light scattering detector under the following conditions.

<GPC measurement conditions>
Column used: Tosoh Corporation, TSKguardcolumn α + TSKgel α-5000 + TSKgel α-4000 + TSKgel α-3000, one by one.
Eluent used: Sodium dihydrogen phosphate · 2H 2 O: 124.8 g, Disodium hydrogen phosphate · 12H 2 O: 286.5 g dissolved in ion-exchanged water: 15588.7 g, acetonitrile: 4000 g mixed solution Use.
Detector: Viscotek's triple detector Model 302
Light scattering detector:
Right angle light scattering: 90 ° scattering angle, low angle light scattering: 7 ° scattering angle, cell capacity: 18 μL, wavelength: 670 nm
Standard sample: Polyethylene glycol SE-8 (Mwl07000) manufactured by Tosoh Corporation is used, its dn / dC is 0.135 ml / g, and the refractive index of the used eluent is 1.333, and the apparatus constant is determined.
Driving amount:
Standard sample: 250 μL of the solution dissolved in the eluent so that the concentration of the measurement object is 0.2 vol% (volume%), and the sample: the above so that the concentration of the measurement object is 1.0 vol% 250 μL of solution dissolved in eluent Injection flow rate: 0.8 ml / min
Column temperature: 40 ° C

The unsaturated polyalkylene glycol monomer (1) includes, for example, Step 1 in which an unsaturated polyalkylene glycol compound represented by the following general formula (6) is reacted with an epoxy alcohol and / or a polyhydric alcohol. It can be obtained by a manufacturing method.
The manufacturing method may further include one or more other steps as necessary.

(.P ^wherein, R 1, ^{R 2} and ^{R 3} are the same or different, .A ¹ O represents a hydrogen atom or a methyl group, the same or different and each represents an oxyalkylene group having 2 to 18 carbon atoms Is 0, 1 or 2. q is 0 or 1. t represents the average number of moles added of the oxyalkylene group represented by A ¹ O, and is a number from 2 to 300.)
In addition, the raw material (unsaturated polyalkylene glycol compound and polyhydric alcohol) used for the said process 1 can use 1 type (s) or 2 or more types, respectively.

In the step 1, the unsaturated polyalkylene glycol compound may be a compound represented by the general formula (6), and R ¹ , R ² , R ³ , p, q in the general formula (6). , A ¹ O and t are the same as the symbols in the general formula (1).
Examples of such unsaturated polyalkylene glycol compounds include vinyl alcohol alkylene oxide adducts, (meth) allyl alcohol alkylene oxide adducts, 3-buten-1-ol alkylene oxide adducts, isoprene alcohol (3-methyl- 3-buten-1-ol) alkylene oxide adduct, 3-methyl-2-buten-1-ol alkylene oxide adduct, 2-methyl-3-buten-2-ol alkylene oxide adduct, 2-methyl-2 -Buten-1-ol alkylene oxide adduct, 2-methyl-3-buten-1-ol alkylene oxide adduct and the like can be mentioned.

The epoxy alcohol or polyhydric alcohol is preferably a compound composed of three elements of carbon, hydrogen and oxygen. Specifically, the above-described compounds and the like are suitable, and among them (poly) glycidol is preferable, and glycidol is more preferable. Moreover, you may use an epoxy alcohol and a polyhydric alcohol together as needed.

In the above step 1, the reaction ratio (molar ratio; total amount of unsaturated polyalkylene glycol compound / epoxy alcohol and polyhydric alcohol) between the unsaturated polyalkylene glycol compound and the epoxy alcohol and / or polyhydric alcohol is 1 / It is preferable to set to 1/100. More preferably, it is 1/1 to 1/50.

The above step 1 is also preferably performed in the presence of a catalyst. Examples of the catalyst include metal hydroxides such as potassium hydroxide, sodium hydroxide, lithium hydroxide and magnesium hydroxide, metal hydrides such as sodium hydride and potassium hydride; butyl lithium, methyl lithium, phenyl lithium and the like 1 type, or 2 or more types of Lewis acid such as boron trifluoride, titanium tetrachloride, etc .; Metal alkoxide such as sodium methoxide, potassium methoxide, etc. can be used.

Regarding the reaction conditions in the above step 1, the reaction temperature is preferably 50 to 200 ° C, more preferably 70 to 160 ° C, and still more preferably 80 to 130 ° C. For example, the reaction time is preferably 0.5 to 24 hours, and more preferably 1 to 10 hours. The reaction pressure may be any of reduced pressure, normal pressure, and increased pressure, but a reaction at normal pressure is sufficient.

In the production method, it is also preferable to perform step 2 in which the polyhydric alcohol derivative obtained in step 1 is reacted with alkylene oxide. That is, it is preferable that the manufacturing method further includes a step 2 in which the polyhydric alcohol derivative obtained in the step 1 is reacted with an alkylene oxide.
The raw materials (polyhydric alcohol derivative and alkylene oxide) used in Step 2 can be used alone or in combination of two or more.

The alkylene oxide used in Step 2 is preferably an alkylene oxide having 2 to 18 carbon atoms, and more preferably an alkylene oxide having 2 to 8 carbon atoms. Suitable specific examples of the alkylene oxide are as described above.

In step 2, the reaction ratio between the polyhydric alcohol derivative (preferably (poly) glycidol derivative) obtained in step 1 and alkylene oxide is set so that the average number of moles of alkylene oxide added is 2 to 300. It is preferable to do. The average number of moles of alkylene oxide added here means the average value of the number of moles of alkylene oxide added in one mole of the terminal polyalkylene glycol chain in the compound obtained by the above step 2. The lower limit of the average added mole number of the alkylene oxide is preferably 2 or more, more preferably 5 or more, still more preferably 8 or more, particularly preferably 10 or more, and most preferably 20 or more. The upper limit is preferably 200 or less, more preferably 150 or less, and still more preferably 100 or less.

The step 2 is also preferably performed in the presence of a catalyst. As a catalyst, the thing similar to the catalyst quoted at the said process 1 can be used 1 type, or 2 or more types, for example.

Regarding the reaction conditions of the above step 2, the reaction temperature is preferably 60 to 200 ° C, more preferably 80 to 150 ° C, and still more preferably 90 to 130 ° C. For example, the reaction time is preferably within 50 hours, more preferably within 40 hours, and even more preferably within 30 hours. The reaction pressure is, for example, preferably 0.01 to 0.5 MPa, more preferably 0.05 to 0.3 MPa, and still more preferably 0.1 to 0.2 MPa.

The unsaturated polyalkylene glycol monomer (1) can also be produced by a production method including the following step 1 ′, step 2 ′ and step 3 ′. In addition, you may include 1 or 2 or more of another process as needed.
Step 1 ′: A step of reacting an alkylene oxide adduct of an alcohol having 1 to 30 carbon atoms with an epoxy alcohol and / or a polyhydric alcohol.
Step 2 ′: a step of reacting the compound obtained in Step 1 ′ with an alkylene oxide.
Step 3 ′: The compound obtained by Step 2 ′ is added to the following general formula (7):

(Wherein R ¹ , R ² and R ³ are the same or different and each represents a hydrogen atom or a methyl group. P is 0, 1 or 2. q is 0 or 1) Reacting a compound having a group to be reacted.
In addition, the raw material used for each process can use 1 type (s) or 2 or more types, respectively.

In the above step 1 ′, as the alkylene oxide adduct of an alcohol having 1 to 30 carbon atoms, one or two or more kinds of alcohol having 1 to 30 carbon atoms may be used in an ordinary manner, or one or two alkylene oxides. Any compound obtained by adding more than one species may be used.
The reaction ratio between the alcohol and the alkylene oxide is preferably set so that the average number of moles of alkylene oxide added is 1 to 300. The average number of moles of alkylene oxide added herein means the average value of the number of moles of alkylene oxide added in 1 mole of polyalkylene glycol chain in the alkylene oxide adduct of an alcohol having 1 to 30 carbon atoms. . The lower limit of the average added mole number of the alkylene oxide is preferably 2 or more, more preferably 5 or more, still more preferably 8 or more, particularly preferably 10 or more, and most preferably 20 or more. The upper limit is preferably 200 or less, more preferably 150 or less, and still more preferably 100 or less.

Although it does not specifically limit as said C1-C30 alcohol, Especially a C1-C10 alcohol is suitable. More preferably, it is a C1-C5 alcohol, More preferably, it is a C1-C3 alcohol. In addition, the alcohol having 1 to 30 carbon atoms may be a saturated alcohol or an unsaturated alcohol. Further, the hydrocarbon group in the alcohol may be linear, branched or cyclic.
In addition, as said alkylene oxide, the form similar to what is used in the said process 2 is suitable.
As the epoxy alcohol and / or polyhydric alcohol, those similar to those used in Step 1 are suitable.

In the above step 1 ′, the reaction ratio of the alkylene oxide adduct of an alcohol having 1 to 30 carbon atoms with the epoxy alcohol and / or the polyhydric alcohol (molar ratio; the total amount of the adduct / epoxy alcohol and the polyhydric alcohol). Is preferably 1/1 to 1/100. More preferably, it is 1/1 to 1/50.

The above step 1 'is also preferably performed in the presence of a catalyst. As a catalyst, the thing similar to the catalyst quoted at the said process 1 can be used 1 type, or 2 or more types, for example.

Regarding the reaction conditions of the above step 1 ', the reaction temperature is, for example, preferably 50 to 200 ° C, more preferably 70 to 160 ° C. For example, the reaction time is preferably 0.5 to 24 hours, and more preferably 1 to 10 hours. The reaction pressure may be any of reduced pressure, normal pressure, and increased pressure, but a reaction at normal pressure is sufficient.

As the alkylene oxide used in the step 2 ', the same form as that used in the step 2 is preferable.

In step 2 ', the reaction ratio between the compound obtained in step 1' and the alkylene oxide is preferably set so that the average number of moles of alkylene oxide added is 2 to 300. The average number of moles of alkylene oxide added here means the average number of moles of alkylene oxide added in 1 mole of the polyalkylene glycol chain formed in step 2 ′ in the compound obtained in step 2 ′. Mean value. The lower limit of the average added mole number of the alkylene oxide is preferably 2 or more, more preferably 5 or more, still more preferably 8 or more, particularly preferably 10 or more, and most preferably 20 or more. The upper limit is preferably 300 or less, more preferably 200 or less, and still more preferably 100 or less.

The above step 2 'is also preferably performed in the presence of a catalyst. As a catalyst, the thing similar to the catalyst quoted at the said process 1 can be used 1 type, or 2 or more types, for example.

Regarding the reaction conditions of the above step 2 ', the reaction temperature is preferably 60 to 200 ° C, and more preferably 80 to 150 ° C, for example. For example, the reaction time is preferably within 50 hours, more preferably within 40 hours, and even more preferably within 30 hours. For example, the reaction pressure is preferably 0.01 to 0.5 MPa, more preferably 0.05 to 0.3 MPa, and still more preferably 0.1 to 0.2 MPa.

In the step 3 ′, examples of the compound having a group represented by the general formula (7) include a compound having a structure in which a hydroxyl group (—OH) or a halogen element (—Q) is bonded to the group. Can be mentioned. In addition, R < ¹ >, R < ² >, R < ³ >, p and q in the said General formula (7) are the same as each symbol in the said General formula (1).

Specific examples of the compound having a group represented by the general formula (7) include, for example, acrylic acid, methacrylic acid, allyl alcohol, allyl chloride, allyl bromide, allyl iodide, methallyl alcohol, methallyl chloride, meta Examples include ril bromide, methallyl iodide, isoprenol, isoprenyl chloride, isoprenyl bromide, and isoprenyl iodide.

In the step 3 ′, the reaction ratio (molar ratio; compound obtained by the step 2 ′ / the general formula (7) between the compound obtained by the step 2 ′ and the compound having the group represented by the general formula (7). ) Is preferably 1/1 to 1/2. More preferably, it is 1/1 to 1 / 1.2.

The step 3 'is also preferably performed in the presence of a catalyst. Examples of the catalyst include acid catalysts such as sulfuric acid and p-toluenesulfonic acid; alkali metal hydroxides such as sodium hydroxide and potassium hydroxide; alkaline earth metal hydroxides such as calcium hydroxide; sodium carbonate And alkali metal carbonates such as sodium hydrogen carbonate; alkaline earth metal carbonates, organic amines such as triethylamine and ethanolamine; and the like.

Regarding the reaction conditions of the above step 3 ', the reaction temperature is preferably 30 to 150 ° C, more preferably 50 to 130 ° C, for example. The reaction time is appropriately determined depending on the reaction conditions such as reaction temperature, reaction solvent, catalyst type, and catalyst amount.

<Unsaturated polyalkylene glycol monomer (2)>
In the monomer component for obtaining the polycarboxylic acid copolymer (2) of the present invention, the unsaturated polyalkylene glycol monomer (2) is the following general formula (2):

(Wherein R ¹ , R ² and R ³ are the same or different and each represents a hydrogen atom or a methyl group. X represents — (A ¹ O) _t —, and A ¹ O represents the same or different. Represents an oxyalkylene group having 2 to 18 carbon atoms, t represents an average addition mole number of the oxyalkylene group represented by A ¹ O, and is a number of 1 to 300. Y ² represents an active group 3 .Z representing the residue of a compound having more than five, identical or ^different, - .p representing the (a _{2 O)} n -R ⁴ is .q is 0, 1 or 2, is 0 or 1 U is 0 or 1. m ² is an integer of 3 or more, and the maximum number is determined depending on the number of active groups of the compound having 3 or more active groups represented by Y ² . a ² O are the same or different, .R ⁴ representing an oxyalkylene group having 2 to 18 carbon atoms are the same or different, hydrogen atoms Or .n representing a hydrocarbon group having 1 to 30 carbon atoms, it represents an average addition mole number of the oxyalkylene group represented by A 2 ^O, same or different, tables in a number of 2-300.) It is a compound.

In the general formula (2), R ¹ , R ² , R ³ , R ⁴ , A ¹ O, t, Z, p and q are the same as the respective symbols in the general formula (1) (preferable The same applies to other forms.)
In addition, u is 0 or 1, and when u = 0, there is no polyalkylene glycol chain represented by X in the general formula (2), that is,-(A ¹ O) _t-. However, even in such a form, the number of branched polyalkylene glycol chain-containing groups represented by -Y ^2- (Z) _m ² (the number of branches: m ² ) is 3 or more, so that early strength development And dispersibility can be sufficiently exhibited. However, in order to make these performances more satisfactory, it is preferable that the general formula (2) has X. That is, it is preferable that u = 1.

Y ² in the general formula (2) represents a residue of a compound having 3 or more active groups. The number of active groups (that is, the number of active hydrogens) of the compound having an active group is preferably 4 or more, more preferably 5 or more, from the viewpoint of further improving dispersibility and early strength development. In consideration of the polymerizability when the unsaturated polyalkylene glycol monomer (2) is subjected to polymerization, the upper limit is preferably 50 or less. More preferably, it is 20 or less, and more preferably 10 or less.
In addition, 1 type may be sufficient as the residue of the compound which has 3 or more of such active groups, and 2 or more types may be sufficient as it.

Specifically, as the residue (Y ² ) of the compound having three or more active groups, for example, as in Y ¹ in the above general formula (1), a polyhydric alcohol residue, a polyvalent amine residue A polyvalent imine residue, a polyvalent amide residue, and the like are preferable. Among them, at least one polyvalent amine selected from the group consisting of a polyvalent amine residue, a polyvalent imine residue, and a polyhydric alcohol residue is preferable. A compound residue is preferred. This makes it possible to obtain a polycarboxylic acid copolymer suitable for various uses such as a dispersant and a cement admixture.
The form of the compound residue having an active group may be any of a chain structure, a branched structure, and a three-dimensionally crosslinked structure, but a branched structure is preferable.

Regarding the residue of the compound having three or more active groups, the polyhydric alcohol constituting the polyhydric alcohol residue may be a compound containing an average of three or more hydroxyl groups in one molecule, A compound composed of three elements of hydrogen and oxygen is preferable. Specifically, for example, among the compounds exemplified as the polyhydric alcohol constituting Y ¹ in the general formula (1), there may be mentioned polyhydric alcohols having 3 or more hydroxyl groups. Among these, polyglycidol is preferable from the viewpoint of easy reaction.
The polyhydric alcohol forms a polyhydric alcohol residue of the unsaturated polyalkylene glycol monomer (2).

The polyvalent amine (polyamine) constituting the polyvalent amine residue may be a compound having an average of 3 or more amino groups in one molecule. For example, Y ¹ in the general formula (1) is represented by Among the compounds exemplified as the constituting polyvalent amine, a polyvalent amine having 3 or more amino groups can be mentioned. Among them, it is preferable to use a polyalkylamine having an average of 3 or more amino groups in one molecule, and the alkylamine constituting the polyalkylamine is preferably an alkylamine having 8 to 18 carbon atoms such as laurylamine. is there.
The polyvalent amine forms the polyvalent amine residue of the unsaturated polyalkylene glycol monomer (2).

The polyvalent imine (polyimine) constituting the polyvalent imine residue may be a compound having an average of 3 or more imino groups in one molecule. For example, Y ¹ in the general formula (1) is represented by Among the compounds exemplified as the constituting polyimine, polyvalent imines having 3 or more imino groups can be mentioned. Among them, it is preferable to use a polyalkylimine having an average of 3 or more imino groups in one molecule, and among the polyalkyleneimines, a polyalkylenimine mainly composed of ethyleneimine is more preferable. The “subject” in this case is as described above.
The polyvalent imine forms the polyvalent imine residue of the unsaturated polyalkylene glycol monomer (2).

The average polymerization number of alkyleneimine per one polyalkyleneimine chain is preferably 3 to 300. By setting it as such a range, it becomes possible to fully exhibit the effect resulting from the structure of the said unsaturated polyalkylene glycol monomer (2), for example, when it is used as a polymer, It can be made suitable for applications such as cement admixture by exhibiting dispersion performance. The lower limit is more preferably 5 or more, and particularly preferably 10 or more. Further, the upper limit is more preferably 200 or less, still more preferably 100 or less, particularly preferably 75 or less, and most preferably 50 or less.

The number average molecular weights of the polyvalent amine and polyvalent imine are preferably in the same range as described above.

Of the residues of the compound having 3 or more active groups, a polyhydric alcohol residue is particularly preferable, and a polyglycidol residue (also referred to as a polyglyceryl group) is most preferable as described above. In this case, Y ² in the general formula (2) is preferably represented by the general formula (5). Thus, the form in which Y ¹ in the general formula (1) or Y ² in the general formula (2) represents the general formula (5) is also one of the preferable forms of the present invention. .
In the case where Y ² represents the general formula (5), it is appropriate that r is 2 or more. A preferred range is as described above.

In the above general formula (2), the residue (Y ² ) of the compound having three or more active groups is bonded to m ² branched chains Z (— (A ¹ O) _n —R ⁴ ). . The number of Z to which Y ² binds, that is, m ² is suitably 3 or more, but when it is 3 or more, the unsaturated polyalkylene glycol monomer (2) A branched structure, that is, a structure in which a polyalkylene glycol chain represented by-(A ² O) _n- extends radially from the residue of a compound having three or more active groups as a base point. By having such a structure, it becomes possible for the polycarboxylic acid copolymer of the present invention to exhibit extremely high dispersion performance and to provide a better dispersant and cement admixture with an early strength. . Preferably it is 4 or more, more preferably 5 or more. In consideration of polymerizability, m ² is preferably 50 or less, more preferably 20 or less, and still more preferably 10 or less.

The m ² is also preferably equal to the number of active groups in the compound having 3 or more active groups. That is, the unsaturated polyalkylene glycol-based monomer (2) is bonded to all active groups (more specifically, active hydrogen atoms constituting the active groups) in the compound having three or more active groups. It is preferable to have a structure in which an alkylene glycol chain — (A ² O) _n — is bonded. As a result, it is possible to provide a dispersant and a cement admixture that can exhibit further superior dispersion performance and early strength, and thus polycarboxylic acid copolymers useful for various applications can be obtained.

The molecular weight (weight average molecular weight and number average molecular weight) of the unsaturated polyalkylene glycol monomer (2) may be in the same range as the molecular weight of the unsaturated polyalkylene glycol monomer (1) described above. Is preferred.

The unsaturated polyalkylene glycol monomer (2) can be obtained, for example, by the same production method as the unsaturated polyalkylene glycol monomer (1). That is, it can be suitably obtained by the above-described manufacturing method including step 1 (more preferably, a manufacturing method including step 1 and step 2) and a manufacturing method including step 1 ′, step 2 ′ and 3 ′. . In this case, it is preferable to set the reaction molar ratio so that the number of branches formed by the polyhydric alcohol is 3 or more when the polyhydric alcohol is reacted in Step 1 and Step 1 ′.

<Unsaturated polyalkylene glycol monomer (3)>
In the monomer component for obtaining the polycarboxylic acid copolymer (3) of the present invention, the unsaturated polyalkylene glycol monomer (3) is the following general formula (3):

^(Wherein, R 1, ^{R 2} and ^{R 3} are the same or different, .R ⁴ represents a hydrogen atom or a methyl group are the same or different, represent a hydrogen atom or a hydrocarbon group having 1 to 30 carbon atoms A ¹ O is the same or different and represents an oxyalkylene group having 2 to 18 carbon atoms, p is 0, 1 or 2. q is 0 or 1. t is A ¹ O. The average added mole number of the oxyalkylene group represented is a number from 1 to 300. m ³ is an integer of 2 or more, and represented by Y ³ — (C ₃ H ₆ O ₂ ) _r —. The maximum number is determined depending on the number of active groups of Y ³ represents the following general formula (5).
_{- (C 3 H 6 O 2} ) r - (5)
r _represents an average addition number of moles of glyceryl group represented by _{(C 3 H 6 O 2)} , the number of 1 to 300. The glyceryl groups represented by (C ₃ H ₆ O ₂ ) are the same or different and have the following formula:

It consists of the structure represented by. ). Such a compound is very useful as an intermediate for the unsaturated polyalkylene glycol monomers (1) and (2) described above.

In the general formula (3), R ¹ , R ² , R ³ , R ⁴ , A ¹ O, t, p and q are the same as the respective symbols in the general formula (1) (Suitable form) Is the same).
The ^{Y 3} in the general formula (3) _is - _(C 3 _{H 6} O _{2) r} - _represents, glyceryl group represented by _{(C 3} H 6 _{O 2)} is expressed by the above expression Consists of structure. A preferable range of r is as described above.

In the above general formula (3), the residue (Y ³ ) of the compound having two or more active groups is bonded to m ³ R ⁴ . M ³ is suitably 2 or more, but is preferably 3 or more. More preferably, it is 4 or more, More preferably, it is 5 or more. In consideration of the polymerizability when polymerization is performed using the unsaturated polyalkylene glycol monomer, m ³ is preferably 50 or less, more preferably 20 or less, and still more preferably 10 or less. .

M ³ is preferably equal to the number of active groups in the compound having two or more active groups. That is, the unsaturated polyalkylene glycol monomer (3) is bonded to all active groups (more specifically, active hydrogen atoms constituting the active groups) in the compound having two or more active groups. It is preferable to have a structure in which a hydrogen atom or a hydrocarbon group represented by ⁴ is bonded. As a result, it is possible to provide a dispersant and a cement admixture that can exhibit better dispersion performance and early strength, so that polycarboxylic acid copolymers useful for various applications can be obtained.

The molecular weight (weight average molecular weight and number average molecular weight) of the unsaturated polyalkylene glycol monomer (3) may be in the same range as the molecular weight of the unsaturated polyalkylene glycol monomer (1) described above. Is preferred.

The unsaturated polyalkylene glycol monomer (3) is represented by, for example, the general formula (6) in the production method of the unsaturated polyalkylene glycol monomer (1) or (2) described above. In the step 1 of reacting an unsaturated polyalkylene glycol compound with an epoxy alcohol and / or a polyhydric alcohol, it can be obtained by using (poly) glycidol as the epoxy alcohol and / or the polyhydric alcohol.

<Unsaturated carboxylic acid monomer>
In the monomer component for obtaining the polycarboxylic acid copolymer of the present invention (each of (1) to (3)), the unsaturated carboxylic acid monomer is represented by the following general formula (4):

（式中、Ｒ^５、Ｒ^６及びＲ^７は、同一又は異なって、水素原子、メチル基又は−（ＣＨ_２）_ｙＣＯＯＭ^２を表す。なお、−（ＣＨ_２）_ｙＣＯＯＭ^２を表す場合、−ＣＯＯＭ^１又は他の−（ＣＨ_２）_ｙＣＯＯＭ^２と無水物を形成していてもよく、この場合は、これらの基のＭ^１及びＭ^２は存在しない。ｙは、０、１又は２である。Ｍ^１及びＭ^２は、同一又は異なって、水素原子、アルカリ金属原子、アルカリ土類金属原子、アンモニウム基、アルキルアンモニウム基又は置換アルキルアンモニウム基を表す。）で表される化合物である。

^(Wherein, R 5, ^{R 6} and ^{R 7} are the same or different and each represents a hydrogen atom, a methyl group or _- represents a _(CH ²⁾ y COOM 2 Note, _{-. (CH} 2) when representing the y COOM ^2, -COOM ¹ or other-(CH ₂ ) _y COOM ² may form an anhydride, in which case M ¹ and M ² of these groups are absent, y is 0, 1 or 2 M ¹ and M ² are the same or different and each represents a hydrogen atom, an alkali metal atom, an alkaline earth metal atom, an ammonium group, an alkylammonium group or a substituted alkylammonium group. .

In the general formula (4), M ¹ and M ² are the same or different and each represents a hydrogen atom, an alkali metal atom, an alkaline earth metal atom, an ammonium group, an alkyl ammonium group, or a substituted alkyl ammonium group. Examples of the alkali metal atom include lithium, sodium, and potassium, and examples of the alkaline earth metal atom include calcium and magnesium. Examples of the alkylammonium group include a triethylamine group, and examples of the substituted alkylammonium group include an alkanolamine group such as an ethanolamine group, a diethanolamine group, and a triethanolamine group.

Specific examples of the unsaturated carboxylic acid monomer represented by the general formula (4) include, for example, unsaturated monocarboxylic acid monomers such as acrylic acid, methacrylic acid, and crotonic acid; maleic acid and itacone. Unsaturated dicarboxylic acid monomers such as acids and fumaric acids; anhydrides or salts of these carboxylic acids (for example, alkali metal salts, alkaline earth metal salts, ammonium salts, alkylammonium salts and substituted alkylammonium salts), etc. Is mentioned. Among these, from the viewpoint of polymerizability, acrylic acid, methacrylic acid, maleic acid, maleic anhydride and / or salts thereof are preferable, and acrylic acid, methacrylic acid and salts thereof are more preferable.

<Other monomers>
The monomer component for obtaining the polycarboxylic acid copolymer of the present invention (each of (1) to (3)) may further contain other monomers as required. The other monomer is a monomer other than the unsaturated polyalkylene glycol monomer and the unsaturated carboxylic acid monomer, and the unsaturated polyalkylene glycol monomer and / or the unsaturated monomer. Although it will not specifically limit if it is a monomer copolymerizable with a saturated carboxylic acid-type monomer, For example, 1 type (s) or 2 or more types, such as the following monomer, can be used.

Half esters and diesters of the above unsaturated dicarboxylic acid monomers and alcohols having 1 to 30 carbon atoms; Half amides and diamides of the above unsaturated dicarboxylic acid monomers and amines having 1 to 30 carbon atoms A half ester or a diester of an alkyl (poly) alkylene glycol obtained by adding 1 to 500 moles of an alkylene oxide having 2 to 18 carbon atoms to the alcohol or amine and the unsaturated dicarboxylic acid monomer; Half esters and diesters of saturated dicarboxylic acid monomers and alkylene glycols having 2 to 18 carbon atoms or polyalkylene glycols having 2 to 500 moles of addition of the alkylene glycol;

1 to 30 carbon atoms and unsaturated monocarboxylic acids such as methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, glycidyl (meth) acrylate, methyl crotonate, ethyl crotonate, propyl crotonate Esters with alcohols: alkoxy (poly) alkylene glycols obtained by adding 1 to 500 moles of alkylene oxides having 2 to 18 carbon atoms to alcohols having 1 to 30 carbon atoms and unsaturated monocarboxylic acids such as (meth) acrylic acid Esters with acids; 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, (poly) ethylene glycol mono (meth) acrylate, (poly) propylene glycol mono (meth) acrylate, (poly) butylene Glycol 1-500 mole adducts of alkylene oxides having 2 to 18 carbon atoms to unsaturated monocarboxylic acids such as (meth) acrylic acid, such as (meth) acrylate; triethylene glycol di (meth) acrylate, ( (Poly) alkylene glycol di (meth) acrylates such as poly) ethylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate and (poly) ethylene glycol (poly) propylene glycol di (meth) acrylate; -Alkanediol mono (meth) acrylates such as butanediol mono (meth) acrylate, 1,5-pentanediol mono (meth) acrylate, 1,6-hexanediol mono (meth) acrylate;

Half amides of maleamic acid and glycols having 2 to 18 carbon atoms or polyalkylene glycols having 2 to 500 addition moles of these glycols; hexanediol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, tri Polyfunctional (meth) acrylates such as methylolpropane di (meth) acrylate; (poly) alkylene glycol dimaleates such as triethylene glycol dimaleate and polyethylene glycol dimaleate; vinyl sulfonate, (meth) allyl sulfonate, 2- ( (Meth) acryloxyethyl sulfonate, 3- (meth) acryloxypropyl sulfonate, 3- (meth) acryloxy-2-hydroxypropyl sulfonate, 3- (meth) acryloxy-2-hydroxypropyls Phophenyl ether, 3- (meth) acryloxy-2-hydroxypropyloxysulfobenzoate, 4- (meth) acryloxybutyl sulfonate, (meth) acrylamidomethylsulfonic acid, (meth) acrylamidoethylsulfonic acid, 2-methylpropanesulfone Unsaturated sulfonic acids such as acid (meth) acrylamide and styrene sulfonic acid, and monovalent metal salts, divalent metal salts, ammonium salts and organic amine salts thereof; unsaturated monocarboxylic acids such as methyl (meth) acrylamide and carbon atom Amides with amines of 1 to 30; Vinyl aromatics such as styrene, α-methylstyrene, vinyltoluene, p-methylstyrene;

Dienes such as butadiene, isoprene, 2-methyl-1,3-butadiene, 2-chloro-1,3-butadiene; (meth) acrylamide, (meth) acrylalkylamide, N-methylol (meth) acrylamide, N, Unsaturated amides such as N-dimethyl (meth) acrylamide; unsaturated cyanides such as (meth) acrylonitrile and α-chloroacrylonitrile; unsaturated esters such as vinyl acetate and vinyl propionate; aminoethyl (meth) acrylate , Unsaturated amines such as methylaminoethyl (meth) acrylate, dimethylaminoethyl (meth) acrylate, dimethylaminopropyl (meth) acrylate, dibutylaminoethyl (meth) acrylate, vinylpyridine, and the like; Divinyl aromatics such as triallyl cyanurate Anurates; Allyls such as (meth) allyl alcohol and glycidyl (meth) allyl ether; Unsaturated amino compounds such as dimethylaminoethyl (meth) acrylate; Methoxypolyethylene glycol vinyl ether, polyethylene glycol monovinyl ether, methoxypolyethylene glycol (meta ) Vinyl ethers or allyl ethers such as allyl ether and polyethylene glycol mono (meth) allyl ether; polydimethylsiloxanepropylaminomaleamic acid, polydimethylsiloxaneaminopropylaminomaleamic acid, polydimethylsiloxane-bis- (propylaminomaleamide) Acid), polydimethylsiloxane-bis- (dipropyleneaminomaleamic acid), polydimethylsiloxane- (1-propyl Propyl-3-acrylate), polydimethylsiloxane- (1-propyl-3-methacrylate), polydimethylsiloxane-bis- (1-propyl-3-acrylate), polydimethylsiloxane-bis- (1-propyl-3-) Siloxane derivatives such as methacrylate);

<Method for producing polycarboxylic acid copolymer>
Next, a method for obtaining the polycarboxylic acid copolymer of the present invention (each of (1) to (3)) will be described.
As a method for obtaining the polycarboxylic acid-based copolymer, an unsaturated polyalkylene glycol-based monomer and an unsaturated carboxylic acid-based monomer, and, if necessary, other single amounts using a polymerization initiator The monomer component containing the monomer may be copolymerized, but the monomer component contained in the monomer component may be such that each structural unit constituting the polycarboxylic acid copolymer is within the above-described range. It is preferable to appropriately set the type and amount used. That is, it is preferable to appropriately set the type and amount of the monomer contained in the monomer component so that the proportion of the structural units constituting the polycarboxylic acid copolymer is in the preferred range described above. .

Therefore, in the monomer component used to obtain each of the polycarboxylic acid-based copolymers, the mixing ratio (mass ratio) of the unsaturated polyalkylene glycol-based monomer and the unsaturated carboxylic acid-based monomer. The unsaturated polyalkylene glycol monomer / unsaturated carboxylic acid monomer) is, for example, preferably 1/99 to 60/30. More preferably, it is 5 / 95-40 / 60.
The monomer component may further contain other monomers, but the proportion is preferably 50% by mass or less in 100% by mass of all monomer components. More preferably, it is 30 mass% or less, More preferably, it is 10 mass% or less. That is, in the monomer component, the proportion of the unsaturated polyalkylene glycol monomer and the unsaturated carboxylic acid monomer is 50% by mass or more in 100% by mass of all monomer components. Is preferable, more preferably 70% by mass or more, and still more preferably 90% by mass or more.

In the polymerization step (copolymerization step) for obtaining the polycarboxylic acid-based copolymer, the method for adding each monomer component is not particularly limited, and may be initially charged in the reactor, or in whole or in part. May be added dropwise. Moreover, the order of the monomer to add is not specifically limited, You may add simultaneously.
In addition, when a part or all of the monomer component is dropped into the reactor, the monomer charging rate is changed continuously or stepwise during the reaction, Two or more kinds of copolymers having different monomer ratios may be synthesized simultaneously during the polymerization reaction by changing the input weight ratio of.

The said polymerization process can be performed by normal methods, such as solution polymerization and block polymerization. The solution polymerization can be carried out either batchwise or continuously. Examples of the solvent used here include water; alcohols such as methyl alcohol, ethyl alcohol, isopropyl alcohol; benzene, toluene, xylene, cyclohexane, n- Examples include aromatic or aliphatic hydrocarbons such as hexane; ester compounds such as ethyl acetate; ketone compounds such as acetone and methyl ethyl ketone; and cyclic ether compounds such as tetrahydrofuran and dioxane. Among these, from the viewpoint of the solubility of the raw material monomer and the resulting polymer, it is preferable to use at least one selected from the group consisting of water and a lower alcohol having 1 to 4 carbon atoms. It is more preferable in that the solvent step can be omitted.

When the polymerization step is performed by an aqueous solution polymerization method, a water-soluble polymerization initiator, for example, a persulfate such as ammonium persulfate, sodium persulfate, or potassium persulfate; hydrogen peroxide; 2 Azoamidine compounds such as 2,2′-azobis-2-methylpropionamidine hydrochloride, cyclic azoamidine compounds such as 2,2′-azobis-2- (2-imidazolin-2-yl) propane hydrochloride, 2-carbamoylazoiso It is preferable to use a water-soluble azo initiator such as an azonitrile compound such as butyronitrile. In addition, at this time, alkali metal sulfites such as sodium hydrogen sulfite, metabisulfite, sodium hypophosphite, Fe (II) salts such as molle salt, sodium hydroxymethanesulfinate dihydrate, hydroxylamine hydrochloride, Accelerators such as thiourea, L-ascorbic acid (salt), and erythorbic acid (salt) can also be used in combination. Among these, a combination of a persulfate and an accelerator such as L-ascorbic acid (salt) is preferable. These radical polymerization initiators and accelerators may be used alone or in combination of two or more.

When performing solution polymerization using a lower alcohol, aromatic or aliphatic hydrocarbon, ester compound or ketone compound as a solvent, examples of radical polymerization initiators include benzoyl peroxide, lauroyl peroxide, and sodium peroxide. Peroxides; hydroperoxides such as t-butyl hydroperoxide and cumene hydroperoxide; azo compounds such as azobisisobutyronitrile are preferably used. At this time, an accelerator such as an amine compound can be used in combination.
Further, when a water-lower alcohol mixed solvent is used, it can be appropriately selected from the above-mentioned various radical polymerization initiators or combinations of radical polymerization initiators and accelerators.

When the polymerization step is carried out by a bulk polymerization method, for example, as a radical polymerization initiator, peroxides such as benzoyl peroxide, lauroyl peroxide, sodium peroxide; t-butyl hydroperoxide, cumene hydroperoxide, etc. It is preferable to perform polymerization at a temperature of 50 to 200 ° C. using hydroperoxide; an azo compound such as azobisisobutyronitrile.

The radical polymerization initiator may be charged into the reaction vessel from the beginning, may be dropped into the reaction vessel, or may be combined according to the purpose.

In the polymerization step, the reaction temperature is not particularly limited. For example, when a persulfate is used as an initiator, the reaction temperature is preferably in the range of 30 to 100 ° C. More preferably, it is the range of 40-95 degreeC, More preferably, it is the range of 45-90 degreeC. Moreover, when combining a persulfate and L-ascorbic acid (salt) as a promoter and making it an initiator, it is preferable to make reaction temperature into the range of 30-100 degreeC. More preferably, it is the range of 40-95 degreeC, More preferably, it is the range of 45-90 degreeC.
Moreover, although superposition | polymerization time is not specifically limited, For example, it is preferable to set it as the range of 0.5 to 10 hours. If the polymerization time is too long or too short, the polymerization rate may not be sufficient or the productivity may not be improved. More preferably, it is 0.5-8 hours, More preferably, it is the range of 1-6 hours.

The amount of all monomer components used in the polymerization step is preferably in the range of 10 to 99% by mass with respect to 100% by mass of all raw materials including the other raw materials and the polymerization solvent. In particular, if the amount of all monomer components used is too lower than this range, the polymerization rate may not be sufficient, or the productivity may not be improved. More preferably, it is 20-98 mass%, More preferably, it is 25-95 mass%, More preferably, it is 30-90 mass%, Especially preferably, it is 30-80 mass%, Most preferably, it is the range of 40-70 mass%.

In the polymerization step, a chain transfer agent can be used to adjust the molecular weight of the resulting polycarboxylic acid copolymer. In particular, it is preferable to use a chain transfer agent when the polymerization reaction is performed at a high concentration of 30% by mass or more with respect to 100% by mass of the total amount of raw materials used during polymerization. . Examples of chain transfer agents include mercaptoethanol, thioglycerol, thioglycolic acid, 2-mercaptopropionic acid, 3-mercaptopropionic acid, thiomalic acid, octyl thioglycolate, octyl 3-mercaptopropionate, 2-mercaptoethanesulfonic acid, etc. These thiol chain transfer agents can be used, and two or more types of chain transfer agents can be used in combination. Furthermore, in order to adjust the molecular weight of the copolymer, it is also effective to use a monomer having high chain mobility such as (meth) allylsulfonic acid (salt) as the other monomer.

In addition, in order to obtain a copolymer having a predetermined molecular weight with good reproducibility, it is important to allow the copolymerization reaction to proceed stably. Therefore, when performing solution polymerization, the dissolved oxygen concentration of the solvent used at 25 ° C. Is preferably 5 ppm or less. More preferably, it is 0.01-4 ppm, More preferably, it is 0.01-2 ppm, Most preferably, it is 0.01-1 ppm. In addition, what is necessary is just to make the dissolved oxygen concentration of the type | system | group containing a monomer into the said range, when performing nitrogen substitution etc. after adding a monomer to a solvent. The dissolved oxygen concentration of the solvent may be adjusted in a polymerization reaction tank, or a solvent in which the dissolved oxygen amount is adjusted in advance may be used. Examples of the method for driving off oxygen in the solvent include the following methods (1) to (5).

(1) After an inert gas such as nitrogen is pressure-filled in a sealed container containing a solvent, the partial pressure of oxygen in the solvent is lowered by lowering the pressure in the sealed container. You may reduce the pressure in an airtight container under nitrogen stream.
(2) The liquid phase portion is vigorously stirred for a long time while the gas phase portion in the container containing the solvent is replaced with an inert gas such as nitrogen.
(3) An inert gas such as nitrogen is bubbled in the solvent in the container for a long time.
(4) The solvent is once boiled and then cooled in an inert gas atmosphere such as nitrogen.
(5) A static mixer (static mixer) is installed in the middle of the pipe, and an inert gas such as nitrogen is mixed in the pipe for transferring the solvent to the polymerization reaction tank.

In the above polymerization step, when a solvent is used, the polymerization may be performed at a pH of 5 or more. In that case, the copolymerization is not sufficient at the same time as the polymerization rate is lowered. Therefore, the copolymerization reaction is preferably carried out at a pH of less than 5. The pH can be adjusted by, for example, inorganic salts such as monovalent metal or divalent metal hydroxides and carbonates; alkaline substances such as ammonia; organic amines; inorganic acids such as hydrochloric acid, phosphoric acid and sulfuric acid, acetic acid It can be carried out using organic acids such as p-toluenesulfonic acid.

The polymerization step may further include other steps. The other steps are not particularly limited as long as they are steps performed in a usual copolymer production method.

The polycarboxylic acid copolymer obtained by the above polymerization step can be used for various purposes as it is, for example, it can be used as a main component of a dispersant, a cement admixture, etc. Therefore, it is preferable to adjust the pH to 5 or more. As described above, the copolymerization reaction is preferably performed at a pH of less than 5, and the pH is preferably adjusted to 5 or more after the copolymerization. The pH can be adjusted using, for example, an alkaline substance such as an inorganic salt such as a monovalent metal or divalent metal hydroxide or carbonate; ammonia; an organic amine; Further, after the reaction is completed, the concentration can be adjusted if necessary. The polycarboxylic acid copolymer may be used in various forms in the form of an aqueous solution, or may be neutralized with a divalent metal hydroxide such as calcium or magnesium to form a polyvalent metal salt. Then, it may be dried or powdered by supporting it on an inorganic powder such as silica-based fine powder and drying it.

The polycarboxylic acid-based copolymer obtained by the polymerization step may be subjected to a step of isolating individual polymers as necessary, but from the viewpoint of work efficiency, production cost, etc. These polymers can be used for various purposes without isolation.

[Use]
The polycarboxylic acid copolymer of the present invention can exhibit good performance as, for example, a water-insoluble inorganic or organic dispersant. Specifically, good performance can be exhibited as dispersants for inorganic pigments such as heavy or light calcium carbonate and clay used for paper coating; dispersants for water slurries such as cement and coal. In addition, for example, cement admixtures; cooling water systems, boiler water systems, seawater desalination equipment, pulp digesters, black liquor concentration tanks, water treatment agents for preventing scales; scale inhibitors; It can also be suitably used for fiber treatment agents such as auxiliaries; adhesives; sealing agents; components for imparting flexibility to various polymers; Furthermore, it can be widely applied in the fields of body detergents such as shampoos, rinses, body soaps, fiber processing, building material processing, paints, ceramics and the like. Above all, it is suitable to be used for cement admixture. In this case, it provides a cement admixture that is particularly excellent in early strength development while exhibiting cement dispersibility equivalent to or higher than that of conventional products at lower cost. it can. It is particularly useful as a cement admixture for secondary concrete products (precast). Thus, the embodiment in which the polycarboxylic acid copolymer is a dispersant copolymer or a cement admixture polycarboxylic acid copolymer is a preferred embodiment of the present invention. A dispersant containing an acid copolymer and a cement admixture containing the polycarboxylic acid copolymer are also included in the present invention.
Hereinafter, a cement admixture will be described as a typical dispersant.

<Cement admixture>
The cement admixture of the present invention contains the polycarboxylic acid copolymer, and in this case, the structural unit derived from the unsaturated carboxylic acid monomer in the polycarboxylic acid copolymer and the unsaturated polyalkylene glycol. In addition to high cement dispersion performance (water reduction performance), early strength development performance, particularly early strength development (for example, after 12 to 24 hours) Will also be excellent.
The cement admixture may contain two or more polycarboxylic acid copolymers, or one or more other polycarboxylic acid copolymers different from the polycarboxylic acid copolymer. May be included.

In the cement admixture, the content of the polycarboxylic acid copolymer of the present invention described above (when two or more polycarboxylic acid copolymers are included, the total content thereof) is not particularly limited, It is preferably 20% by mass or more and 100% by mass or less in 100% by mass of solid content (that is, non-volatile content) in the cement admixture. More preferably, it is 40 mass% or more, More preferably, it is 50 mass% or more, Most preferably, it is 60 mass% or more.
In the present specification, “cement admixture” refers to a cement additive added to a cement composition such as cement paste, mortar, concrete, etc., and is an agent composed only of the above polycarboxylic acid copolymer. Moreover, it may be an agent containing not only the polycarboxylic acid copolymer but also other components and additives as required.

The content of the cement admixture is not particularly limited as long as it contains the polycarboxylic acid-based copolymer. For example, the reaction product obtained by the polymerization may be used as it is as a cement admixture. Alternatively, the polycarboxylic acid copolymer may be isolated and used as a cement admixture. Moreover, the said cement admixture may also contain a solvent and another additive as needed.

The cement admixture may further contain other commonly used cement dispersants and cement additives (materials) as necessary, and can be used in combination.
The other cement dispersant is not particularly limited, for example, various sulfonic acid-based dispersants having a sulfonic acid group in the molecule, and various polycarboxylic acid-based dispersions having a polyoxyalkylene chain and a carboxyl group in the molecule. Agents and the like.
Examples of the cement additive (material) include, for example, water-soluble polymer substances, polymer emulsions, retarders, early strengthening agents / accelerators, antifoaming agents, AE (air entrainment) agents, water reducing agents, AE water reducing agents, Superplasticizer, surfactant, waterproofing agent, rust preventive agent, crack reducing agent, expansion material, cement wetting agent, thickener, separation reducing agent, quick setting agent, flocculant, drying shrinkage reducing agent, strength enhancer, Examples thereof include a self-leveling agent, a rust preventive agent, a coloring agent, an antifungal agent, a blast furnace slag, fly ash, cinder ash, clinker ash, husk ash, silica fume, silica powder, and gypsum.
The blending ratio of these cement dispersant and cement additive (material) is not particularly limited. For example, the total amount thereof is 10% by mass or less with respect to 100% by mass of the solid content of the polycarboxylic acid copolymer. It is preferable to set so.

The cement admixture can be used for various hydraulic materials, that is, cement compositions such as cement and gypsum, and other hydraulic materials. Specific examples of a hydraulic composition containing such a hydraulic material, water and the above cement admixture, and further containing aggregates (fine aggregates such as sand and coarse aggregates such as crushed stone) as necessary. Examples thereof include cement paste, mortar, concrete, plaster and the like. Among these hydraulic compositions, a cement composition using cement as the hydraulic material is most preferable, and a cement composition containing the cement admixture, cement and water is also one aspect of the present invention.

<Cement composition>
The cement composition of the present invention contains the above cement admixture, cement and water, and examples of the cement include Portland cement (ordinary, early strength, ultra-early strength, moderate heat, sulfate-resistant and their respective low alkali types. ); Various mixed cements (blast furnace cement, silica cement, fly ash cement); white Portland cement; alumina cement; super fast cement (1 clinker fast cement, 2 clinker fast cement, magnesium phosphate cement); grout cement; Oil well cement; Low heat generation cement (low heat generation type blast furnace cement, fly ash mixed low heat generation type blast furnace cement, high content cement of belite); Ultra high strength cement; Cement-based solidification material; Cement produced from one or more types of ash) Other, these blast furnace slag, fly ash, cinder ash, clinker ash, husk ash, silica fume, silica powder, and a film obtained by adding a fine powder and gypsum limestone powder.
The cement composition may also include an aggregate if necessary. Aggregates include gravel, crushed stone, granulated slag, recycled aggregate, etc., as well as silica, clay, zircon, high alumina, silicon carbide, graphite, chromium, chromic, magnesia, etc. Examples include fireproof aggregates.

In the cement composition, the unit water amount per 1 m ^3, the amount of cement used, and the water / cement ratio are not particularly limited. For example, the unit water amount is preferably 100 to 185 kg / m ³ , more preferably 120 to 175 kg / m ³ . Preferably the cement usage is 250~800kg / ^{m 3,} more preferably from 120~175kg / ^{m 3.} Moreover, it is preferable that water / cement ratio (mass ratio) is 0.1-0.7, More preferably, it is 0.2-0.65. Thus, the cement composition of the present invention can be widely used from poor blending to rich blending, and is effective for both high-strength concrete with a large amount of unit cement and poor blended concrete with a unit cement amount of 300 kg / m ³ or less. It is. Further, the cement composition of the present invention has a relatively high water reduction rate region, that is, water / cement ratio (mass ratio) = 0.15 to 0.6 (preferably 0.15 to 0.5). Even in a low cement ratio region, it can be used satisfactorily.

Here, since the cement admixture of the present invention can exhibit excellent performances even in a high water reduction rate region with high performance and has excellent workability, it is used for ready-mixed concrete and secondary concrete products (precast concrete). It can also be effectively applied to concrete, centrifugal concrete, vibration compaction concrete, steam-cured concrete, shotcrete, and the like. Also, medium-fluidity concrete (concrete with a slump value of 22-25 cm), high-fluidity concrete (concrete with a slump value of 25 cm or more and a slump flow value of 50-70 cm), self-filling concrete, self-leveling material It is also effective for mortar and concrete that require high fluidity.

In the cement composition, the blending ratio of the cement admixture of the present invention is, for example, 0.01 to 10% of the polycarboxylic acid copolymer in terms of solid content with respect to 100% by mass of the total amount of cement. It is preferable to set the mass%. If it is less than 0.01% by mass, the performance may not be sufficient. On the other hand, if it exceeds 10% by mass, the effect will substantially reach its peak, which may be disadvantageous in terms of economy. More preferably, it is 0.02-5 mass%, More preferably, it is 0.05-3 mass%. In the present specification, the solid content can be measured as follows.
(Solid content measurement method)
1. Weigh the aluminum dish precisely.
2. Weigh the solid content to be accurately weighed in the aluminum dish weighed in 1 and 1.
3. A solid content measurement product precisely weighed in 2 is placed in a dryer adjusted to 130 ° C. in a nitrogen atmosphere for 1 hour.
4. After 1 hour, remove from the dryer and allow to cool in a desiccator at room temperature for 15 minutes.
After 5 and 15 minutes, remove from the desiccator and accurately weigh the aluminum dish and the measurement object.
The solid content is measured by subtracting the mass of the aluminum dish obtained in 1 from the mass obtained in 6 and 5 and dividing the mass of the fixed content obtained in 2.

Since the polycarboxylic acid copolymer of the present invention has the above-described configuration, it is remarkably excellent in various performances, particularly early strength development performance and dispersion performance. Therefore, it is particularly useful for a dispersant or a cement admixture, and productivity and workability can be further improved in the field where it is handled. Therefore, the cement admixture containing this greatly contributes to the civil engineering / construction field and the like that handle concrete.

The present invention will be described in more detail with reference to the following examples. However, the present invention is not limited to these examples. Unless otherwise specified, “part” means “part by weight” and “%” means “% by mass”.
In the following production examples, the measurement conditions for the weight average molecular weight (GPC measurement method) were as described above.

<Unsaturated polyalkylene glycol monomer>
Production Example 1
A SUS autoclave reaction vessel equipped with a thermometer, a stirrer, a raw material introduction tube and a nitrogen introduction tube was charged with 145.2 g of an ethylene oxide 8 mol adduct of methallyl alcohol and 6.6 g of potassium hydroxide as an addition reaction catalyst, and stirred. The reaction vessel was purged with nitrogen and heated to 105 ° C. Next, a pipe equipped with a glass trap was connected from the top of the reaction vessel while stirring, and the inside of the reaction vessel was depressurized to 10 Torr using a vacuum pump. Thereafter, dehydration was performed at the same temperature for 3 hours while cooling the glass trap in an ethanol dry ice bath. After dehydration, the temperature was lowered to 95 ° C. in a nitrogen atmosphere. Then, 76.2 g of glycidol was introduced into the reactor over 2 hours while maintaining 95 ° C. under normal pressure. Further, the reaction was completed by maintaining at 95 ° C. for 2 hours.
The obtained reaction product (A-1) had a weight average molecular weight of 860 and a number average molecular weight of 710.

Production Example 2
154.3 g of reaction product (A-1) obtained in Production Example 1 (including 4.5 g of potassium hydroxide) in a SUS autoclave reaction vessel equipped with a thermometer, a stirrer, a raw material introduction tube and a nitrogen introduction tube The reaction vessel was purged with nitrogen while stirring, and then heated to 105 ° C. Next, a pipe equipped with a glass trap was connected from the top of the reaction vessel while stirring, and the inside of the reaction vessel was depressurized to 10 Torr using a vacuum pump. Thereafter, dehydration was performed at the same temperature for 1 hour while cooling the glass trap in an ethanol dry ice bath. After dehydration, the temperature was lowered to 95 ° C. in a nitrogen atmosphere. Then, 845.7 g of ethylene oxide was introduced into the reactor while maintaining the temperature at 95 ° C. under a safe pressure (the dropping time was 362 minutes), and the temperature was maintained until the alkylene oxide addition reaction was completed to complete the reaction (ripening time). 60 minutes).
The obtained reaction product (A-2) had a weight average molecular weight of 7,400 and a number average molecular weight of 4,500.

Production Example 3
A SUS autoclave reaction vessel equipped with a thermometer, a stirrer, a raw material introduction tube and a nitrogen introduction tube was charged with 475 g of the reaction product (A-2) obtained in Production Example 2 (including 2.1 g of potassium hydroxide). The reaction vessel was purged with nitrogen while stirring, and then heated to 105 ° C. Next, a pipe equipped with a glass trap was connected from the top of the reaction vessel while stirring, and the inside of the reaction vessel was depressurized to 10 Torr using a vacuum pump. Thereafter, dehydration was performed at the same temperature for 1 hour while cooling the glass trap in an ethanol dry ice bath. After dehydration, the temperature was lowered to 95 ° C. in a nitrogen atmosphere. Then, while maintaining 95 ° C. under safe pressure, 402.1 g of ethylene oxide was introduced into the reactor (the dropping time was 157 minutes), and the temperature was maintained until the alkylene oxide addition reaction was completed to complete the reaction (ripening time). 60 minutes).
The obtained reaction product (A-3) had a weight average molecular weight of 13,600 and a number average molecular weight of 7,700.

Production Example 4
A SUS autoclave reaction vessel equipped with a thermometer, a stirrer, a raw material introduction tube and a nitrogen introduction tube was charged with 243.2 g of a 20-mol ethylene oxide adduct of methallyl alcohol and 8.9 g of potassium hydroxide as an addition reaction catalyst, and stirred The reaction vessel was purged with nitrogen and heated to 105 ° C. Next, a pipe equipped with a glass trap was connected from the top of the reaction vessel while stirring, and the inside of the reaction vessel was depressurized to 10 Torr using a vacuum pump. Thereafter, dehydration was performed at the same temperature for 3 hours while cooling the glass trap in an ethanol dry ice bath. After dehydration, the temperature was lowered to 95 ° C. in a nitrogen atmosphere. And 56.8g of glycidol was introduce | transduced in the reactor over 2 hours, maintaining 95 degreeC under a normal pressure. Further, the reaction was completed by maintaining at 95 ° C. for 2 hours.
The obtained reaction product (A-4) had a weight average molecular weight of 1500 and a number average molecular weight of 1200.

Production Example 5
In a SUS autoclave reaction vessel equipped with a thermometer, stirrer, raw material introduction tube and nitrogen introduction tube, 174.6 g of reaction product (A-4) obtained in Production Example 4 (including 5.0 g of potassium hydroxide) The reaction vessel was purged with nitrogen while stirring, and then heated to 105 ° C. Next, a pipe equipped with a glass trap was connected from the top of the reaction vessel while stirring, and the inside of the reaction vessel was depressurized to 10 Torr using a vacuum pump. Thereafter, dehydration was performed at the same temperature for 1 hour while cooling the glass trap in an ethanol dry ice bath. After dehydration, the temperature was lowered to 95 ° C. in a nitrogen atmosphere. Then, 525.4 g of ethylene oxide was introduced into the reactor while maintaining the temperature at 95 ° C. under a safe pressure (the dropping time was 238 minutes), and the temperature was maintained until the alkylene oxide addition reaction was completed to complete the reaction (ripening time). 60 minutes).
The obtained reaction product (A-5) had a weight average molecular weight of 9,100 and a number average molecular weight of 4,800.

Production Example 6
523.2 g of reaction product (A-5) obtained in Production Example 5 (including 3.8 g of potassium hydroxide) in a SUS autoclave reaction vessel equipped with a thermometer, stirrer, raw material introduction tube and nitrogen introduction tube The reaction vessel was purged with nitrogen while stirring, and then heated to 105 ° C. Next, a pipe equipped with a glass trap was connected from the top of the reaction vessel while stirring, and the inside of the reaction vessel was depressurized to 10 Torr using a vacuum pump. Thereafter, dehydration was performed at the same temperature for 1 hour while cooling the glass trap in an ethanol dry ice bath. After dehydration, the temperature was lowered to 95 ° C. in a nitrogen atmosphere. Then, 376.8 g of ethylene oxide was introduced into the reactor while maintaining the temperature at 95 ° C. under a safe pressure (the dropping time was 192 minutes), and the temperature was maintained until the alkylene oxide addition reaction was completed to complete the reaction (ripening time). 60 minutes).
The obtained reaction product (A-6) had a weight average molecular weight of 16,300 and a number average molecular weight of 8,100.

Production Example 7
A SUS autoclave reaction vessel equipped with a thermometer, a stirrer, a raw material introduction tube and a nitrogen introduction tube was charged with 371.8 g of a 50-mole ethylene oxide adduct of methallyl alcohol and 8.0 g of potassium hydroxide as an addition reaction catalyst. The reaction vessel was purged with nitrogen and heated to 105 ° C. Next, a pipe equipped with a glass trap was connected from the top of the reaction vessel while stirring, and the inside of the reaction vessel was depressurized to 10 Torr using a vacuum pump. Thereafter, dehydration was performed at the same temperature for 3 hours while cooling the glass trap in an ethanol dry ice bath. After dehydration, the temperature was lowered to 95 ° C. in a nitrogen atmosphere. And 36.4g of glycidol was introduce | transduced in the reactor over 2 hours, maintaining 95 degreeC under a normal pressure. Further, the reaction was completed by maintaining at 95 ° C. for 2 hours.
The obtained reaction product (A-7) had a weight average molecular weight of 3,200 and a number average molecular weight of 2,900.

Production Example 8
In a SUS autoclave reaction vessel equipped with a thermometer, a stirrer, a raw material introduction tube and a nitrogen introduction tube, 209.0 g of the reaction product (A-7) obtained in Production Example 7 (including 4.0 g of potassium hydroxide) The reaction vessel was purged with nitrogen while stirring, and then heated to 105 ° C. Next, a pipe equipped with a glass trap was connected from the top of the reaction vessel while stirring, and the inside of the reaction vessel was depressurized to 10 Torr using a vacuum pump. Thereafter, dehydration was performed at the same temperature for 1 hour while cooling the glass trap in an ethanol dry ice bath. After dehydration, the temperature was lowered to 95 ° C. in a nitrogen atmosphere. Then, 591.0 g of ethylene oxide was introduced into the reactor while maintaining the temperature at 95 ° C. under a safe pressure (the dropping time was 191 minutes), and the reaction was terminated by maintaining the temperature until the alkylene oxide addition reaction was completed (ripening time). 60 minutes).
The obtained reaction product (A-8) had a weight average molecular weight of 16,400 and a number average molecular weight of 9,800.

Production Example 9
A SUS autoclave reaction vessel equipped with a thermometer, a stirrer, a raw material introduction tube and a nitrogen introduction tube was charged with 261.7 g of a 50-mole ethylene oxide adduct of methallyl alcohol and 5.0 g of potassium hydroxide as an addition reaction catalyst, and stirred. The reaction vessel was purged with nitrogen and heated to 105 ° C. Next, a pipe equipped with a glass trap was connected from the top of the reaction vessel while stirring, and the inside of the reaction vessel was depressurized to 10 Torr using a vacuum pump. Thereafter, dehydration was performed at the same temperature for 3 hours while cooling the glass trap in an ethanol dry ice bath. After dehydration, the temperature was lowered to 95 ° C. in a nitrogen atmosphere. And 59.7g of glycidol was introduce | transduced in the reactor over 4 hours, maintaining 95 degreeC under a normal pressure. Further, the reaction was completed by maintaining at 95 ° C. for 2 hours.
The obtained reaction product (A-9) had a weight average molecular weight of 3,500 and a number average molecular weight of 3,200.

Production Example 10
140.2 g of reaction product (A-9) obtained in Production Example 9 (including 2.2 g of potassium hydroxide) in a SUS autoclave reaction vessel equipped with a thermometer, a stirrer, a raw material introduction tube and a nitrogen introduction tube The reaction vessel was purged with nitrogen while stirring, and then heated to 105 ° C. Next, a pipe equipped with a glass trap was connected from the top of the reaction vessel while stirring, and the inside of the reaction vessel was depressurized to 10 Torr using a vacuum pump. Thereafter, dehydration was performed at the same temperature for 1 hour while cooling the glass trap in an ethanol dry ice bath. After dehydration, the temperature was lowered to 95 ° C. in a nitrogen atmosphere. Then, 709.8 g of ethylene oxide was introduced into the reactor while maintaining the temperature at 95 ° C. under a safe pressure (the dropping time was 344 minutes), and the temperature was maintained until the alkylene oxide addition reaction was completed to complete the reaction (ripening time). 60 minutes).
The obtained reaction product (A-10) had a weight average molecular weight of 31,700 and a number average molecular weight of 13,700.

Production Examples 1 to 10 are summarized in Table 1.

<Polycarboxylic acid copolymer>
Production Example 11
In a glass reactor equipped with a thermometer, a stirrer, a dropping device, a nitrogen introduction tube and a reflux cooling device, 285.3 g of ion-exchanged water and 280.7 g of the reaction product (A-3) obtained in Production Example 3 Then, 3.9 g of acrylic acid and 0.72 g of acetic acid were charged, the inside of the reactor was replaced with nitrogen under stirring, and the mixture was heated to 80 ° C. in a nitrogen atmosphere. While maintaining the inside of the reaction vessel at 80 ° C., an aqueous solution in which 14.7 g of acrylic acid was dissolved in 116.0 g of ion-exchanged water was added for 3 hours, and 0.48 g of 3-mercaptopropionic acid was added to 149.5 g of ion-exchanged water. The dissolved aqueous solution was dropped in 3 hours, and an aqueous solution in which 3.5 g of ammonium persulfate was dissolved in 145.3 g of ion-exchanged water was dropped over 3.5 hours. Then, after maintaining the temperature at 80 ° C. for 1 hour, the polymerization reaction was completed. Thereafter, the acidic reaction solution was adjusted to pH 6.0 with an aqueous sodium hydroxide solution and ion-exchanged water at a temperature equal to or lower than the polymerization reaction temperature, and the weight average molecular weight was 110000 and Mw / Mn was 3.65. An aqueous solution of the polymer (1) was obtained.

Production Example 12
In a glass reactor equipped with a thermometer, a stirrer, a dropping device, a nitrogen introduction tube and a reflux cooling device, 286.2 g of ion-exchanged water and 281.9 g of the reaction product (A-6) obtained in Production Example 6 Then, 3.6 g of acrylic acid and 0.75 g of acetic acid were charged, the inside of the reaction apparatus was purged with nitrogen under stirring, and heated to 80 ° C. in a nitrogen atmosphere. While maintaining the inside of the reaction vessel at 80 ° C., an aqueous solution in which 13.7 g of acrylic acid was dissolved in 124.0 g of ion-exchanged water was added in 3 hours, and 0.91 g of 3-mercaptopropionic acid was added to 149.1 g of ion-exchanged water. The dissolved aqueous solution was dropped in 3 hours, and an aqueous solution in which 3.3 g of ammonium persulfate was dissolved in 136.5 g of ion-exchanged water was dropped over 3.5 hours. Then, after maintaining the temperature at 80 ° C. for 1 hour, the polymerization reaction was completed. Thereafter, the acidic reaction solution was adjusted to pH 6.0 using an aqueous sodium hydroxide solution and ion-exchanged water at a temperature not higher than the polymerization reaction temperature, and the weight average molecular weight was 90000 and Mw / Mn was 3.19. An aqueous solution of the polymer (2) was obtained.

Production Example 13
In a glass reactor equipped with a thermometer, a stirrer, a dropping device, a nitrogen introducing tube and a reflux cooling device, 288.8 g of ion-exchanged water and 284.3 g of the reaction product (A-8) obtained in Production Example 8 Then, 3.1 g of acrylic acid and 1.42 g of acetic acid were charged, and the inside of the reaction apparatus was purged with nitrogen under stirring, and heated to 80 ° C. in a nitrogen atmosphere. While maintaining the inside of the reaction vessel at 80 ° C., an aqueous solution in which 11.2 g of acrylic acid was dissolved in 119.5 g of ion exchange water was added in 3 hours, and 0.61 g of 3-mercaptopropionic acid was added to 149.4 g of ion exchange water. The dissolved aqueous solution was dropped in 3 hours, and an aqueous solution in which 2.8 g of ammonium persulfate was dissolved in 138.8 g of ion-exchanged water was dropped over 3.5 hours. Then, after maintaining the temperature at 80 ° C. for 1 hour, the polymerization reaction was completed. Thereafter, the acidic reaction solution was adjusted to pH 6.0 with an aqueous sodium hydroxide solution and ion-exchanged water at a temperature lower than the polymerization reaction temperature, and the weight average molecular weight was 125000 and Mw / Mn was 3.87. An aqueous solution of the polymer (3) was obtained.

Production Example 14
In a glass reactor equipped with a thermometer, a stirrer, a dropping device, a nitrogen introduction tube and a reflux cooling device, 284.4 g of ion-exchanged water and 278.7 g of the reaction product (A-8) obtained in Production Example 8 Then, 4.3 g of acrylic acid and 1.40 g of acetic acid were charged, the inside of the reaction apparatus was purged with nitrogen under stirring, and heated to 80 ° C. in a nitrogen atmosphere. While maintaining the inside of the reaction vessel at 80 ° C., an aqueous solution in which 15.6 g of acrylic acid was dissolved in 117.5 g of ion-exchanged water was added in 3 hours, and 0.86 g of 3-mercaptopropionic acid was added to 149.1 g of ion-exchanged water. The dissolved aqueous solution was dropped in 3 hours, and an aqueous solution in which 3.7 g of ammonium persulfate was dissolved in 144.4 g of ion-exchanged water was dropped over 3.5 hours. Then, after maintaining the temperature at 80 ° C. for 1 hour, the polymerization reaction was completed. Thereafter, the acidic reaction solution was adjusted to pH 6.0 using an aqueous sodium hydroxide solution and ion-exchanged water at a temperature equal to or lower than the polymerization reaction temperature, and the weight average molecular weight was 174000 and Mw / Mn was 4.76. An aqueous solution of the polymer (4) was obtained.

Production Example 15
In a glass reactor equipped with a thermometer, a stirrer, a dropping device, a nitrogen inlet tube and a reflux cooling device, 166.2 g of ion-exchanged water, 383.5 g of the reaction product (A-10) obtained in Production Example 10 Then, 3.3 g of acrylic acid and 1.09 g of acetic acid were charged, the inside of the reactor was purged with nitrogen under stirring, and the mixture was heated to 80 ° C. in a nitrogen atmosphere. While maintaining the inside of the reaction vessel at 80 ° C., an aqueous solution in which 12.1 g of acrylic acid was dissolved in 134.9 g of ion-exchanged water was added in 3 hours, and 0.67 g of 3-mercaptopropionic acid was added to 149.3 g of ion-exchanged water. The dissolved aqueous solution was dropped in 3 hours, and an aqueous solution in which 2.9 g of ammonium persulfate was dissolved in 146.0 g of ion-exchanged water was dropped over 3.5 hours. Then, after maintaining the temperature at 80 ° C. for 1 hour, the polymerization reaction was completed. Thereafter, the acidic reaction solution is adjusted to pH 6.0 with an aqueous sodium hydroxide solution and ion-exchanged water at a temperature not higher than the polymerization reaction temperature, and the weight average molecular weight is 105000 and Mw / Mn is 3.32. An aqueous solution of the polymer (5) was obtained.

Production Example 16
In a glass reactor equipped with a thermometer, a stirrer, a dropping device, a nitrogen inlet tube and a reflux cooling device, 166.2 g of ion-exchanged water, 383.5 g of the reaction product (A-10) obtained in Production Example 10 Then, 3.3 g of acrylic acid and 1.09 g of acetic acid were charged, the inside of the reactor was purged with nitrogen under stirring, and the mixture was heated to 80 ° C. in a nitrogen atmosphere. While maintaining the inside of the reaction vessel at 80 ° C., an aqueous solution in which 12.1 g of acrylic acid was dissolved in 134.6 g of ion-exchanged water was added for 3 hours, and 1.34 g of 3-mercaptopropionic acid was added to 148.7 g of ion-exchanged water. The dissolved aqueous solution was dropped in 3 hours, and an aqueous solution in which 2.9 g of ammonium persulfate was dissolved in 146.0 g of ion-exchanged water was dropped over 3.5 hours. Then, after maintaining the temperature at 80 ° C. for 1 hour, the polymerization reaction was completed. Thereafter, the acidic reaction solution was adjusted to pH 6.0 using an aqueous sodium hydroxide solution and ion-exchanged water at a temperature not higher than the polymerization reaction temperature, and the weight average molecular weight was 82000 and Mw / Mn was 2.97. An aqueous solution of the polymer (6) was obtained.

Production Example 17
In a glass reactor equipped with a thermometer, a stirrer, a dropping device, a nitrogen inlet tube and a reflux cooling device, 163.3 g of ion-exchanged water and 374.9 g of the reaction product (A-10) obtained in Production Example 10 Then, 5.0 g of acrylic acid and 1.07 g of acetic acid were charged, the inside of the reaction apparatus was purged with nitrogen under stirring, and heated to 80 ° C. in a nitrogen atmosphere. While maintaining the inside of the reaction vessel at 80 ° C., an aqueous solution in which 19.0 g of acrylic acid was dissolved in 137.6 g of ion-exchanged water was added in 3 hours, and 1.97 g of 3-mercaptopropionic acid was added to 148.0 g of ion-exchanged water. The dissolved aqueous solution was dropped in 3 hours, and an aqueous solution in which 4.2 g of ammonium persulfate was dissolved in 144.9 g of ion-exchanged water was dropped over 3.5 hours. Then, after maintaining the temperature at 80 ° C. for 1 hour, the polymerization reaction was completed. Thereafter, the acidic reaction solution is adjusted to pH 6.0 using an aqueous sodium hydroxide solution and ion-exchanged water at a temperature equal to or lower than the polymerization reaction temperature, and the weight average molecular weight is 90000 and Mw / Mn is 3.37. An aqueous solution of the polymer (7) was obtained.

Production Example 18
In a glass reactor equipped with a thermometer, a stirrer, a dropping device, a nitrogen inlet tube and a reflux cooling device, 167.7 g of ion-exchanged water and 387.9 g of the reaction product (A-10) obtained in Production Example 10 Then, 2.4 g of acrylic acid and 1.10 g of acetic acid were charged, the inside of the reactor was purged with nitrogen under stirring, and the mixture was heated to 80 ° C. in a nitrogen atmosphere. While maintaining the inside of the reaction vessel at 80 ° C., an aqueous solution in which 8.6 g of acrylic acid was dissolved in 136.5 g of ion-exchanged water was added in 3 hours, and 0.20 g of 3-mercaptopropionic acid was added to 149.8 g of ion-exchanged water. The dissolved aqueous solution was dropped in 3 hours, and an aqueous solution in which 2.2 g of ammonium persulfate was dissolved in 143.6 g of ion-exchanged water was dropped over 3.5 hours. Then, after maintaining the temperature at 80 ° C. for 1 hour, the polymerization reaction was completed. Thereafter, the acidic reaction solution was adjusted to pH 6.0 with an aqueous sodium hydroxide solution and ion-exchanged water at a temperature not higher than the polymerization reaction temperature, and the weight average molecular weight was 100,000 and Mw / Mn was 3.17. An aqueous solution of the polymer (8) was obtained.

Comparative production example 1
In a glass reaction apparatus equipped with a thermometer, a stirrer, a dropping apparatus, a nitrogen introduction tube and a reflux cooling apparatus, 286.8 g of ion-exchanged water, 283.1 g of an ethylene oxide 200 mol adduct of methallyl alcohol (also referred to as MAL200), Acrylic acid (3.4 g) and acetic acid (0.21 g) were charged, the inside of the reactor was purged with nitrogen under stirring, and the mixture was heated to 80 ° C. in a nitrogen atmosphere. While maintaining the inside of the reaction vessel at 80 ° C., an aqueous solution in which 13.3 g of acrylic acid was dissolved in 123.3 g of ion-exchanged water was added in 3 hours, and 1.55 g of 3-mercaptopropionic acid was added to 148.4 g of ion-exchanged water. The dissolved aqueous solution was dropped in 3 hours, and an aqueous solution in which 3.0 g of ammonium persulfate was dissolved in 137.0 g of ion-exchanged water was added dropwise over 3.5 hours. Then, after maintaining the temperature at 80 ° C. for 1 hour, the polymerization reaction was completed. Thereafter, the acidic reaction solution was adjusted to a pH of 6.0 or less using an aqueous sodium hydroxide solution and ion-exchanged water at a temperature equal to or lower than the polymerization reaction temperature, and the weight average molecular weight was 82000 and Mw / Mn was 2.18. An aqueous solution of polymer (9) was obtained.

Comparative production example 2
In a glass reactor equipped with a thermometer, a stirrer, a dropping device, a nitrogen inlet tube and a reflux cooling device, 282.6 g of ion-exchanged water, 278.0 g of an adduct of 150 mol of methallyl alcohol in ethylene oxide (also referred to as MAL150), 4.4 g of acrylic acid and 0.21 g of acetic acid were charged, the inside of the reaction apparatus was purged with nitrogen under stirring, and heated to 80 ° C. in a nitrogen atmosphere. While maintaining the inside of the reaction vessel at 80 ° C., an aqueous solution in which 17.4 g of acrylic acid was dissolved in 119.0 g of ion-exchanged water was added for 3 hours, and 1.84 g of 3-mercaptopropionic acid was added to 148.2 g of ion-exchanged water. The dissolved aqueous solution was dropped in 3 hours, and an aqueous solution in which 4.0 g of ammonium persulfate was dissolved in 144.5 g of ion-exchanged water was dropped over 3.5 hours. Then, after maintaining the temperature at 80 ° C. for 1 hour, the polymerization reaction was completed. Thereafter, the acidic reaction solution was adjusted to pH 6.0 with an aqueous sodium hydroxide solution and ion-exchanged water at a temperature not higher than the polymerization reaction temperature, and the weight average molecular weight was 87000 and Mw / Mn was 2.47. An aqueous solution of the polymer (10) was obtained.

Comparative production example 3
In a glass reactor equipped with a thermometer, a stirrer, a dripping device, a nitrogen introduction tube and a reflux cooling device, 278.4 g of ion-exchanged water, an ethylene oxide 50 mol adduct of 3-methyl-3-buten-1-ol ( (Also referred to as IPN50) 272.8 g, 5.4 g of acrylic acid, and 0.21 g of acetic acid were charged, the inside of the reactor was purged with nitrogen under stirring, and the mixture was heated to 80 ° C. in a nitrogen atmosphere. While maintaining the inside of the reaction vessel at 80 ° C., an aqueous solution in which 21.6 g of acrylic acid was dissolved in 129.8 g of ion-exchanged water was added for 3 hours, and 1.27 g of 3-mercaptopropionic acid was added to 148.7 g of ion-exchanged water. An aqueous solution in which 5.7 g of ammonium persulfate was dissolved in 136.1 g of ion-exchanged water was dropped over 3 hours in 3 hours. Then, after maintaining the temperature at 80 ° C. for 1 hour, the polymerization reaction was completed. Thereafter, the acidic reaction solution was adjusted to pH 6.0 with an aqueous sodium hydroxide solution and ion-exchanged water at a temperature not higher than the polymerization reaction temperature, and the weight average molecular weight was 103,000 and Mw / Mn was 4.69. An aqueous solution of the polymer (11) was obtained.

Production Examples 11 to 18 and Comparative Production Examples 1 to 3 are summarized in Table 2.

<Examples 1-8, Comparative Examples 1-3>
Each of the copolymers (1) to (11) obtained in Production Examples and Comparative Production Examples was mixed in the following composition, and mortar flow value and mortar compressive strength were evaluated as cement dispersants. The results are shown in Table 3.
<Mortar evaluation method>
The mortar test was performed in an environment where the temperature was 20 ° C. ± 1 ° C. and the relative humidity was 60% ± 10%.
The mortar formulation was C / S / W = 600/1350/210 (g). However,
C: Ordinary Portland cement (manufactured by Taiheiyo Cement)
S: Standard sand for cement strength test (Cement Association)
W: As an ion exchange aqueous solution W of a polymer (copolymer) and an antifoaming agent, an addition amount of the polymer aqueous solution shown in Table 3 was weighed and an antifoaming agent MA-404 (manufactured by Pozoris) was used. In the form, 15% by mass was added to the solid content of the polymer, and ion-exchanged water was further added to obtain a predetermined amount, which was sufficiently uniformly dissolved. In Table 3, the addition amount of the polymer is represented by mass% of the polymer solid content with respect to the cement mass.
A stainless beater (stirring blade) was attached to a Hobart mortar mixer (model number N-50; manufactured by Hobart), C and W were added, and kneaded at a first speed for 30 seconds. Further, S was added over 30 seconds while kneading at a first speed. After the completion of S addition, after kneading for 30 seconds in duplicate, the mixer was stopped, the mortar was scraped off for 15 seconds, and then allowed to stand for 75 seconds. The mixture was allowed to stand for 75 seconds and then kneaded at a second speed for 60 seconds to prepare a mortar.

The mortar was transferred from the kneading vessel to a 1 L polyethylene container, stirred 20 times with a spatula, and then immediately packed in a half of a flow cone (described in JIS R5201-1997) placed on a flow table (described in JIS R5201-1997). I struck with a stick with a turn, and stuffed the mortar until the flow cone was filled, and struck with a stick with a turn 15 times. Finally, I made up the shortage and smoothed the surface of the flow cone. Immediately after that, the flow cone is pulled up vertically, and the diameter of the expanded mortar (the diameter of the longest part (major axis) and the diameter of the part forming 90 degrees with respect to the major axis) is measured in two places, and the average value is zero. The flow value was used. Immediately after measuring the zero stroke flow value, 15 falling motions were given in 15 seconds, and the diameter of the expanded mortar (the diameter of the longest part (major axis) and the diameter of the part forming 90 degrees with respect to the major axis) was 2 The points were measured and the average value was taken as the 15-stroke flow value. Table 3 shows the 15-stroke flow value immediately after mortar preparation (initial stage).

<Measurement of compressive strength>
The mortar prepared by the above method is packed in a cylindrical formwork (diameter 5 cm, height 10 cm) placed on a horizontal table to one third of the formwork capacity, and struck 20 times with a stick, then the mold The frame container was vibrated to remove coarse bubbles. Further, the mortar was filled to the full extent of the formwork, struck 20 times with a stick, and then the formwork container was vibrated. In order to prevent drying, the upper surface was covered with a PET film and cured for 12 hours and 24 hours in an environment at room temperature of 20 ° C., and cured for 3 hours and 4 hours in a constant temperature and humidity chamber at 60 ° C. A sample was used.
Using the specimen prepared by the above method, the compressive strength was measured according to the compressive strength measuring method of the concrete test (JIS A1108; 2006). Table 3 shows the measurement results of the compressive strength of the specimen.

Claims (7)

A monomer component containing an unsaturated polyalkylene glycol monomer represented by the following general formula (1) and an unsaturated carboxylic acid monomer represented by the following general formula (4) is polymerized. A polycarboxylic acid copolymer obtained.

(.Y ^wherein, R 1, ^{R 2} and ^{R 3} are the same or different, .A ¹ O represents a hydrogen atom or a methyl group, the same or different and each represents an oxyalkylene group having 2 to 18 carbon atoms ¹ represents a residue of a compound having two or more active groups, Z represents the same or different and represents — (A ² O) _n —R ⁴ , A ² O represents the same or different and represents the number of carbon atoms Represents an oxyalkylene group having 2 to 18. R ⁴ is the same or different and represents a hydrogen atom or a hydrocarbon group having 1 to 30 carbon atoms, n is an average addition of an oxyalkylene group represented by A ² O The number of moles is the same or different and is a number of 2 to 300. p is 0, 1 or 2. q is 0 or 1. t is an oxyalkylene represented by A ¹ O. Represents the average number of moles added of the group, and is a number from 5 to 300. m ¹ is an integer of 2 or more. In other words, the maximum number is determined depending on the number of active groups of the compound having two or more active groups represented by Y ^1. )

(In the formula, R ⁵ , R ⁶ and R ⁷ are the same or different and each represents a hydrogen atom, a methyl group or — (CH ₂ ) _y COOM ^2. Note that when — (CH ₂ ) _y COOM ² is represented, -COOM ¹ or other-(CH ₂ ) _y COOM ² may form an anhydride, in which case M ¹ and M ² of these groups are absent, y is 0, 1 or 2 M ¹ and M ² are the same or different and each represents a hydrogen atom, an alkali metal atom, an alkaline earth metal atom, an ammonium group, an alkylammonium group, or a substituted alkylammonium group. A monomer component containing an unsaturated polyalkylene glycol monomer represented by the following general formula (2) and an unsaturated carboxylic acid monomer represented by the following general formula (4) is polymerized. A polycarboxylic acid copolymer obtained.

(Wherein R ¹ , R ² and R ³ are the same or different and each represents a hydrogen atom or a methyl group. X represents — (A ¹ O) _t —, and A ¹ O represents the same or different. Represents an oxyalkylene group having 2 to 18 carbon atoms, t represents an average addition mole number of the oxyalkylene group represented by A ¹ O, and is a number of 5 to 300. Y ² represents an active group 3 .Z representing the residue of a compound having more than five, identical or ^different, - .p representing the (a _{2 O)} n -R ⁴ is .q is 0, 1 or 2, is 0 or 1 .u is 1 .m ² is an integer of 3 or more, the number of the maximum number is determined depending on the activity groups of the compound having an active group represented by Y ² 3 or more .A ² O are the same or different, .R ⁴ representing an oxyalkylene group having 2 to 18 carbon atoms are the same or different, and a hydrogen atom .N representing a hydrocarbon group having 1 to 30 carbon atoms, represents an average addition mole number of the oxyalkylene group represented by A 2 ^O, identical or different, are a number from 2 to 300.)

(In the formula, R ⁵ , R ⁶ and R ⁷ are the same or different and each represents a hydrogen atom, a methyl group or — (CH ₂ ) _y COOM ^2. Note that when — (CH ₂ ) _y COOM ² is represented, -COOM ¹ or other-(CH ₂ ) _y COOM ² may form an anhydride, in which case M ¹ and M ² of these groups are absent, y is 0, 1 or 2 M ¹ and M ² are the same or different and each represents a hydrogen atom, an alkali metal atom, an alkaline earth metal atom, an ammonium group, an alkylammonium group, or a substituted alkylammonium group. The polycarboxylic acid according to claim 1, wherein Y ¹ in the general formula (1) or Y ² in the general formula (2) represents the following general formula (5). Copolymer.
_{- (C 3 H 6 O 2} ) r - (5)
(In the formula, r represents the average added mole number of the glyceryl group represented by (C ₃ H ₆ O ₂ ) and is a number of 1 to 300. In addition, when Y ² represents the general formula (5) , R is 2 or more The glyceryl groups represented by (C ₃ H ₆ O ₂ ) are the same or different and have the following formula:

It consists of the structure represented by. In addition, the terminal OH group in the said structure couple _| bonds _with- (Z) _m1 in the said General formula (1), _or- (Z) _m2 in the said General formula (2) . ) A monomer component containing an unsaturated polyalkylene glycol monomer represented by the following general formula (3) and an unsaturated carboxylic acid monomer represented by the following general formula (4) is polymerized. A polycarboxylic acid copolymer obtained.

^(Wherein, R 1, ^{R 2} and ^{R 3} are the same or different, .R ⁴ represents a hydrogen atom or a methyl group are the same or different, represent a hydrogen atom or a hydrocarbon group having 1 to 30 carbon atoms A ¹ O is the same or different and represents an oxyalkylene group having 2 to 18 carbon atoms, p is 0, 1 or 2. q is 0 or 1. t is A ¹ O. The average addition mole number of the oxyalkylene group represented is a number of 5 to 300. m ³ is an integer of 2 or more, and represented by Y ³ — (C ₃ H ₆ O ₂ ) _r —. The maximum number is determined depending on the number of active groups of Y ³ represents the following general formula (5).
_{- (C 3 H 6 O 2} ) r - (5)
r _represents an average addition number of moles of glyceryl group represented by _{(C 3 H 6 O 2)} , the number of 1 to 300. The glyceryl groups represented by (C ₃ H ₆ O ₂ ) are the same or different and have the following formula:

It consists of the structure represented by. In addition, the terminal OH group in the said structure couple _| bonds _with- (R _< ⁴ _> ) _m3 in General formula (3) . )

(In the formula, R ⁵ , R ⁶ and R ⁷ are the same or different and each represents a hydrogen atom, a methyl group or — (CH ₂ ) _y COOM ^2. Note that when — (CH ₂ ) _y COOM ² is represented, -COOM ¹ or other-(CH ₂ ) _y COOM ² may form an anhydride, in which case M ¹ and M ² of these groups are absent, y is 0, 1 or 2 M ¹ and M ² are the same or different and each represents a hydrogen atom, an alkali metal atom, an alkaline earth metal atom, an ammonium group, an alkylammonium group, or a substituted alkylammonium group. A dispersant comprising the polycarboxylic acid copolymer according to claim 1. A cement admixture comprising the polycarboxylic acid copolymer according to any one of claims 1 to 4. A cement composition comprising the cement admixture according to claim 6, cement and water.