JP2012116950A - Polyalkylene glycol-based polymer, cement admixture, and cement composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a polyalkylene glycol-based polymer capable of exhibiting the performance such as water reducibility and workability in a cement composition and the like in high levels, and useful for various uses, particularly for usage for a cement admixture; and to provide a cement admixture and a cement composition using the same.SOLUTION: The polymer has a structural unit originated from a vinylic monomer and a polyalkylene glycol chain as a main chain. The polymer has a structure in which a terminal oxygen atom in at least one terminal of the polyalkylene glycol chain is bonded to a main chain terminal of a structural unit originated from the vinylic monomer directly or through an organic residue. The vinylic monomer is a polyalkylene glycol-based polymer containing essentially an unsaturated polyalkylene glycol-based polymer having a polyalkylene glycol chain having essentially a ≥3C oxyalkylene group.

Description

The present invention relates to a polyalkylene glycol polymer, a cement admixture and a cement composition. More specifically, polyalkylene glycol polymers used for various applications such as cement admixtures, adhesives and sealants, softening ingredients, detergent builders, etc. as soft segments, and obtained by using it. The present invention relates to a cement admixture and a cement composition.

A polymer containing a polyalkylene glycol chain (hereinafter, also referred to as a polyalkylene glycol polymer) has properties such as hydrophilicity, hydrophobicity, and steric repulsion by appropriately adjusting the chain length and the constituent alkylene oxide. As a soft segment, it is widely used in various applications such as adhesive and sealant applications, flexibility imparting component applications, and detergent builder applications.
In recent years, the use of cement admixtures added to cement compositions such as cement paste, mortar and concrete has been studied. Such a cement admixture is usually used as a water reducing agent or the like, and exerts the action of improving the strength and durability of the cured product by reducing the cement composition by increasing the fluidity of the cement composition. Used for that purpose. As a water reducing agent, a water reducing agent such as naphthalene was conventionally used, but the polyalkylene glycol chain can act as a dispersing group to disperse cement particles due to its steric repulsion, and therefore contains a polyalkylene glycol chain. The polycarboxylic acid-based water reducing agent has been newly proposed as exhibiting a high water reducing action, and has recently been used as a high-performance AE water reducing agent.

With respect to a polymer containing a conventional polyalkylene glycol chain, for example, both ends obtained by decomposing a thioester group formed after adding a thiocarboxylic acid to a polyether having a double bond at both ends or one end A polyether having a mercapto group at one end (for example, see Patent Document 1) or a compound having a mercapto group as a biodegradable water-soluble polymer used in a detergent builder is introduced into a polyether compound by an ester reaction. A polymer obtained by subjecting a modified polyether compound to block or graft polymerization of a monoethylenically unsaturated monomer component is disclosed (for example, see Patent Document 2). Further, it is disclosed that a novel polymer having a polymer unit comprising a polyalkylene glycol chain and a constituent unit derived from an unsaturated monomer bonded to at least one end of the chain is particularly useful as a cement admixture. (For example, refer to Patent Document 3). Furthermore, it is disclosed that a cement admixture comprising a polycarboxylic acid polymer having a polyalkylene glycol chain having a specific structure improves water-reducing properties of a cement composition or the like (see, for example, Patent Document 4). ).

However, a polymer containing a conventional polyalkylene glycol chain has not yet reached a level where the extremely high performance (dispersibility (water reduction) and workability in a cement composition, etc.) that has recently been demanded can be sufficiently exhibited. Therefore, there has been room for improvement to make the compound useful in more fields by making it suitable for use as a cement admixture.

Japanese Patent Publication No. 7-13141 JP-A-7-109487 JP 2007-119736 A JP-T-2006-525219

The present invention has been made in view of the above-mentioned present situation, and can exhibit performances such as water reduction and workability in cement compositions and the like at a higher level, and is useful for various uses, particularly for cement admixtures. It is an object of the present invention to provide a polyalkylene glycol polymer, a cement admixture and a cement composition using the same.

The present inventor has made various studies on a polymer containing a polyalkylene glycol chain. As a result, the polymer has a structural unit derived from a vinyl monomer and a polyalkylene glycol chain in the main chain. When the terminal oxygen atom at at least one of the chain ends is bonded to the main chain end of the structural unit derived from the vinyl monomer, directly or through an organic residue, It was found that high water reduction performance can be achieved by adding a small amount. In addition, the polymer is bonded to a residue of a compound having 3 or more active hydrogens by 3 or more polyalkylene glycol chains, and the terminal oxygen atom at at least one other end of the polyalkylene glycol chains is directly or When the structure is bonded to the main chain terminal of a structural unit derived from a vinyl monomer via an organic residue, that is, a structure having a multi-branched structure, the water content of the cement composition is reduced more due to its steric repulsion. I found out that it can perform well. Further, in the polymer as described above, the vinyl monomer essentially includes an unsaturated polyalkylene glycol monomer having a polyalkylene glycol chain having an oxyalkylene group having 3 or more carbon atoms as an essential component. The present inventors have found that the workability (handleability, workability) and state of a cement composition using the polymer are improved. The cement admixture obtained by using the polymer of the present invention has been found to be able to exhibit unprecedented performance (such as water reduction and handling properties in cement compositions), and a cement composition comprising the same. It has been found that the product is particularly useful in the field, and the present invention has been achieved.

That is, the present invention is a polymer having a structural unit derived from a vinyl monomer and a polyalkylene glycol chain in the main chain, wherein the polymer is a terminal oxygen at at least one of the terminals of the polyalkylene glycol chain. The atom has a structure bonded to the main chain terminal of the structural unit derived from the vinyl monomer directly or through an organic residue, and the vinyl monomer is an oxyalkylene group having 3 or more carbon atoms. It is a polyalkylene glycol polymer characterized by essentially containing an unsaturated polyalkylene glycol monomer having a polyalkylene glycol chain.
The present invention is also a polymer having a polyalkylene glycol chain and having a multi-branched structure, wherein the polymer has 3 or more polyalkylene glycol chains bonded to the residue of a compound having 3 or more active hydrogens. And a terminal oxygen atom at at least one other terminal of the polyalkylene glycol chain has a structure in which the main chain terminal of the constituent unit derived from the vinyl monomer is bonded directly or through an organic residue, The vinyl-based monomer essentially includes an unsaturated polyalkylene glycol-based monomer having a polyalkylene glycol chain having an oxyalkylene group having 3 or more carbon atoms as an essential component. There is also.
The present invention is also a cement admixture containing the polyalkylene glycol polymer.
The present invention is also a cement composition containing the above cement admixture.
The present invention is described in detail below.

<Polyalkylene glycol polymer>
The polyalkylene glycol polymer of the present invention is a polymer having a vinyl monomer-derived constitutional unit and a polyalkylene glycol chain in its main chain, wherein the terminal is at least one of the terminals of the polyalkylene glycol chain. It has a structure in which an oxygen atom is bonded to the main chain terminal of a structural unit derived from a vinyl monomer directly or through an organic residue, and the vinyl monomer has an oxyalkylene group having 3 or more carbon atoms. It essentially contains an unsaturated polyalkylene glycol monomer having a polyalkylene glycol chain.
Details of the structure of the polyalkylene glycol polymer in the present invention will be described later.
In the following, it has a structure in which the terminal oxygen atom at at least one of the terminals of the polyalkylene glycol chain of the present invention is bonded to the main chain terminal of the structural unit derived from the vinyl monomer directly or via an organic residue. The vinyl monomer is a polyalkylene glycol polymer that essentially contains an unsaturated polyalkylene glycol monomer having a polyalkylene glycol chain having an oxyalkylene group having 3 or more carbon atoms as an essential component. “Polymer (i)” and a polymer that forms a structural unit derived from a vinyl monomer to which the polyalkylene glycol chain is bonded directly or via an organic residue are also referred to as “polymer (ii)”.

In the polyalkylene glycol polymer (i), the vinyl monomer for forming the polymer (ii) is unsaturated having a polyalkylene glycol chain having an oxyalkylene group having 3 or more carbon atoms as an essential component. A polyalkylene glycol monomer (hereinafter also referred to as “monomer (A)”) is essential. That is, the polyalkylene glycol polymer (i) of the present invention is a structural unit derived from an unsaturated polyalkylene glycol monomer (A) having a polyalkylene glycol chain essentially comprising an oxyalkylene group having 3 or more carbon atoms. Is included.
The monomer (A) is a monomer having at least one polymerizable double bond and one polyalkylene glycol chain having an oxyalkylene group having 3 or more carbon atoms in the molecule. Hereinafter, the polyalkylene glycol chain of the monomer (A) is also referred to as polyalkylene glycol chain (A). When a plurality of the polyalkylene glycol chains (A) are present in one molecule of the monomer (A), these may be the same or different.

The oxyalkylene group having 3 or more carbon atoms, which is essential for the polyalkylene glycol chain (A), has higher hydrophobicity than an oxyethylene group having 2 carbon atoms, and such a hydrophobic group is introduced. When the above polyalkylene glycol polymer is used as a cement admixture (dispersant), which is one of the preferred applications, the polyalkylene glycol chains (A) exhibit a light hydrophobic interaction in an aqueous solution. As a result, the viscosity of the cement composition is adjusted, so that workability and the state of the composition are improved.
When an oxyalkylene group having 3 or more carbon atoms is introduced, the amount introduced is 5 mol% or more with respect to 100 mol% of all oxyalkylene groups (alkylene glycol units) constituting the polyalkylene glycol chain (A). It is preferable. Thereby, workability | operativity and states of a cement composition etc. can fully be improved. As described above, the unsaturated polyalkylene glycol monomer (A) having a polyalkylene glycol chain essentially comprising an oxyalkylene group having 3 or more carbon atoms is a polyalkylene glycol chain possessed by the monomer (A). It is one of the preferred embodiments of the present invention that the oxyalkylene group having 3 or more carbon atoms is contained in an amount of 5 mol% or more with respect to 100 mol% of all oxyalkylene groups constituting the above. The introduction amount is more preferably 8 mol% or more, and still more preferably 10 mol% or more.
In order to maintain sufficient water solubility of the polyalkylene glycol polymer, the introduction amount is preferably 50 mol% or less. More preferably, it is 25 mol% or less, More preferably, it is 15 mol% or less. Moreover, it is preferable that it is 1 mol% or more for workability | operativity improvement.
As the oxyalkylene group having 3 or more carbon atoms, a propylene oxide group and a butylene oxide group are preferable from the viewpoint of ease of production, and among them, a propylene oxide group is more preferable.

The polyalkylene glycol chain (A) is also preferably composed mainly of an oxyethylene group having 2 carbon atoms (ethylene oxide). Thereby, the obtained polymer (ii) becomes sufficiently hydrophilic, and sufficient water solubility and cement particle dispersion performance are imparted to the polyalkylene glycol polymer of the present invention.
The “main body” as used herein means that when the polyalkylene glycol chain (A) is composed of two or more types of alkylene oxides, it accounts for the majority of the total number of alkylene oxides present. When “dominating” is expressed in terms of mol% of ethylene oxide in 100 mol% of all alkylene oxides, 50 to 100 mol% is preferable. Thereby, the polyalkylene glycol chain (A) has higher hydrophilicity. 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.

When the polyalkylene glycol chain (A) is composed of an oxyethylene group having 2 carbon atoms and an oxyalkylene group having 3 or more carbon atoms, these sequences may be random or block. Although the block arrangement is better, the hydrophilicity of the hydrophilic block is more strongly expressed and the hydrophobicity of the hydrophobic block is more strongly expressed compared to the random arrangement. This is preferable because dispersibility and workability are further improved. In particular, it is preferably arranged in an ABA block shape as (oxygen group having 2 carbon atoms)-(oxyalkylene group having 3 or more carbon atoms)-(oxyethylene group having 2 carbon atoms).
The polyalkylene glycol chain (A) is preferably substantially linear.
Specific examples of the monomer (A) will be described later.

Next, the structure of the polyalkylene glycol polymer (polymer (i)) in the present invention will be described.
The polyalkylene glycol polymer in the present invention has a polyalkylene glycol chain and a structural unit derived from a vinyl monomer, and a terminal oxygen atom at at least one terminal of the polyalkylene glycol chain (PAG) is directly Alternatively, it has a structure bonded to the main chain terminal of a structural unit (BL) derived from a vinyl monomer through an organic residue, and the vinyl monomer has an oxyalkylene group having 3 or more carbon atoms as an essential component. And an unsaturated polyalkylene glycol monomer (A) having a polyalkylene glycol chain to be contained. The polyalkylene glycol polymer has a polyalkylene glycol chain (PAG) and a structural unit (BL) derived from a vinyl monomer bonded to the polyalkylene glycol chain directly or through an organic residue. As long as it has other structural parts.

When the direct bond between the polyalkylene glycol chain (PAG) and the vinyl monomer-derived structural unit (BL) or the organic residue is Y, the polyalkylene glycol polymer in the present invention has the structure. A polyalkylene glycol chain (PAG), a structural unit derived from a vinyl monomer (BL), and one composed of three structural sites of Y (hereinafter also referred to as polymer (i-1)), and And those having other structural sites other than hydrogen atoms (hereinafter also referred to as polymer (i-2)).
Examples of the polymer (i-1) composed of a polyalkylene glycol chain (PAG), a structural unit derived from a vinyl monomer (BL), and three structural sites of Y include the following structures: There are things.

The following general formula (a):
(BL) -Y- (PAG) -Y- (BL) (a)
As shown by the above, the polymer (ii) is bonded to both ends of the polyalkylene glycol chain directly or via an organic residue,
The following general formula (b):
(PAG) -Y- (BL) (b)
As shown by the above, the polymer (ii) is bonded to one end of the polyalkylene glycol chain directly or through an organic residue,
The following general formula (c):
(PAG) -Y- (BL) -Y- (PAG) (c)
As represented by the following, a form in which a polyalkylene glycol chain is bonded to both ends of the polymer (ii) directly or via an organic residue,
The following general formula (d):
-[(PAG) -Y- (BL)]-(d)
The form etc. comprised by the repetition of the repeating unit represented by these. In these polymers (a) to (d), when the polyalkylene glycol chain (PAG) is located at the end of the polymer structure, the polyalkylene glycol chain (PAG) has a hydrogen atom at the end. It will be. That is, the terminal structure of the polyalkylene glycol chain (PAG) is a hydroxyl group.

Hereinafter, the polyalkylene glycol chain represented by “PAG” in the above general formulas (a) to (d) is also referred to as “polyalkylene glycol chain (I)”, and is a vinyl monomer represented by “BL”. The polyalkylene glycol chain of the unsaturated polyalkylene glycol-based monomer contained in the vinyl-based monomer in the derived structural site is also referred to as “polyalkylene glycol chain (II)”. The polyalkylene glycol chain (A) described above corresponds to the polyalkylene glycol chain (II). The polyalkylene glycol chains (I) and (II) are preferably substantially linear.

The polyalkylene glycol chain (I) may be any one composed of an alkylene oxide having 2 or more carbon atoms (polyalkylene oxide), and the alkylene oxide is preferably an alkylene oxide having 2 to 18 carbon atoms. is there. More preferably, it is an alkylene oxide having 2 to 8 carbon atoms, such as ethylene oxide, propylene oxide, butylene oxide, isobutylene oxide, 1-butene oxide, 2-butene oxide, trimethylethylene oxide, tetramethylene oxide, tetramethylethylene oxide, butadiene. Examples include monooxide and octylene oxide. 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 (I) is preferably selected as appropriate according to the use required for the polyalkylene glycol polymer (i) of the present invention. When used for production, it is preferable that a relatively short chain alkylene oxide (oxyalkylene group) having about 2 to 8 carbon atoms is mainly used from the viewpoint of affinity with cement particles. 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 (I) is composed of two or more types of alkylene oxides, it accounts for the majority of the total number of alkylene oxides present. When “dominating” is expressed in terms of mol% of ethylene oxide in 100 mol% of all alkylene oxides, 50 to 100 mol% is preferable. Thereby, the polymer (i) has higher hydrophilicity. 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 polyalkylene glycol chain (I) may also contain an oxyalkylene group having 3 or more carbon atoms with higher hydrophobicity as a part thereof. When such a hydrophobic group is introduced, when used as a cement admixture (dispersant), the viscosity of the cement composition is adjusted by showing a light hydrophobic interaction between polyalkylene glycol chains in an aqueous solution. This is because workability may be improved. When introducing an oxyalkylene group having 3 or more carbon atoms, the amount introduced is, for example, to maintain sufficient water solubility with respect to 100 mol% of all oxyalkylene groups (alkylene glycol units) constituting the polyalkylene glycol chain. Is preferably 50 mol% or less. More preferably, it is 25 mol% or less, More preferably, it is 10 mol% or less. Moreover, it is preferable that it is 1 mol% or more for workability | operativity improvement. More preferably, it is 2.5 mol% or more, More preferably, it is 5 mol% or more.
As the oxyalkylene group having 3 or more carbon atoms, a propylene oxide group and a butylene oxide group are preferable from the viewpoint of ease of production, and among them, a propylene oxide group is more preferable.
In addition, depending on the use requested | required of the said polymer (i), the aspect which does not contain C3 or more alkylene oxide may be preferable.

When the polyalkylene glycol chain (I) is composed of an oxyethylene group having 2 carbon atoms and an oxyalkylene group having 3 or more carbon atoms, these sequences may be random or block. Although the block arrangement is better, the hydrophilicity of the hydrophilic block is more strongly expressed and the hydrophobicity of the hydrophobic block is more strongly expressed compared to the random arrangement. This is preferable because dispersibility and workability are further improved. In particular, it is preferably arranged in an ABA block shape as (oxygen group having 2 carbon atoms)-(oxyalkylene group having 3 or more carbon atoms)-(oxyethylene group having 2 carbon atoms).

Here, the polyalkylene glycol chain (I) represented by “PAG” and the structural unit derived from the vinyl monomer represented by “BL” may be hydrolyzed depending on the structure represented by “Y”. May be cut off. When the hydrolysis resistance needs to be improved, it is preferable to introduce an oxyalkylene group having 3 or more carbon atoms at the terminal of the polyalkylene glycol chain (I).
Examples of the oxyalkylene group having 3 or more carbon atoms include an oxypropylene group, an oxybutylene group, an oxystyrene group, and an alkyl glycidyl ether residue. Of these, an oxypropylene group and an oxybutylene group are preferable because of ease of production.
The introduction amount of the oxyalkylene group having 3 or more carbon atoms depends on the degree of hydrolysis resistance required, but the introduction amount is 50 mol% or more with respect to both ends of the polyalkylene glycol chain (I). Is preferable. More preferably, it is 100 mol% or more, More preferably, it is 150 mol% or more, Especially preferably, it is 200 mol% or more.

In order to improve hydrolysis resistance, the end of the polyalkylene glycol chain (I) is preferably a secondary alcohol residue. In order to introduce a secondary alcohol group to the terminal of the polyalkylene glycol chain (I), a method generally used may be used. For example, the polyalkylene glycol used as a raw material for the polyalkylene glycol chain (I) may have 3 carbon atoms. What is necessary is just to add the above alkylene oxide. In this addition reaction, at least one compound selected from the group consisting of alkali metals, alkaline earth metals and oxides or hydroxides thereof is used as a catalyst in order to increase the introduction rate of secondary alcohol groups. Is preferably used. More preferred are sodium hydroxide, potassium hydroxide, magnesium hydroxide and calcium hydroxide, and most preferred are sodium hydroxide and potassium hydroxide.
The reaction temperature during the addition reaction is preferably 50 to 200 ° C. in order to increase the introduction rate of secondary alcohol groups. More preferably, it is 70-170 degreeC, More preferably, it is 90-150 degreeC, Most preferably, it is 100-130 degreeC.

The average number of repeating alkylene oxides in the polyalkylene glycol chain (I) (average added mole number of oxyalkylene groups) is preferably 1 to 1000. By setting the number to 1 or more, the polymer (i) can sufficiently exhibit the performance based on the polyalkylene glycol chain. When n exceeds 1000, the polymer (i) There is a possibility that the viscosity of the raw material compound used for producing the product may not be suitable from the viewpoint of workability, for example, the reactivity may not be sufficient. The lower limit value of the average number of repetitions is more preferably 7, more preferably 10, and the upper limit value is more preferably 800, still more preferably 600.
The average number of repeating alkylene oxides (average number of moles of oxyalkylene group added) is the average number of moles of alkylene oxide added in 1 mole of the polyalkylene glycol chain of the polymer (i). Means.

The structural site represented by Y is a direct bond or an organic residue, but the bond between the polyalkylene glycol chain (PAG) and the structural unit (BL) derived from the vinyl monomer can be facilitated. And preferably an organic residue. The organic residue is preferably a group having a molecular weight of 1000 or less. If it exceeds 1000, the introduction of the group becomes difficult and the economic efficiency may be impaired. More preferably, it is 500 or less, More preferably, it is 300 or less.

The organic residue is also preferably one containing a sulfur atom, specifically, for example, —S—Y ² —COO—, —S—Y ² —CO—, —S—Y ² —. CO—NH—, —S—Y ² —CO—NH—CH ₂ —CH ₂ —, —S—Y ² —, —S—Y ² —O—, —S—Y ² —N—, —S— Y ² —S— or the like is preferable. Here, Y ² is a divalent organic residue, preferably a linear, branched or cyclic alkylene group having 1 to 18 carbon atoms or an aromatic group (phenyl group) having 6 to 11 carbon atoms. Alkylphenyl group, pyridinyl group, thiophene, pyrrole, furan, thiazole, etc.), for example, hydroxyl group, amino group, acetylamino group, cyano group, carbonyl group, carboxyl group, halogen group, sulfonyl group, nitro group , A group which may be partially substituted with a substituent such as a formyl group.
Thus, when the said organic residue has a sulfur atom, it is suitable for the main chain terminal of the said polymer (ii) to couple | bond through this sulfur atom. In such a form, as will be described later, at the time of production, monomers are successively added via sulfur atoms due to the reactivity of sulfur atoms to form polymer (ii) sites. Therefore, it is advantageous for manufacturing.

Among the organic residues containing the sulfur atom, those containing a carbonyl group (—C (O) —) or an amide group (—N (H) —C (O) —) are suitable, and thus the sulfur A form in which the organic residue containing an atom contains a carbonyl group or an amide group is also one of the preferred forms of the present invention. Such a form is useful for industrial production because it is easy to manufacture and can be manufactured at low cost.
In this case, the carbon atom contained in the carbonyl group (including the —CO group in the amide group) is adjacent to the terminal oxygen atom of the polyalkylene glycol chain at the bonding site between the organic residue and the polyalkylene glycol chain. It is preferable to do. That is, the polymer (i) is preferably one in which a polyalkylene glycol chain and Y ² are bonded through an ester bond or an amide bond.

The polymer (ii) that forms the structural unit (BL) derived from the vinyl monomer may be one kind of polymer or a mixture of two or more kinds of polymers. The vinyl monomer forming it essentially contains the unsaturated polyalkylene glycol monomer (A) having a polyalkylene glycol chain essentially comprising an oxyalkylene group having 3 or more carbon atoms as described above. That is, the polymer (ii) includes a structural unit derived from the monomer (A). The structural unit derived from the monomer (A) is a structure in which a polymerizable double bond of the monomer (A) is opened by a polymerization reaction (a double bond (C = C) is a single bond ( -C-C-).
The monomer (A) is particularly limited as long as it has at least one polymerizable double bond and one polyalkylene glycol chain having an oxyalkylene group having 3 or more carbon atoms in the molecule. For example, the following formula (1-1);

(.AO ^wherein, R 4, ^{R 5} and ^{R 6} are the same or different, .R ⁷ represents a hydrogen atom or a methyl group, represents a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms are the same Or, differently, it represents one or two or more oxyalkylene groups having 2 to 18 carbon atoms, and an oxyalkylene group having 3 to 18 carbon atoms is essential. When it exists above, the said group may be introduce | transduced in the block form, and may be introduce | transduced in random form, y is an integer of 0-2, z is 0 or 1. r is. Represents the average number of moles added of the oxyalkylene group and is a number from 1 to 300.).

In the general formula (1-1), among the terminal group represented by ^{R 7,} examples of the hydrocarbon group having 1 to 20 carbon atoms, aliphatic alkyl group having 1 to 20 carbon atoms, 3 to 20 carbon atoms An alicyclic alkyl group, a C2-C20 alkenyl group, a C2-C20 alkynyl group, a C6-C20 aryl group, etc. are mentioned.
The terminal group represented by R ⁷ is preferably a hydrophilic group from the viewpoint of dispersibility of cement particles when used for cement admixture, specifically, a hydrogen atom or carbon. The hydrocarbon group of number 1-8 is preferable. A hydrogen atom or a hydrocarbon group having 1 to 6 carbon atoms is more preferable, a hydrogen atom or a hydrocarbon group having 1 to 3 carbon atoms is still more preferable, and a hydrogen atom or a methyl group is particularly preferable.

In the general formula (1-1), the oxyalkylene group represented by AO is as described above.
The above r is a number from 1 to 300, but if it exceeds 300, there is a risk that production problems may occur, and when used as a cement admixture, the viscosity of the cement composition becomes high and workability is improved. May not be enough. From the viewpoint of production, r is suitably 300 or less, preferably 200 or less, more preferably 150 or less, still more preferably 100 or less, particularly preferably 75 or less, and most preferably 50 or less. Further, from the viewpoint of strongly dispersing cement particles, r is preferably 4 or more. More preferably, it is 6 or more, More preferably, it is 10 or more, Most preferably, it is 25 or more.

The monomer (A) is more preferably the following general formula (1-2);

^(Wherein, R 4, ^{R 5} and ^{R 6} are the same or different, .R ⁷ represents a hydrogen atom or a methyl group, the .R ^a represents a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, The same or different, and represents an alkylene group having 3 to 18 carbon atoms, y is an integer of 0 to 2. z is 0 or 1. s and t are the average number of moles of oxyethylene group added. Each represents a number of 1 to 200. u represents an average number of added moles of the oxyalkylene group and is a number of 1 to 50. s + t + u is a compound represented by a number of 3 to 200).
In the general formula (1-2), R ⁴ , R ⁵ , R ⁶ , R ⁷ , y and z are the same as those in the general formula (1-1).
In the compound represented by the general formula (1-2), among the compounds represented by the general formula (1-1), an oxyethylene group and an oxyalkylene group having 3 or more carbon atoms are ABA. It has polyalkylene glycol chains arranged in a block form.

Specific examples of the unsaturated polyalkylene glycol monomer represented by the general formula (1-1) include an unsaturated alcohol polyalkylene glycol adduct and a polyalkylene glycol ester monomer.
The unsaturated alcohol polyalkylene glycol adduct may be a compound having a structure in which a polyalkylene glycol chain having an oxyalkylene group having 3 or more carbon atoms as an essential component is added to an alcohol having an unsaturated group.
The polyalkylene glycol ester monomer may be a monomer having a structure in which an unsaturated group and a polyalkylene glycol chain essentially comprising an oxyalkylene group having 3 or more carbon atoms are bonded via an ester bond. An unsaturated carboxylic acid polyalkylene glycol ester-based compound is preferable, and (alkoxy) polyalkylene glycol mono (meth) acrylate is particularly preferable.

Examples of the unsaturated alcohol polyalkylene glycol adduct include vinyl alcohol alkylene oxide adduct, (meth) allyl alcohol alkylene oxide adduct, 3-buten-1-ol alkylene oxide adduct, 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 -Butene-1-ol alkylene oxide adducts and 2-methyl-3-buten-1-ol alkylene oxide adducts are preferred.

Specific examples of the unsaturated alcohol polyalkylene glycol adduct include polyethylene polypropylene glycol mono (3-methyl-3-butenyl) ether.

Examples of the (alkoxy) polyalkylene glycol mono (meth) acrylate include methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, 1-pentanol, 2-pentanol, and 3-pen. C1-C30 aliphatic alcohols such as butanol, 1-hexanol, 2-hexanol, 3-hexanol, octanol, 2-ethyl-1-hexanol, nonyl alcohol, lauryl alcohol, cetyl alcohol, stearyl alcohol, cyclohexanol C3-C30 unsaturated alcohols such as C3-C30 alicyclic alcohols such as (meth) allyl alcohol, 3-buten-1-ol, 3-methyl-3-buten-1-ol Oxyalkylene with 3 or more carbon atoms Alkoxy polyalkylene glycols having 1 to 300 moles of an oxyalkylene group having 2 to 18 carbon atoms as an essential group, particularly an alkoxy polyalkylene mainly composed of ethylene oxide and an oxyalkylene group having 3 or more carbon atoms as an essential component Esterified products of glycols and (meth) acrylic acid are preferred.

As the esterified product, the following (alkoxy) polyethylene glycol (poly) (C3-C4 alkylene glycol) (meth) acrylic acid esters and the like are suitable.

Methoxy {polyethylene glycol (poly) propylene glycol} mono (meth) acrylate, methoxy {polyethylene glycol (poly) butylene glycol} mono (meth) acrylate, methoxy {polyethylene glycol (poly) propylene glycol (poly) butylene glycol} mono (meta) ) Acrylate, ethoxy {polyethylene glycol (poly) propylene glycol} mono (meth) acrylate, ethoxy {polyethylene glycol (poly) butylene glycol} mono (meth) acrylate, ethoxy {polyethylene glycol (poly) propylene glycol (poly) butylene glycol} Mono (meth) acrylate, propoxy {polyethylene glycol (poly) propylene glycol} mono (meth) acrylate, Propoxy {polyethylene glycol (poly) butylene glycol} mono (meth) acrylate, propoxy {polyethylene glycol (poly) propylene glycol (poly) butylene glycol} mono (meth) acrylate.
Butoxy {polyethylene glycol (poly) propylene glycol} mono (meth) acrylate, butoxy {polyethylene glycol (poly) butylene glycol} mono (meth) acrylate, butoxy {polyethylene glycol (poly) propylene glycol (poly) butylene glycol} mono (meta) ) Acrylate, pentoxy {polyethylene glycol (poly) propylene glycol} mono (meth) acrylate, pentoxy {polyethylene glycol (poly) butylene glycol} mono (meth) acrylate, pentoxy {polyethylene glycol (poly) propylene glycol (poly) butylene glycol} Mono (meth) acrylate, hexoxy {polyethylene glycol (poly) propylene glycol} mono (meth) acrylate DOO, hexoxy {polyethylene glycol (poly) butylene glycol} mono (meth) acrylate, hexoxy {polyethylene glycol (poly) propylene glycol (poly) butylene glycol} mono (meth) acrylate.

Heptoxy {polyethylene glycol (poly) propylene glycol} mono (meth) acrylate, heptoxy {polyethylene glycol (poly) butylene glycol} mono (meth) acrylate, heptoxy {polyethylene glycol (poly) propylene glycol (poly) butylene glycol} mono (meta) ) Acrylate, octoxy {polyethylene glycol (poly) propylene glycol} mono (meth) acrylate, octoxy {polyethylene glycol (poly) butylene glycol} mono (meth) acrylate, octoxy {polyethylene glycol (poly) propylene glycol (poly) butylene glycol} Mono (meth) acrylate, nonanoxy {polyethylene glycol (poly) propylene glycol} mono (meth) a Relate, Nonanokishi {polyethylene glycol (poly) butylene glycol} mono (meth) acrylate, Nonanokishi {polyethylene glycol (poly) propylene glycol (poly) butylene glycol} mono (meth) acrylate.

Decanoxy {polyethylene glycol (poly) propylene glycol} mono (meth) acrylate, decanoxy {polyethylene glycol (poly) butylene glycol} mono (meth) acrylate, decanoxy {polyethylene glycol (poly) propylene glycol (poly) butylene glycol} mono (meta ) Acrylate, undecananoxy {polyethylene glycol (poly) propylene glycol} mono (meth) acrylate, undecanoxy {polyethylene glycol (poly) butylene glycol} mono (meth) acrylate, undecanoxy {polyethylene glycol (poly) propylene glycol (poly) butylene glycol} Mono (meth) acrylate, dodecananoxy {polyethylene glycol (poly) propylene glycol Le} mono (meth) acrylate, dodecanoxy {polyethylene glycol (poly) butylene glycol} mono (meth) acrylate, dodecanoxy {polyethylene glycol (poly) propylene glycol (poly) butylene glycol} mono (meth) acrylate.

Tridecananoxy {polyethylene glycol (poly) propylene glycol} mono (meth) acrylate, tridecanoxy {polyethylene glycol (poly) butylene glycol} mono (meth) acrylate, tridecanoxy {polyethylene glycol (poly) propylene glycol (poly) butylene glycol} mono (meta) ) Acrylate, tetradecananoxy {polyethylene glycol (poly) propylene glycol} mono (meth) acrylate, tetradecanoxy {polyethylene glycol (poly) butylene glycol} mono (meth) acrylate, tetradecanoxy {polyethylene glycol (poly) propylene glycol (poly) Butylene glycol} mono (meth) acrylate, pentadecananoxy {polyethylene glycol ( Li) propylene glycol} mono (meth) acrylate, Pentadekanokishi {polyethylene glycol (poly) butylene glycol} mono (meth) acrylate, Pentadekanokishi {polyethylene glycol (poly) propylene glycol (poly) butylene glycol} mono (meth) acrylate.

Hexadecanoxy {polyethylene glycol (poly) propylene glycol} mono (meth) acrylate, hexadecanoxy {polyethylene glycol (poly) butylene glycol} mono (meth) acrylate, hexadecanoxy {polyethylene glycol (poly) propylene glycol (poly) butylene glycol} Mono (meth) acrylate, heptadecananoxy {polyethylene glycol (poly) propylene glycol} mono (meth) acrylate, heptadecanoxy {polyethylene glycol (poly) butylene glycol} mono (meth) acrylate, heptadecanoxy {polyethylene glycol (poly) propylene glycol (Poly) butylene glycol} mono (meth) acrylate, octadecananoxy {polyethyleneglycol Le (poly) propylene glycol} mono (meth) acrylate, Okutadekanokishi {polyethylene glycol (poly) butylene glycol} mono (meth) acrylate, Okutadekanokishi {polyethylene glycol (poly) propylene glycol (poly) butylene glycol} mono (meth) acrylate.

Nonadecanoxy {polyethylene glycol (poly) propylene glycol} mono (meth) acrylate, nonadecanoxy {polyethylene glycol (poly) butylene glycol} mono (meth) acrylate, nonadecanoxy {polyethylene glycol (poly) propylene glycol (poly) butylene glycol} mono (meta) ) Acrylate, cyclopentoxy {polyethylene glycol (poly) propylene glycol} mono (meth) acrylate, cyclopentoxy {polyethylene glycol (poly) butylene glycol} mono (meth) acrylate, cyclopentoxy {polyethylene glycol (poly) propylene glycol (Poly) butylene glycol} mono (meth) acrylate, cyclohexoxy {polyethylene glycol (poly Propylene glycol} mono (meth) acrylate, cyclohexoxy {polyethylene glycol (poly) butylene glycol} mono (meth) acrylate, cyclohexoxy {polyethylene glycol (poly) propylene glycol (poly) butylene glycol} mono (meth) acrylate.

As the above (alkoxy) polyalkylene glycol mono (meth) acrylate, in addition to the above-mentioned compounds, phenoxy {polyethylene glycol (poly) propylene glycol} mono (meth) acrylate, phenoxy {polyethylene glycol (poly) butylene glycol} mono (Meth) acrylate, phenoxy {polyethylene glycol (poly) propylene glycol (poly) butylene glycol} mono (meth) acrylate, (meth) allyloxy {polyethylene glycol (poly) propylene glycol} mono (meth) acrylate, (meth) allyloxy { Polyethylene glycol (poly) butylene glycol} mono (meth) acrylate, (meth) allyloxy {polyethylene glycol (poly) propylene glycol ( Li) butylene glycol} mono (meth) acrylate are preferred.

As the above (alkoxy) polyalkylene glycol mono (meth) acrylate, alkoxy {polyethylene glycol (poly) propylene glycol} mono (meth) acrylate is preferable, and methoxy {polyethylene glycol (poly) propylene glycol} mono (meth) acrylate. Is more preferable.

As the unsaturated polyalkylene glycol monomer (A), in addition to those described above, (alkoxy) polyalkylene glycol monomaleic acid ester, (alkoxy) polyalkylene glycol dimaleic acid ester and the like are suitable. As such a monomer, the following are suitable.

An alkyl (poly) alkylene glycol obtained by adding 1 to 500 moles of an alkylene oxide having 2 to 18 carbon atoms to an alcohol having 1 to 30 carbon atoms or an amine having 1 to 30 carbon atoms, and the above unsaturated dicarboxylic acid-based monomer. Half-esters and diesters with dimers; Half-esters and diesters of unsaturated dicarboxylic acid monomers and polyalkylene glycols having an average addition mole number of 2 to 500 carbon atoms with glycols; maleamic acid and carbon numbers Half-amides of 2 to 18 glycols with an average addition mole number of 2 to 500 polyalkylene glycols; polypropylene glycol di (meth) acrylate, (poly) ethylene glycol (poly) propylene glycol di (meth) acrylate (poly ) Alkylene glycol di (meth) acrylates; Glycol dimaleate, (poly) alkylene glycol dimaleate such as polypropylene glycol dimaleate.

What is necessary is just to adjust suitably content of the said monomer (A) according to the required performance. From the viewpoint of sufficiently exerting the performance derived from the monomer (A), it is preferably 10% by mass or more, more preferably 50% by mass or more, and further more preferably 70% by mass or more with respect to 100% by mass of the total vinyl monomer. Preferably, 80 mass% or more is most preferable. When other vinyl monomers are used in combination, the content of the monomer (A) is preferably 99% by mass or less, more preferably 95% by mass or less, from the viewpoint of sufficiently exerting their performance. 90 mass% or less is still more preferable, and 85 mass% or less is the most preferable.

It is preferable that the vinyl monomer further contains an unsaturated carboxylic acid monomer. Thereby, the hydrophilicity of a polymer is improved and it becomes possible to make it useful by various uses. That is, it is preferable that the vinyl monomer contains the unsaturated carboxylic acid monomer (a) and the unsaturated polyalkylene glycol monomer (A). That is, it is preferable that the polymer (ii) includes a structural unit derived from the unsaturated carboxylic acid monomer (a) and a structural unit derived from the monomer (A).

When the vinyl monomer is in a form containing an unsaturated carboxylic acid monomer (a) and an unsaturated polyalkylene glycol monomer (A), in the vinyl monomer component, The blending ratio of the unsaturated carboxylic acid monomer (a) and the unsaturated polyalkylene glycol monomer (A) can be appropriately set within a range not impairing the effects of the present invention, and is particularly limited. However, it is preferably 5/95 to 50/50 (unsaturated carboxylic acid monomer (a) / unsaturated polyalkylene glycol monomer (A) (molar ratio)). More preferably, it is 10 / 90-40 / 60, More preferably, it is 20 / 80-30 / 70.

Examples of the unsaturated carboxylic acid monomer (a) (hereinafter also simply referred to as “monomer (a)”) include, for example, the following formula (2);

^(Wherein, R 1, ^{R 2} and ^{R 3} are the same or different and each represents a hydrogen atom, a methyl group or _{(CH ²⁾} x COOM _{2 Note, -. (CH 2) x} COOM 2 is -COOM ¹ Or other — (CH ₂ ) _x COOM ² may form an anhydride, x is an integer of 0 to ^2. M ¹ and M ² are the same or different and are a hydrogen atom, monovalent A compound represented by a metal, a divalent metal, a trivalent metal, a quaternary ammonium base or an organic amine base) is preferable.
The structural unit derived from the monomer (a) is a structure in which a polymerizable double bond of the monomer (a) represented by the general formula (2) is opened by a polymerization reaction (double bond (C = C) corresponds to a single bond (-C—C—).

In the general formula (2), examples of the metal atom represented by M ¹ and M ² include monovalent metal atoms such as alkali metal atoms such as lithium, sodium and potassium; alkaline earth metals such as calcium and magnesium And divalent metal atoms such as atoms; trivalent metal atoms such as aluminum and iron. Examples of the organic amine base include alkanolamine groups such as ethanolamine group, diethanolamine group, triethanolamine group, and triethylamine group.

Specific examples of the unsaturated carboxylic acid monomer represented by the general formula (2) include monocarboxylic acid monomers such as acrylic acid, methacrylic acid, and crotonic acid; maleic acid, itaconic acid, fumaric acid, and the like. Dicarboxylic acid monomers such as acids; anhydrides or salts of these carboxylic acids (for example, alkali metal salts, alkaline earth metal salts, trivalent metal salts, ammonium salts, organic amine salts) and the like. Among these, acrylic acid, methacrylic acid, maleic acid, maleic anhydride and salts thereof are preferable from the viewpoint of polymerizability, and acrylic acid, methacrylic acid and salts thereof are more preferable.

The content of the unsaturated carboxylic acid monomer (a) may be appropriately adjusted according to the required performance. From the viewpoint of sufficiently exerting the performance derived from the monomer (a), the content is preferably 1% by mass or more, more preferably 2% by mass or more, and further more preferably 5% by mass or more with respect to 100% by mass of the total vinyl monomers. Preferably, 7.5% by mass or more is most preferable. Moreover, from a viewpoint which fully exhibits the performance of another vinyl-type monomer, 99 mass% or less is preferable, 50 mass% or less is more preferable, 30 mass% or less is further more preferable, and 25 mass% or less is the most preferable.

The vinyl monomer may further contain an unsaturated polyalkylene glycol monomer (b) other than the unsaturated polyalkylene glycol monomer (A) described above. That is, the vinyl monomer includes an unsaturated carboxylic acid monomer (a), an unsaturated polyalkylene glycol monomer (A), and an unsaturated polyalkylene glycol monomer (b). It may be.
The unsaturated polyalkylene glycol monomer (b) (hereinafter also simply referred to as “monomer (b)”) has one polymerizable double bond and one polyalkylene glycol chain in the molecule. It is a monomer which has the above and the polyalkylene glycol chain does not contain an oxyalkylene group having 3 or more carbon atoms. Examples of the monomer (b) include the following formula (1-3);

(In the formula, R ⁴ , R ⁵ and R ⁶ are the same or different and each represents a hydrogen atom or a methyl group. R ⁷ represents a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms. Represents an ethylene group, y is an integer of 0 to 2. z is 0 or 1. r represents an average added mole number of an oxyethylene group, and is a number of 1 to 300. Are preferred.
In the general formula (1-3), R ⁴ , R ⁵ , R ⁶ , R ⁷ , r, y, and z are the same as those in the general formula (1-1).
In addition, the structural unit derived from the monomer (b) is a structure (double bond () in which a polymerizable double bond of the monomer (b) represented by the general formula (1-3) is opened by a polymerization reaction. C = C) corresponds to a single bond (—C—C—).

Specific examples of the unsaturated polyalkylene glycol monomer represented by the general formula (1-3) include, for example, unsaturated alcohol polyalkylene glycol adducts and polyalkylene glycol ester monomers described above. What does not correspond to a saturated polyalkylene glycol-type monomer (A) is mentioned.
The unsaturated alcohol polyalkylene glycol adduct may be a compound having a structure in which a polyethylene glycol chain is added to an alcohol having an unsaturated group.
The polyalkylene glycol ester-based monomer may be a monomer having a structure in which an unsaturated group and a polyethylene glycol chain are bonded via an ester bond, and an unsaturated carboxylic acid polyethylene glycol ester-based compound is Among them, (alkoxy) polyethylene glycol mono (meth) acrylate is preferable.

Examples of the unsaturated alcohol polyethylene glycol adduct include vinyl alcohol ethylene oxide adduct, (meth) allyl alcohol ethylene oxide adduct, 3-buten-1-ol ethylene oxide adduct, isoprene alcohol (3-methyl-3-butene- 1-ol) ethylene oxide adduct, 3-methyl-2-buten-1-ol ethylene oxide adduct, 2-methyl-3-buten-2-ol ethylene oxide adduct, 2-methyl-2-buten-1-ol ethylene oxide The adduct, 2-methyl-3-buten-1-ol ethylene oxide adduct is preferred.

Specific examples of the unsaturated alcohol polyethylene glycol adduct include, for example, polyethylene glycol monovinyl ether, methoxypolyethylene glycol monovinyl ether, polyethylene glycol mono (meth) allyl ether, methoxypolyethylene glycol mono (meth) allyl ether, polyethylene glycol mono ( 2-methyl-2-propenyl) ether, polyethylene glycol mono (2-butenyl) ether, polyethylene glycol mono (3-methyl-3-butenyl) ether, polyethylene glycol mono (3-methyl-2-butenyl) ether, polyethylene glycol Mono (2-methyl-3-butenyl) ether, polyethylene glycol mono (2-methyl-2-butenyl) ether, polyethyleneglycol Rumono (1,1-dimethyl-2-propenyl) ether, methoxypolyethyleneglycolmono (3-methyl-3-butenyl) ether, ethoxypolyethyleneglycolmono (3-methyl-3-butenyl) ether, 1-propoxypolyethyleneglycolmono (3-methyl-3-butenyl) ether, cyclohexyloxypolyethylene glycol mono (3-methyl-3-butenyl) ether, 1-octyloxypolyethylene glycol mono (3-methyl-3-butenyl) ether, nonylalkoxy polyethylene glycol mono (3-methyl-3-butenyl) ether, lauryl alkoxy polyethylene glycol mono (3-methyl-3-butenyl) ether, stearyl alkoxy polyethylene glycol mono (3-methyl-3 Butenyl) ether, phenoxy polyethylene glycol mono (3-methyl-3-butenyl) ether, naphthoxy polyethylene glycol mono (3-methyl-3-butenyl) ether, methoxy polyethylene glycol monoallyl ether, ethoxy polyethylene glycol monoallyl ether, phenoxy Polyethylene glycol monoallyl ether, methoxy polyethylene glycol mono (2-methyl-2-propenyl) ether, ethoxy polyethylene glycol mono (2-methyl-2-propenyl) ether, phenoxy polyethylene glycol mono (2-methyl-2-propenyl) ether Etc. are suitable.

Examples of the (alkoxy) polyethylene glycol mono (meth) acrylate include esterified products of an alkoxypolyethylene glycol obtained by adding 1 to 25 moles of an ethylene oxide group having 2 to 18 carbon atoms to an alcohol and (meth) acrylic acid. Is preferred.
Examples of the alcohols include methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, 1-pentanol, 2-pentanol, 3-pentanol, 1-hexanol, and 2-hexanol. C1-C30 aliphatic alcohols such as 3-hexanol, octanol, 2-ethyl-1-hexanol, nonyl alcohol, lauryl alcohol, cetyl alcohol and stearyl alcohol; C3-C30 fats such as cyclohexanol Cyclic alcohols; unsaturated alcohols having 3 to 30 carbon atoms such as (meth) allyl alcohol, 3-buten-1-ol, 3-methyl-3-buten-1-ol, and the like.

Specifically, the following (alkoxy) polyethylene glycol (meth) acrylic acid esters and the like are preferable as the esterified product.
Methoxypolyethyleneglycol mono (meth) acrylate, ethoxypolyethyleneglycol mono (meth) acrylate, propoxypolyethyleneglycolmono (meth) acrylate, butoxypolyethyleneglycolmono (meth) acrylate, pentoxypolyethyleneglycolmono (meth) acrylate, hexoxypolyethyleneglycol Mono (meth) acrylate, heptoxypolyethylene glycol mono (meth) acrylate, octoxypolyethylene glycol mono (meth) acrylate, nonanoxypolyethylene glycol mono (meth) acrylate, decanoxypolyethylene glycol mono (meth) acrylate, undecanoxy Polyethylene glycol mono (meth) acrylate, dodecanoxy polyethylene glycol Rumono (meth) acrylate, tridecanoxy polyethylene glycol mono (meth) acrylate, tetradecanoxy polyethylene glycol mono (meth) acrylate, pentadecanoxy polyethylene glycol mono (meth) acrylate, hexadecanoxy polyethylene glycol mono (meth) ) Acrylate, heptadecanoxy polyethylene glycol mono (meth) acrylate, octadecanoxy polyethylene glycol mono (meth) acrylate, nonadecanoxy polyethylene glycol mono (meth) acrylate, cyclopentoxypolyethylene glycol mono (meth) acrylate, Cyclohexoxypolyethylene glycol mono (meth) acrylate.

As the (alkoxy) polyalkylene glycol mono (meth) acrylate, besides the above-mentioned compounds, phenoxypolyethylene glycol mono (meth) acrylate, (meth) allyloxypolyethylene glycol mono (meth) acrylate and the like are suitable.

As the polyalkylene glycol unsaturated monomer (b), (alkoxy) polyethylene glycol monomaleic acid ester, (alkoxy) polyethylene glycol dimaleic acid ester and the like are suitable in addition to those described above. As such a monomer, the following are suitable.

A half ester of an alkyl (poly) ethylene glycol obtained by adding 1 to 500 mol of ethylene oxide to an alcohol having 1 to 30 carbon atoms or an amine having 1 to 30 carbon atoms and an unsaturated dicarboxylic acid monomer as described above, Diester; half ester of unsaturated dicarboxylic acid monomer and polyethylene glycol having an average addition mole number of ethylene oxide of 2 to 500; diester; half amide of maleic acid and ethylene oxide having an average addition mole number of polyethylene glycol of 2 to 500 (Poly) ethylene glycol di (meth) acrylates such as triethylene glycol di (meth) acrylate and (poly) ethylene glycol di (meth) acrylate; polyethylene glycol dimaleate and polyethylene glycol dimaleate (poly ) Echile Glycol dimaleate class.

The content of the unsaturated polyalkylene glycol monomer (b) may be appropriately adjusted according to the required performance. From the viewpoint of sufficiently exerting the performance derived from the monomer (b), the content is preferably 1% by mass or more, more preferably 10% by mass or more, and further more preferably 20% by mass or more with respect to 100% by mass of the total vinyl monomers. Preferably, 30% by mass or more is most preferable. Moreover, from a viewpoint which fully exhibits the performance of another vinyl-type monomer, 99 mass% or less is preferable, 50 mass% or less is more preferable, 45 mass% or less is further more preferable, and 40 mass% or less is the most preferable.

The vinyl monomer component used to obtain the polymer (ii) is also an unsaturated polyalkylene glycol monomer (A), an unsaturated carboxylic acid monomer (a), and an unsaturated poly Other copolymerizable monomers (hereinafter also referred to as “monomer (c)”) other than the alkylene glycol monomer (b) may be included.
In this case, the polymer (ii) further contains a structural unit derived from the monomer (c), and the structural unit derived from the monomer (c) is a monomer by polymerization reaction. It corresponds to a structure (a structure in which a double bond (C = C) is converted to a single bond (-C-C-)) having a polymerizable double bond in (c).
When using the said monomer (c), it is suitable to set it as 30 mass% or less with respect to 100 mass% of all the vinyl-type monomer components. More preferably, it is 25 mass% or less, More preferably, it is 20 mass% or less.

Specific examples of the monomer (c) include the following compounds, and one or more of these can be used.
Half esters and diesters of unsaturated dicarboxylic acid monomers such as maleic acid, maleic anhydride, fumaric acid, itaconic acid, citraconic acid and the like and alcohols having 23 to 30 carbon atoms; And polyfunctional (meth) such as hexanediol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, trimethylolpropane di (meth) acrylate, etc. Acrylates: 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;

Amides of unsaturated monocarboxylic acids and amines having 1 to 30 carbon atoms such as methyl (meth) acrylamide; vinyl aromatics such as styrene, α-methylstyrene, vinyltoluene, p-methylstyrene; Alkanediol mono (meth) acrylates such as 4-butanediol mono (meth) acrylate, 1,5-pentanediol mono (meth) acrylate, 1,6-hexanediol mono (meth) acrylate; butadiene, isoprene, 2- Dienes such as methyl-1,3-butadiene and 2-chloro-1,3-butadiene; (meth) acrylamide, (meth) acrylalkylamide, N-methylol (meth) acrylamide, N, N-dimethyl (meth) Unsaturated amides such as acrylamide; (meth) acrylonitrile, α-chloroa Unsaturated cyanides such as acrylonitrile; unsaturated esters such as vinyl acetate and vinyl propionate.

Among the polyalkylene glycol polymers in the present invention, the structure includes a polyalkylene glycol chain (PAG), a structural unit derived from a vinyl monomer (BL), and three structural sites of Y, and further a hydrogen atom As the polymer (i-2) having other structural sites other than the following general formula (3);

(In the formula, X represents a residue of a compound having one or more active hydrogens. AO is the same or different and represents an oxyalkylene group having 2 to 18 carbon atoms. Y ¹ is the same or different. And Z represents an unsaturated polyalkylene glycol-based monomer having a polyalkylene glycol chain which is the same or different and has an oxyalkylene group having 3 or more carbon atoms as an essential component. Represents a polymer that forms a structural unit derived from a vinyl monomer, n is the same or different and represents the average number of added moles of an oxyalkylene group, and is a number from 1 to 1000. m is from 1 to 50. It is an integer represented by.

In the general formula (3), specific examples and preferred examples of the oxyalkylene group represented by AO are the same as those of the alkylene oxide having 2 or more carbon atoms constituting the polyalkylene glycol chain (PAG).
Further, the organic residue represented by Y ^1, and, as the polymer forming the constitutional unit derived from the vinyl monomer represented by Z, respectively, above Y, and, from a vinyl monomer The same as the polymer (ii) forming the structural unit (BL). M is a polyalkylene glycol chain bonded to a compound having one or more active hydrogens represented by X and having a structural unit derived from the vinyl monomer bonded through a direct bond or an organic residue. Represents the number of

The polymer represented by the general formula (3) includes a polyalkylene glycol polymer having a multi-branched structure, and a polyalkylene glycol polymer having a non-multi-branched (straight chain) structure that does not have a multi-branched structure. including. The polyalkylene glycol polymer having a multi-branched structure here is a polymer chain containing a polyalkylene glycol chain bonded to at least three or more sites having active hydrogen of a compound having three or more active hydrogens. Means a structure in which the polymer chain is branched radially from the residue of a compound having three or more active hydrogens, and a non-multi-branched polyalkylene glycol polymer is such an active hydrogen. Means a structure that does not have the above polymer chain branched radially from the residue of a compound having 3 or more.
In addition, if the polyalkylene glycol polymer having a non-multi-branched structure does not have a structure in which the polymer chain is branched radially from the residue of a compound having 3 or more active hydrogens, for example, The structural unit (BL) derived from the vinyl monomer has a branched structure branched from the main chain as in the case where the unsaturated monomer having a polyalkylene glycol chain is used as a raw material. It may be a thing.

The polyalkylene glycol polymer having a non-multi-branched (straight chain) structure has one or two polyalkylene glycol chains bonded to the residue of a compound having one or more active hydrogens, and the polyalkylene It has a structure in which the terminal oxygen atom at at least one of the other ends of the glycol chain is bonded to the main chain end of the constituent unit derived from the vinyl monomer directly or through an organic residue. In this case, the structure of the polyalkylene glycol polymer having a non-multi-branched (straight chain) structure is as follows: (1) one polyalkylene glycol chain is bonded to the residue of a compound having one or more active hydrogens, The polymer has a structure in which the residue of the compound having one or more active hydrogens is located at the end of the structure of the polyalkylene glycol polymer, and (2) the residue of the compound having two or more active hydrogens. Two structures of a polyalkylene glycol chain are bonded, and the polymer has a structure having a structure in which a residue of a compound having one or more active hydrogens is located between two polyalkylene glycol chains. It will have.

The polyalkylene glycol polymer having a non-branched (straight chain) structure in the form (1) above has a structure in which one polyalkylene glycol chain is bonded to the residue of a compound having one active hydrogen. Is preferred. The polyalkylene glycol polymer having a non-multi-branched (straight chain) structure in the form (2) has a structure in which two polyalkylene glycol chains are bonded to the residue of a compound having two active hydrogens. Preferably there is.

The polyalkylene glycol polymer having a multi-branched structure has at least one polyalkylene glycol chain bonded to the residue of a compound having 3 or more active hydrogens and at least one other end of the polyalkylene glycol chain. In which the terminal oxygen atom is bonded to the main chain terminal of the structural unit derived from the vinyl monomer directly or through an organic residue.
The multi-branched polyalkylene glycol-based polymer has a multi-branched structure. As described above, the multi-branched structure is a structure that is branched radially from the residue of a compound having three or more active hydrogens. It means that there is. That is, it means a structure in which the polymer (ii) is bonded from a residue of a compound having 3 or more active hydrogens as a starting point through a polyalkylene glycol chain and an organic residue. The steric repulsion resulting from this multi-branched structure dramatically improves the performance of dispersing cement particles.
When the polyalkylene glycol-based polymer of the present invention contains a multi-branched polyalkylene glycol-based polymer, the polymer has a hydrolyzable group, and is synergistic with steric repulsion due to the multi-branched structure. Due to the effect, the cement dispersion performance and slump retention performance are particularly excellent.
Thus, a polymer having a polyalkylene glycol chain and having a multi-branched structure, wherein the polymer has 3 or more polyalkylene glycol chains bonded to the residue of a compound having 3 or more active hydrogens, And the terminal oxygen atom at at least one other end of the polyalkylene glycol chain has a structure in which the main chain terminal of the constituent unit derived from the vinyl monomer is bonded directly or via an organic residue, The vinyl monomer essentially contains an unsaturated polyalkylene glycol monomer having a polyalkylene glycol chain having an oxyalkylene group having 3 or more carbon atoms as an essential component. 1 is one of the preferred embodiments of the present invention.
The “main chain” in the polyalkylene glycol polymer having the multi-branched structure includes a polyalkylene glycol chain that is branched radially from the residue of the compound having three or more active hydrogens. The main chain of the polymer chain, that is, the main chain of the polymer chain bonded to the residue is meant.

When the compound having active hydrogen is used for the production of a polyalkylene glycol polymer having a multi-branched structure, the number of active hydrogens of the compound having active hydrogen needs to be 3 or more. From the viewpoint of polymerizability when the polymerization is performed using the polyalkylene glycol chain-containing thiol compound, the number is preferably 50 or less. The lower limit value of the number of active hydrogens is preferably 4, more preferably 5, and the upper limit value is more preferably 20, more preferably 10.

The residue of the compound having active hydrogen means a group having a structure obtained by removing active hydrogen from a compound having active hydrogen, and the active hydrogen means hydrogen to which an alkylene oxide can be added.
Specific examples of the residue of a compound having one or more active hydrogens include, for example, alcohol residues, monovalent or polyvalent amines having a structure in which active hydrogen is removed from the hydroxyl group of a monovalent or polyhydric alcohol. An amine residue having a structure in which active hydrogen is removed from the amino group of an imine residue having a structure in which active hydrogen is removed from an imino group of a monovalent or polyvalent imine, active from an amide group of a monovalent or polyvalent amide compound Amide residues having a structure excluding hydrogen are preferable. Of these, amine residues, imine residues and alcohol residues are preferred. This makes it possible to obtain a compound suitable for various applications.
In addition, as a form of the compound residue which has active hydrogen, any of the structure bridge | crosslinked in the chain form, the branched form, and the three-dimensional form may be sufficient.

In a preferred form of the residue of the compound having active hydrogen, the polyvalent amine (polyamine) may be a compound having an average of 3 or more amino groups in one molecule, for example, methylamine, ethylamine, propyl Alkylamines such as amine, butylamine, 2-ethylbutylamine, octylamine, dimethylamine, dipropylamine, dimethylethanolamine, dibutylamine, trimethylamine, triethylamine, cyclobutylamine, cyclohexylamine, laurylamine; alkyleneamines such as allylamine; aniline Homopolymers and copolymers obtained by polymerizing one or more monoamine compounds such as aromatic amines such as diphenylamine; nitrogen compounds such as ammonia, urea, and thiourea by a conventional method are suitable. . Such a compound forms a polyvalent amine residue in the polyalkylene glycol polymer. 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 polyalkyleneimine may be a compound having an average of 3 or more imino groups in one molecule. For example, ethyleneimine, propyleneimine, 1,2-butyleneimine, 2,3-butyleneimine, 1, A homopolymer or copolymer obtained by polymerizing one or more alkyleneimines having 2 to 8 carbon atoms such as 1-dimethylethyleneimine by a conventional method is preferable. Such a compound forms a polyalkyleneimine residue in the polyalkylene glycol polymer. Polyalkyleneimines are three-dimensionally crosslinked by polymerization, and usually have a primary amino group or secondary amino group (imino group) having an active hydrogen atom in addition to a tertiary amino group in the structure. become.
Among these, from the viewpoint of performance exhibited by the polyalkylene glycol-based polymer, it is more preferable that the polyalkyleneimine is mainly composed of ethyleneimine.

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 that forms the polyalkyleneimine chain is mostly ethyleneimine, which improves the hydrophilicity of the polyalkyleneglycol polymer and is suitable for many applications. The above-described effects are sufficiently exhibited, so that ethyleneimine is used as an alkyleneimine to form a polyalkyleneimine chain (polyalkyleneimine residue) to the extent that the above-described effects are sufficiently exhibited. This means “occupies the majority”. 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 the alkyleneimine per one polyalkyleneimine chain is preferably 2 or more, and preferably 300 or less. By setting it as such a range, it becomes possible to more fully exhibit the effect resulting from the structure of the polyalkylene glycol polymer, for example, exhibiting cement dispersion performance for use as a cement admixture or the like. It can be made suitable. As a lower limit, More preferably, it is 3, More preferably, it is 5, Especially preferably, it is 10. Moreover, as an upper limit, More preferably, it is 200, More preferably, it is 100, Especially preferably, it is 50, Most preferably, it is 25. 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 polyalkyleneimine, 100-100000 are preferable, More preferably, it is 300-50000, More preferably, it is 600-10000, Most preferably, it is 800-5000.

The polyhydric alcohol may be a compound containing an average of 3 or more hydroxyl groups in one molecule, but is preferably a compound composed of three elements of carbon, hydrogen and oxygen. Specifically, for example, polyglycidol, glycerin, polyglycerin, trimethylolethane, trimethylolpropane, 1,3,5-pentatriol, erythritol, pentaerythritol, dipentaerythritol, sorbitol, sorbitan, sorbitol glycerin condensate, Adonitol, arabitol, xylitol, mannitol and the like are preferable. 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. Such a compound forms a polyhydric alcohol residue in the polyalkylene glycol polymer.
Among these, trimethylolpropane and sorbitol are more preferable from the viewpoint of industrial production efficiency.

The number of the polyalkylene glycol chains to which the compound having 3 or more active hydrogens is bonded is preferably equal to the number of active hydrogens in the compound having 3 or more active hydrogens. That is, it is preferable to have a structure in which a polyalkylene glycol chain is bonded to all active hydrogen atoms in the compound having three or more active hydrogens. This makes it possible to provide a cement admixture that can exhibit further superior dispersibility, so that the compound can be applied to various applications.

Here, when schematically showing the structure in which the number of the polyalkylene glycol chains to which the compound having 3 or more active hydrogens is bonded is equal to the number of active hydrogens in the compound having 3 or more active hydrogens, It can be expressed as follows:
In the following formula (A), the residue of the compound having 3 or more active hydrogens is a glycerin residue (polyhydric alcohol residue), and all the active hydrogens possessed by glycerin include a polyalkylene glycol chain and a sulfur atom. 1 schematically shows a structure in which a polymer (ii) is bonded via an organic residue.
Further, in the following formula (B), the residue of a compound having 3 or more active hydrogens is a sorbitol residue (polyhydric alcohol residue), and all the active hydrogens possessed by sorbitol have a polyalkylene glycol chain and a sulfur atom. FIG. 2 schematically shows a structure in which an organic residue contained therein is bonded, and a structural unit derived from a vinyl monomer is bonded to some of the sulfur atoms.

The structure and chain length of the polyalkylene glycol chain in the polyalkylene glycol polymer having the multi-branched structure are the same as the structure and chain length in the polyalkylene glycol chain (I).

The polyalkylene glycol polymer having a non-multi-branched (straight chain) structure and the polyalkylene glycol-based polymer having a multi-branched structure also have a polyalkylene glycol chain that is not bonded to a structural unit derived from the vinyl monomer. You may have.
The terminal of such a polyalkylene glycol chain (residue of the compound having active hydrogen or the terminal opposite to the hydrogen atom) is, for example, a hydrogen atom, a monovalent metal atom, a divalent metal atom, an ammonium group, or an organic amine. Group, hydrocarbon group having 1 to 30 carbon atoms, oxo hydrocarbon group, amide hydrocarbon group, carboxyl hydrocarbon group, sulfonyl (hydrocarbon) group having 0 to 30 carbon atoms, -O-C (= O) -R It is preferable to have a structure bonded to any one of mercaptocarboxylic acid residues represented by —SH (R represents a hydrocarbon group having 1 to 30 carbon atoms), and two or more in one molecule In the case of having the polyalkylene glycol chain, the terminal structure may be the same or different. Among such terminal structures, from the viewpoint of versatility, a hydrogen atom or a hydrocarbon group having 1 to 30 carbon atoms, more preferably a structure bonded to a hydrogen atom or a carbon hydrogen group having 1 to 10 carbon atoms, Among the hydrocarbon groups having 1 to 10 carbon atoms, an alkyl group and an alkylene group are preferable.
That is, for example, when the polyalkylene glycol polymer (i) is a polymer represented by the general formula (3), the polymer is represented by the following general formula (4);

(In the formula, X, AO, Y ¹ , Z, n and m are the same as those in the general formula (3), and Y ³ is the same or different and represents a direct bond or an organic residue. N ′ represents , The same or different and represents the average number of added moles of the oxyalkylene group, and is a number of 1 to 1000, and preferred forms include the same forms as n above, where n and n ′ are the same. Q may be the same or different and each represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms or an alkylene group, or —O—C (═O) —R—SH (where R is Represents a hydrocarbon group having 1 to 30 carbon atoms.) P is an integer of 0 or more, and has 1 or 2 or more active hydrogens represented by X The maximum number depends on the number of active hydrogens in the compound and the number of m.) It may be ones.
Y ³ is the same as Y described above.
P is a number whose maximum number is determined depending on the number of active hydrogens and the number of m of the compound having one or more active hydrogens represented by X, wherein X is a compound having three or more active hydrogens A compound having 3 or more active hydrogens in order to sufficiently exert the effect due to the polyalkylene glycol chain bonded to the structural unit derived from the vinyl monomer via an organic residue. It is preferable that p is a number of [(total number of active hydrogens of a compound having 3 or more active hydrogens) −3] or less so that the number of the polyalkylene glycol chains to which is bonded is 3 or more. .

As an example of a suitable form of the polyalkylene glycol polymer of the present invention, for example, the following general formula (5);

（式中、Ｘ’は、活性水素を１若しくは２個以上有する化合物の残基、Ｚ−Ｙ^１−で表される基又は水素原子を表す。ＡＯは、同一又は異なって、炭素数２〜１８のオキシアルキレン基を表す。Ｙ^１は、同一又は異なって、直接結合又は有機残基を表す。Ｚは、同一又は異なって、炭素数３以上のオキシアルキレン基を必須とするポリアルキレングリコール鎖を有する不飽和ポリアルキレングリコール系単量体を必須に含むビニル系単量体由来の構成単位を形成する重合体を表す。ｎは、同一又は異なって、オキシアルキレン基の平均付加モル数を表し、１〜１０００の数である。ｍは、１〜５０の整数である。）で表される構造を有する形態を挙げることができる。
上記一般式（５）におけるＡＯ、Ｙ^１、Ｚ、ｎ及びｍについては上述したとおりである。上記一般式（５）においてＸ’がＺ−Ｙ^１−で表される基又は水素原子である場合、ｍは１である。
上記一般式（５）においてＸ’がＺ−Ｙ^１−で表される基であり、かつｍが１である形態は、上記一般式（ａ）で表される構造を有する重合体に該当し、Ｘ’が水素原子であり、かつｍが１である形態は、上記一般式（ｂ）においてポリアルキレングリコール鎖（ＰＡＧ）の一末端が水素原子である構造を有する重合体に該当する。また、Ｘ’が活性水素を１若しくは２個以上有する化合物の残基である形態は、上記一般式（３）で表される構造を有する重合体に該当する。
このように、上記ポリアルキレングリコール系重合体が上記一般式（５）で表される構造を有するものであることは、本発明の好ましい実施形態の１つである。

(In the formula, X ′ represents a residue of a compound having one or more active hydrogens, a group represented by ZY ¹ — or a hydrogen atom. AO is the same or different and has 2 to 2 carbon atoms. 18 represents an oxyalkylene group, Y ¹ is the same or different and represents a direct bond or an organic residue, Z is the same or different, and a polyalkylene glycol chain having an oxyalkylene group having 3 or more carbon atoms as an essential component Represents a polymer that forms a structural unit derived from a vinyl-based monomer that essentially contains an unsaturated polyalkylene glycol-based monomer having n, wherein n is the same or different and represents the average number of moles of oxyalkylene groups added. , 1 to 1000. m is an integer of 1 to 50).
AO, Y ¹ , Z, n and m in the general formula (5) are as described above. In the general formula (5), when X ′ is a group represented by Z—Y ¹ — or a hydrogen atom, m is 1.
In the general formula (5), X ′ is a group represented by Z—Y ¹ — and m is 1, which corresponds to a polymer having a structure represented by the general formula (a). , X ′ is a hydrogen atom, and m is 1 corresponds to a polymer having a structure in which one end of the polyalkylene glycol chain (PAG) is a hydrogen atom in the general formula (b). The form in which X ′ is the residue of a compound having one or more active hydrogens corresponds to the polymer having the structure represented by the general formula (3).
Thus, it is one of the preferable embodiments of the present invention that the polyalkylene glycol polymer has a structure represented by the general formula (5).

The polyalkylene glycol polymer of the present invention may have a weight average molecular weight (Mw) of 1 million or less in consideration of its handleability and retention of cement composition when used for cement admixture. Is preferred. More preferably, it is 500,000 or less, more preferably 300,000 or less, still more preferably 200,000 or less, and particularly preferably 150,000 or less. Further, when used for cement admixture, it is preferable that Mw is 1000 or more from the viewpoint that performance is better when adsorbed to cement particles to some extent, and the adsorption power increases as Mw increases. More preferably, it is 5000 or more, More preferably, it is 10,000 or more, More preferably, it is 20,000 or more, Most preferably, it is 30,000 or more.
The polyalkylene glycol polymer preferably has a number average molecular weight (Mn) of 500,000 or less. More preferably, it is 250,000 or less, More preferably, it is 150,000 or less, More preferably, it is 100,000 or less, Especially preferably, it is 75,000 or less. Mn is also preferably 1000 or more. More preferably, it is 2500 or more, More preferably, it is 5000 or more, More preferably, it is 10,000 or more, Especially preferably, it is 15000 or more.
The polyalkylene glycol polymer preferably has a peak top molecular weight (Mp) of 1 million or less. More preferably, it is 500,000 or less, More preferably, it is 300,000 or less, Most preferably, it is 200,000 or less. Mp is preferably 1000 or more. More preferably, it is 5000 or more, More preferably, it is 10,000 or more, Especially preferably, it is 20,000 or more.
In addition, the weight average molecular weight, number average molecular weight, and peak top molecular weight of a polymer can be calculated | required by the gel permeation chromatography (GPC) analysis method mentioned later.

<Method for producing polyalkylene glycol polymer>
Next, the method for producing the polyalkylene glycol polymer in the present invention will be described.
In the present invention, the polyalkylene glycol polymer is a vinyl monomer in the presence of a polymer initiator having a polyalkylene glycol chain and a radical generating site and / or a polymer chain transfer agent having a polyalkylene glycol chain. It can be produced by polymerizing body components. By using the polymer initiator and / or polymer chain transfer agent, a polyalkylene glycol chain is introduced into the polyalkylene glycol polymer in the present invention.

In the polymerization reaction, the amount of the polyalkylene glycol chain used and the monomer (A), monomer (a), monomer (b) and monomer (c) of the vinyl monomer component. The relationship between the polyalkylene glycol chain / (monomer (A) + monomer (a) + monomer (b) + monomer (c)) In terms of expression, when the monomer (a) is the main component, it is preferably 5/95 to 99/1, more preferably 10/90 to 97/3, still more preferably 20/80 to 95/5, Especially preferably, it is 30 / 70-92.5 / 7.5. When the monomer (A) and / or (b) is the main component, it is preferably 2/98 to 95/5, more preferably 4/96 to 90/10, and still more preferably 8/92. To 80/20, more preferably 10/90 to 75/25, more preferably 15/85 to 70/30, more preferably 17.5 / 82.5 to 65/35, particularly preferably 20/80 to 60/40. In particular, the monomer (a) has a ratio of monomer (a) / (the above polyalkylene glycol chain + monomer (A) + monomer (b) + monomer (c)) (unit: % By mass), preferably 1 to 50/99 to 50, more preferably 2.5 to 40 / 97.5 to 60, and still more preferably 5 to 35/95 to 65.

First, a method for producing a polyalkylene glycol polymer in the present invention by polymerizing a vinyl monomer component in the presence of a polymer initiator having a polyalkylene glycol chain and a radical generation site will be described. .
As a method for polymerizing a vinyl monomer component in the presence of a polymer initiator having a polyalkylene glycol chain and a radical generating site, a polymer azo initiator having a polyalkylene glycol chain and a radical generating site described later can be used. By using the agent, the azo group in the polymer azo initiator is decomposed by heat, radicals are generated, and polymerization of the vinyl monomer component is started therefrom. Can be mentioned.

First, the polymer (i-1), that is, a polyalkylene glycol chain (PAG), a structural unit derived from a vinyl monomer (BL), and a structure composed of three structural sites Y is manufactured. Examples of the method include the following methods.

The following general formula (e);
-[YN = NY- (PAG)]-(e)
A method of polymerizing a vinyl monomer component in the presence of a polymeric azo initiator having a repeating unit represented by:
The following general formula (f);
(PAG) -YN = NY- (PAG) (f)
A method of polymerizing a vinyl monomer component in the presence of a polymer azo initiator represented by In these polymeric azo initiators (e) to (f), when the polyalkylene glycol chain (PAG) is located at the end of the structure, the polyalkylene glycol chain (PAG) has a hydrogen atom at the end. It will be. That is, the terminal structure of the polyalkylene glycol chain (PAG) is a hydroxyl group.
“PAG” and “Y” in the general formulas (e) to (f) are the same as those in the general formulas (a) to (d).
As a preferable form of the polymeric azo initiator having a repeating unit represented by the general formula (e), the following general formula (6);

(Wherein Y ⁴ is the same or different and represents an organic residue. A ¹ O is the same or different and represents an oxyalkylene group having 2 to 18 carbon atoms. N is the same or different and represents oxy The average addition mole number of an alkylene group is a number of 1-1000.) The polymeric azo initiator which has a repeating unit represented by this is mentioned. These polymeric azo initiators may be used alone or in combination of two or more.

In the general formula (6), the organic residue represented by Y ⁴ is the same as the organic residue in Y ¹ of the general formula (3). The oxyalkylene group having 2 to 18 carbon atoms represented by A ¹ O is the same as AO described above. The average added mole number of the oxyalkylene group represented by n is as described above. As a more preferable form of the polymeric azo initiator having a repeating unit represented by the general formula (e), the following general formula (7);

(In formula, R < ⁸ > is the same or different, and the C1-C20 alkylene group which may have a substituent, a carbonyl group, a carboxyl group, or the carbon number which may have a substituent. 1 to 20 represents an alkylene group bonded to a carbonyl group or a carboxyl group, and R ⁹ is the same or different and is an alkyl group having 1 to 20 carbon atoms or an alkyl group having 1 to 10 carbon atoms substituted with a carboxyl group. group, .R ¹⁰ representing a phenyl group or a substituted phenyl group are the same or different, a cyano group, an acetoxy group, .A 1 ^O representing a carbamoyl group or a carbonyl group substituted with an alkoxy group having 1 to 10 carbon atoms Are the same or different and each represents an oxyalkylene group having 2 to 18 carbon atoms, and n is the same or different and represents the average number of moles added of the oxyalkylene group. 0 is the number of.) Polymeric azo initiator having a repeating unit represented by the like.

Examples of the substituent for R ⁸ in the general formula (7) include an alkyl group, an alkenyl group, a hydroxyl group, a cyano group, a carboxyl group, and an amino group. The oxyalkylene group having 2 to 18 carbon atoms represented by A ¹ O is the same as AO described above. The average added mole number of the oxyalkylene group represented by n is as described above.
As a more preferable form of the polymeric azo initiator having a repeating unit represented by the general formula (e), the following general formula (8);

(Wherein, ^{A 1} O may be the same or different, .n representing an oxyalkylene group having 2 to 18 carbon atoms are the same or different and each represents an average addition mole number of the oxyalkylene group, 1-1000 Number of And a polymeric azo initiator having a repeating unit represented by:
The oxyalkylene group having 2 to 18 carbon atoms represented by A ¹ O in the general formula (8) is the same as AO described above. The average added mole number of the oxyalkylene group represented by n is as described above.

Among the polymeric azo initiators having a repeating unit represented by the general formula (6), a polymeric azo initiator having a repeating unit in which A ¹ O is an oxyethylene group is particularly suitable. Is a polymer azo initiator VPE series commercially available from Wako Pure Chemical Industries, Ltd., for example, VPE-0201 (number average molecular weight about 1.5 to 30,000, molecular weight of polyethylene oxide part about 2,000, m = 45), VPE-0401 (number average molecular weight of about 2.5 to 40,000, polyethylene oxide moiety molecular weight of about 4,000, m = 90), VPE-0601 (number average molecular weight of about 2.5 to 40,000, polyethylene oxide) And the molecular weight of the portion is about 6,000, m = 135).

As a preferable form of the polymer azo initiator represented by the general formula (f), the following general formula (9);

(Wherein Y ⁵ is the same or different and represents an organic residue. A ² O is the same or different and represents an oxyalkylene group having 2 to 18 carbon atoms; k is the same or different and represents oxy The average added mole number of an alkylene group is represented, and it is a number of 1-1000.) The high molecular azo initiator represented by this is mentioned. These polymeric azo initiators may be used alone or in combination of two or more.

In the general formula (9), the organic residue represented by Y ⁵ is the same as the organic residue in Y ¹ of the general formula (3). The oxyalkylene group having 2 to 18 carbon atoms represented by A ² O is the same as AO in the general formula (3). The average added mole number of the oxyalkylene group represented by k is the same as n in the general formula (3). As a more preferable form of the polymer azo initiator represented by the general formula (f), the following general formula (10);

(In the formula, R ^{11 s} are the same or different and may have a substituent, an alkylene group having 1 to 20 carbon atoms, a carbonyl group, a carboxyl group, or a carbon number that may have a substituent. 1 to 20 represents an alkylene group bonded to a carbonyl group or a carboxyl group, and R ¹² is the same or different and is an alkyl group having 1 to 20 carbon atoms or an alkyl group having 1 to 10 carbon atoms substituted with a carboxyl group. group, .R ¹³ representing a phenyl group or a substituted phenyl group are the same or different, a cyano group, an acetoxy group, a represents .A 2 ^O carbamoyl group or a carbonyl group substituted with an alkoxy group having 1 to 10 carbon atoms Are the same or different and each represents an oxyalkylene group having 2 to 18 carbon atoms, k is the same or different and represents the average number of moles added of the oxyalkylene group; Is the number of 000.) A polymer azo initiator represented by like.

Examples of the substituent for R ¹¹ in the general formula (10) include an alkyl group, an alkenyl group, a hydroxyl group, a cyano group, a carboxyl group, and an amino group. Moreover, the oxyalkylene group having 2 to 18 carbon atoms represented by A 2 ^O, and, for the average number of moles of the oxyalkylene group represented by k are as described above.
As a more preferable form of the polymeric azo initiator represented by the general formula (f), the following general formula (11);

(In the formula, A ² O is the same or different and represents an oxyalkylene group having 2 to 18 carbon atoms; k is the same or different and represents the average number of added moles of the oxyalkylene group; The polymeric azo initiator represented by these is mentioned.
In the general formula (11), the oxyalkylene group having 2 to 18 carbon atoms represented by A ² O and the average added mole number of the oxyalkylene group represented by k are as described above.

The polymer azo initiator represented by the general formula (9) includes, for example, an azo initiator having a carboxyl group at both ends of the azo group (V-501 or the like, manufactured by Wako Pure Chemical Industries, Ltd.), and polyalkylene glycol. Can be obtained by esterification. As a method of esterification, since a azo initiator will decompose | disassemble when a heating process is performed, the manufacturing method which does not include a heating process is required. As such a production method, (1) a method in which an azo initiator is reacted with thionyl chloride to synthesize an acid chloride, and then a polyalkylene glycol is reacted to obtain a polymer azo initiator; (2) an azo initiator And polyalkylene glycol are subjected to dehydration condensation using dicyclohexylcarbodiimide (DCC) and 4-dimethylaminopyridine as required, to obtain a polymer azo initiator.

The amount (% by mass) of the polymer azo initiator having a repeating unit represented by the general formula (6) or the polymer azo initiator represented by the general formula (9) The relationship between the monomer component (A), monomer (a), monomer (b) and monomer (c) used (mass%) of the monomer component is the polymer azo initiator / ( Expressed as a ratio of monomer (A) + monomer (a) + monomer (b) + monomer (c)), it is preferable when monomer (a) is the main component. Is 5/95 to 99/1, more preferably 10/90 to 97/3, still more preferably 20/80 to 95/5, and particularly preferably 30/70 to 92.5 / 7.5. When the monomer (A) and / or (b) is the main component, it is preferably 2/98 to 95/5, more preferably 4/96 to 90/10, and still more preferably 8/92. To 80/20, more preferably 10/90 to 75/25, more preferably 15/85 to 70/30, more preferably 17.5 / 82.5 to 65/35, particularly preferably 20/80 to 60/40. In particular, the monomer (a) has a ratio (unit: monomer (a) / (polymer azo initiator + monomer (A) + monomer (b) + monomer (c))). % By mass), preferably 1 to 50/99 to 50, more preferably 2.5 to 40 / 97.5 to 60, and still more preferably 5 to 35/95 to 65.

Next, in addition to the polymer (i-2), that is, the polyalkylene glycol chain (PAG), the structural unit derived from the vinyl monomer (BL), and the three structural sites of Y, a hydrogen atom As a method for producing one having other structural sites other than the following general formula (12);

(In the formula, X represents a residue of a compound having 1 or 2 or more active hydrogens. R ¹⁴ represents a hydrocarbon group having 1 to 20 carbon atoms. Y ⁵ is the same or different and represents an organic residue. A ² O is the same or different and represents an oxyalkylene group having 2 to 18 carbon atoms, k is the same or different and represents the average number of added moles of the oxyalkylene group, and is a number from 1 to 1000. A method of polymerizing a vinyl monomer component in the presence of a polymeric azo initiator represented by

In the general formula (12), the residue of the compound having one or more active hydrogens represented by X is the same as X in the general formula (3). The organic residue represented by Y ⁵ are the same as the organic residue in Y ¹ in the general formula (3). The oxyalkylene group having 2 to 18 carbon atoms represented by A ² O is the same as AO in the general formula (3). The average added mole number of the oxyalkylene group represented by k is the same as n in the general formula (3). The above m is also as described above.

R ¹⁴ in the general formula (12) represents a hydrocarbon group having 1 to 20 carbon atoms, and for example, a hydrocarbon group having 1 to 4 carbon atoms is preferable. More preferably, it is a methyl group.
By using a polymer azo initiator in which m in the general formula (12) is 1 or 2, the non-multi-branched polyalkylene glycol polymer can be produced, and the general formula (12 ) Is a residue of a compound having 3 or more active hydrogens, and a polymer azo initiator having m of 3 or more is used to produce a polyalkylene glycol polymer having the above multi-branched structure be able to.

In the polymerization reaction, a polymer azo initiator having a repeating unit represented by the general formula (6) or a polymer azo initiator represented by the general formula (9) is usually used. A radical polymerization initiator may be used in combination. As the radical polymerization initiator that is usually used, any known radical polymerization initiator can be used.

Next, a method for producing the polyalkylene glycol polymer of the present invention by polymerizing the vinyl monomer component in the presence of a polymer chain transfer agent having a polyalkylene glycol chain will be described.
As such a production method, for example, the following general formula (13):

(In the formula, AO is the same or different and represents an oxyalkylene group having 2 to 18 carbon atoms. Y ⁶ represents a direct bond or an organic residue. N represents the average number of moles of the oxyalkylene group added. It is preferable to employ a production method including a step of polymerizing a vinyl monomer component in the presence of a polyalkylene glycol chain-containing compound having a structure represented by: 1 to 1000.

In the method for producing the polyalkylene glycol polymer, the polyalkylene glycol chain-containing compound may be any compound having the structure represented by the general formula (13).
Specific examples and preferred examples of the oxyalkylene group represented by AO in the general formula (13) are the same as those of the alkylene oxide having 2 or more carbon atoms constituting the polyalkylene glycol chain (I). The organic residue represented by Y ⁶ is the same as Y described above.
The polyalkylene glycol polymer to be obtained by the production method is the polymer (i-1), that is, the polyalkylene glycol chain (PAG), the structural unit derived from the vinyl monomer (BL), and , Y is a polymer composed of three structural sites, when the polyalkylene glycol chain represented by (AO) _n is located at the end of the structure of the polyalkylene glycol chain-containing compound, The alkylene glycol chain has a hydrogen atom at the terminal. That is, the terminal structure of the polyalkylene glycol chain is a hydroxyl group.

In the general formula (13), the organic residue represented by Y ⁶ is preferably a group containing a sulfur atom as described above. In this case, in this case, the sulfur atom and the general formula (13) A form in which a hydrogen atom present at the terminal is bonded is preferable. That is, the polyalkylene glycol chain-containing compound represented by the general formula (13) is preferably a compound having a mercapto group (thiol group, SH group) (hereinafter, such a compound is referred to as “polyalkylene”). Also referred to as “glycol chain-containing thiol compound”). This makes it possible to carry out the polymerization utilizing the unique reactivity of the mercapto group, and to produce the polyalkylene glycol polymer of the present invention more efficiently and simply at a low cost. Become.

In the above production method, when the polyalkylene glycol chain-containing thiol compound is used, a radical generated from the mercapto group by heat, light, radiation, or the like, or a radical generated by a polymerization initiator separately used as necessary , Chain transfer to the mercapto group, or when the mercapto groups are bonded to each other to form a disulfide bond, the disulfide bond is cleaved, and the monomers are successively introduced via the sulfur atom (S). Addition forms a structural unit derived from a vinyl monomer (site of polymer (ii)), and thus the polyalkylene glycol polymer of the present invention can be obtained efficiently.

According to the production method, the polyalkylene glycol polymer (i-1), that is, the polyalkylene glycol chain (PAG), the structural unit derived from the vinyl monomer (BL), and the three structural sites of Y are used. In the case of producing a polyalkylene glycol-based polymer, the polyalkylene glycol chain-containing thiol compound includes (poly) alkylene glycol and a thiol compound having a carboxyl group (hereinafter also simply referred to as “thiol compound”). It is preferable that it is obtained by a production method including a step of dehydrating and condensing.
In the dehydration condensation step, the thiol compound having a carboxyl group may be a mercaptocarboxylic acid group-containing compound having a carboxyl group (carboxylic acid group) and a mercapto group in one molecule.
Examples of such a mercaptocarboxylic acid group-containing compound include thioglycolic acid, 2-mercaptopropionic acid, 3-mercaptopropionic acid, mercaptoisobutyric acid, thiomalic acid, mercaptostearic acid, mercaptoacetic acid, mercaptobutyric acid, mercaptooctanoic acid. , Mercaptobenzoic acid, mercaptonicotinic acid, cysteine, N-acetylcysteine, mercaptothiazole acetic acid and the like. Among these, thioglycolic acid, 3-mercaptopropionic acid, thiomalic acid, and mercaptoisobutyric acid are preferable.

In the dehydration condensation step of the (poly) alkylene glycol and the thiol compound, it is preferable that a dehydration condensation reaction is performed between the hydroxyl group of the (poly) alkylene glycol and the carboxyl group of the thiol compound. Such a reaction can be carried out using an ordinary ester reaction method in a normal liquid phase. Alternatively, the pressure may be reduced or an entrainer such as xylene may be used.
In addition, from the property of the mercapto group which the said thiol compound has, it is suitable to perform the said dehydration condensation process under an acid catalyst. The acid catalyst is as described above.
As described above, the dehydration condensation step of the (poly) alkylene glycol and the thiol compound is preferably an esterification reaction step using an acid catalyst.

The mixing ratio of the (poly) alkylene glycol and the thiol compound may be appropriately set according to the desired purity, cost, reaction rate, synthesis method, etc. of the polyalkylene glycol chain-containing thiol compound. For example, when it is desired to obtain a highly pure polyalkylene glycol chain-containing thiol compound in a short time, the molar ratio of the carboxyl group of the thiol compound to the amount of hydroxyl group provided for the reaction of the (poly) alkylene glycol. A large excess is preferred. Specifically, from the viewpoint of reaction rate, the molar ratio is preferably 2 times or more, more preferably 3 times or more, and from the viewpoint of production cost, it is preferably 10 times or less, More preferably, it is 5 times or less. In addition, although the crude product after reaction may be used as it is, it may refine | purify as needed and an unreacted substance may be removed.

The reaction time of the dehydration condensation step may be appropriately set according to the type and amount of the acid catalyst used, the mixing ratio of the (poly) alkylene glycol and the thiol compound, the solution concentration, and the like.

The reaction crude product obtained by the dehydration condensation step is solidified by cooling the reaction solution after the dehydration condensation step (that is, the pH-adjusted reaction solution) or the pH-adjusted reaction solution to room temperature. Is preferred. Thereby, the reaction crude product can be easily obtained from the reaction solution. The solidified product of the obtained reaction crude product may be purified. In this case, after solidifying the reaction crude product is dried and ground, impurities such as unreacted raw material compounds dissolve. The solidified product may be washed using a solvent that does not dissolve the thiol compound, such as diethyl ether.

In the present invention, the polymerization reaction of the vinyl monomer component is carried out in the presence of a polyalkylene glycol chain-containing compound typified by the polyalkylene glycol chain-containing thiol compound thus obtained.
For example, when the polymerization reaction is carried out in the presence of the polyalkylene glycol chain-containing thiol compound, monomers are successively added via the terminal sulfur atom (S) as described above, and the polymer ( ii) is formed, and thus the polymer (i) of the present invention is produced as a main component. However, the structure of the polymer (ii) is repeated two or more times, or the monomer (A ), A monomer (a), a monomer (b), and a polymer having a structural unit derived from one or more monomers among the monomers (c) may be produced as a secondary product.

The amount of the polyalkylene glycol chain-containing compound (preferably polyalkylene glycol chain-containing thiol compound) used in the polymerization reaction is 1 to 99 parts by weight with respect to 100 parts by weight of the vinyl monomer component. Is preferred. If the amount is 1 part by weight or less, the effect due to the polyalkylene glycol chain-containing compound may not be sufficiently exhibited. If the amount exceeds 99 parts by weight, the performance derived from the vinyl monomer may not be sufficiently exhibited. is there. The lower limit of the amount used is more preferably 2 parts by weight, still more preferably 4 parts by weight, and the upper limit is more preferably 80 parts by weight, still more preferably 50 parts by weight. Yes, still more preferably 30 parts by weight, particularly preferably 15 parts by weight.

The polymerization reaction can be performed by a method such as solution polymerization or bulk polymerization using a radical polymerization initiator as necessary.
Among the solution polymerizations described above, in aqueous solution polymerization, it is preferable to use a water-soluble radical polymerization initiator because it is not necessary to remove insoluble components after polymerization. For example, persulfates such as ammonium persulfate, sodium persulfate, and potassium persulfate; hydrogen peroxide; azoamidine compounds such as 2,2′-azobis-2-methylpropionamidine hydrochloride, 2,2′-azobis-2- Cyclic azoamidine compounds such as (2-imidazolin-2-yl) propane hydrochloride, azonitrile compounds such as 2-carbamoylazoisobutyronitrile, 2,4′-azobis {2-methyl-N- [2- (1- Water-soluble azo initiators such as azoamide compounds such as (hydroxybutyl)] propionamide}, macroazo compounds such as esters of 4,4′-azobis (4-cyanovaleric acid) and (alkoxy) polyethylene glycol, These 1 type (s) or 2 or more types can be used.

In solution polymerization and bulk polymerization using lower alcohols, aromatic or aliphatic hydrocarbons, esters or ketones as solvents, radical polymerization initiators such as benzoyl peroxide, lauroyl peroxide, sodium peroxide, etc. Peroxides such as t-butyl hydroperoxide and cumene hydroperoxide; azonitrile compounds such as azobisisobutyronitrile, 2,4′-azobis {2-methyl-N- [2- (1- Hydroxybutyl)] propionamide} and other water-soluble azo initiators such as macroazo compounds such as esters of 4,4′-azobis (4-cyanovaleric acid) and (alkoxy) polyethylene glycol Or 2 or more types can be used. Among these, a water-soluble azo initiator is preferable as will be described later. In this case, an accelerator such as an amine compound can be used in combination.
Furthermore, when using a mixed solvent of water and a lower alcohol, it can be appropriately selected from the above-mentioned various radical polymerization initiators or a combination of the above radical polymerization initiator and accelerator.

In the polymerization reaction, a normal chain transfer agent may be used in combination. Examples of chain transfer agents that can be used include thiol chain transfer agents such as mercaptoethanol, thioglycerol, thioglycolic acid, 3-mercaptopropionic acid, thiomalic acid, and 2-mercaptoethanesulfonic acid; secondary such as isopropyl alcohol Alcohol; phosphorous acid, hypophosphorous acid and salts thereof (sodium hypophosphite, potassium hypophosphite, etc.), sulfurous acid, hydrogen sulfite, dithionite, metabisulfite and salts thereof (sodium sulfite, hydrogen sulfite) And hydrophilic chain transfer agents such as lower oxides of sodium, sodium dithionite, sodium metabisulfite, and the like, and salts thereof.

The chain transfer agents may be used alone or in combination of two or more, and for example, a hydrophilic chain transfer agent and a hydrophobic chain transfer agent may be used in combination.
The amount of the chain transfer agent used may be appropriately set according to the aspect and amount of the polyalkylene glycol chain-containing thiol compound, but is preferably 0.1 mol with respect to the total amount of vinyl monomer components of 100 mol. More preferably, it is 0.25 mol or more, more preferably 0.5 mol or more, preferably 20 mol or less, more preferably 15 mol or less, and still more preferably 10 mol or less.

In the above polymerization reaction, the polymerization conditions such as the polymerization temperature are appropriately determined depending on the polymerization method used, the solvent, the polymerization initiator, and the chain transfer agent, but the polymerization temperature is preferably 0 ° C. or higher, It is preferable that it is 150 degrees C or less. More preferably, it is 30 degreeC or more, More preferably, it is 50 degreeC or more. More preferably, it is 120 degrees C or less, More preferably, it is 100 degrees C or less.

The method for charging the vinyl monomer component into the reaction vessel is not particularly limited, and a method in which the entire amount is initially charged into the reaction vessel; a method in which the entire amount is divided or continuously charged into the reaction vessel; Any of the methods of initially charging the reaction vessel into the reaction vessel and dividing or continuously charging the remainder into the reaction vessel may be used. The radical polymerization initiator and the chain transfer agent 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.

The reaction product obtained by the above polymerization reaction may contain various polymers as by-products as described above in addition to the polyalkylene glycol-based polymer. Although you may attach to the process to isolate, you may use for various uses normally, without isolating each polymer from viewpoints, such as working efficiency and manufacturing cost.

By the production method (a production method including a step of polymerizing a vinyl monomer component in the presence of a polyalkylene glycol chain-containing compound), the polyalkylene glycol polymer (i-2), that is, the polyalkylene glycol chain. (PAG), a structural unit derived from a vinyl monomer (BL), and in addition to the three structural sites of Y, when producing a polyalkylene glycol polymer having other structural sites other than hydrogen atoms, The production method comprises the following general formula (14):

(In the formula, X represents a residue of a compound having one or more active hydrogens. AO is the same or different and represents an oxyalkylene group having 2 to 18 carbon atoms. Y ¹ is the same or different. And n is the same or different and represents the average number of added moles of the oxyalkylene group, which is a number from 1 to 1000. m is an integer from 1 to 50. A step of polymerizing the vinyl monomer component in the presence of the polyalkylene glycol chain-containing compound.

In the general formula (14), a residue of a compound having one or more active hydrogens represented by X, an oxyalkylene group having 2 to 18 carbon atoms represented by AO, and an organic residue represented by Y ¹ The average added mole number of the group and the oxyalkylene group represented by n is as described above. M represents the number of polyalkylene glycol chains bonded to the polymer (ii) through an organic residue to which a compound having an active hydrogen represented by X or a hydrogen atom is bonded, and this is also described above. Just as you did.

When the polyalkylene glycol polymer (i-2) is produced, the polyalkylene glycol chain-containing thiol compound includes a compound obtained by adding alkylene oxide to a compound having active hydrogen, and a thiol compound having a carboxyl group. It is preferable that it is obtained by a production method including a step of dehydrating and condensing.
In such a production method, as described above, the compound having active hydrogen is preferably an alcohol, an amine, an imine, an amide compound or the like, and among them, an amine, a (poly) alkyleneimine, and an alcohol are preferable. These are as described above.
The alkylene oxide is also as described above.
The reaction molar ratio between the compound having active hydrogen and the alkylene oxide is preferably set as appropriate so that the average number of repetitions of the alkylene oxide in the polyalkylene glycol chain is within the preferable range.

As a method for adding alkylene oxide to the compound having active hydrogen, polymerization can be carried out by a usual method, and a method using an acid catalyst or an alkali catalyst is preferable. As the acid catalyst, Lewis acid catalysts such as boron trifluoride, metal and metalloid halogen compounds; mineral acids such as hydrogen chloride, hydrogen bromide and sulfuric acid; paratoluenesulfonic acid and the like are suitable, and alkali catalysts Is preferably potassium hydroxide, sodium hydroxide or sodium hydride.

The reaction time in the addition reaction step may be appropriately set according to the type and amount of the catalyst used, the number of moles of the alkylene oxide added to the compound having one or more active hydrogens, the solution concentration, and the like.
A commercially available compound can also be used as a compound obtained by adding alkylene oxide to the compound having active hydrogen (hereinafter also simply referred to as “addition product”).

In the production method, the polyalkylene glycol chain-containing thiol compound is obtained by dehydrating and condensing a compound obtained by adding alkylene oxide to the compound having active hydrogen thus obtained and a thiol compound having a carboxyl group. Can be obtained. This dehydration condensation step is as described above.
In addition, by performing a polymerization reaction of the vinyl monomer component in the presence of a polyalkylene glycol chain-containing compound typified by the polyalkylene glycol chain-containing thiol compound thus obtained, the above polyalkylene glycol-based polymer can be obtained. Combined (i-2) can be obtained. The polymerization reaction of the vinyl monomer component is as described above.

The polyalkylene glycol polymer (i) of the present invention can be suitably used for various applications such as adhesives, sealing agents, components for imparting flexibility to various polymers, cement admixtures, detergent builders and the like. In particular, as described above, since extremely high cement dispersion performance and slump retention performance can be exhibited, it is preferable to use it for cement admixture. Thus, a cement admixture containing the polyalkylene glycol polymer is also one aspect of the present invention.
The cement admixture can be used in addition to a cement composition such as cement paste, mortar, concrete, etc., and such a cement composition containing the cement admixture is also one aspect of the present invention.

As the above-mentioned cement composition, those containing cement, water, fine aggregate, coarse aggregate, and the like are suitable. 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 exothermic cement (low exothermic blast furnace cement, fly ash mixed low exothermic blast furnace cement, high content of belite); ultra high strength cement; cement-based solidified material; Cement produced from one or more of incineration ash and sewage sludge incineration ash G) other such, 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.
As the above aggregate, in addition to gravel, crushed stone, granulated slag, recycled aggregate, etc., siliceous, clay, zircon, high alumina, silicon carbide, graphite, chrome, chromic, magnesia, etc. Refractory aggregate and the like.

Examples of the unit water amount per 1 m ³ of the cement composition, the cement use amount, and the water / cement ratio (mass ratio) include, for example, a unit water amount of 100 to 185 kg / m ³ , a use cement amount of 200 to 800 kg / m ³ , and a water / cement ratio. The cement ratio (mass ratio) is preferably 0.1 to 0.7, and more preferably, the unit water amount is 120 to 175 kg / m ³ , the cement amount used is 250 to 800 kg / m ³ , and the water / cement ratio ( (Mass ratio) = 0.2 to 0.65. Thus, the cement admixture containing the polymer (i) of the present invention can be used in a wide range from poor blending to rich blending, and has a high water reduction rate region, that is, a water / cement ratio (mass ratio). ) = 0.15 to 0.5 (preferably 0.15 to 0.4), and can be used in an area where the water / cement ratio is low. Further, the high-strength concrete has a large unit cement amount and a small water / cement ratio. It is effective for any poor blended concrete having a unit cement amount of 300 kg / m ³ or less.

As the cement admixture of the present invention, the fluidity, retention and workability can be exhibited with high performance in a balanced manner even in a high water reduction rate region, and since it has excellent workability, ready-mixed concrete, concrete secondary products ( It can be used effectively for concrete for precast concrete), concrete for centrifugal molding, concrete for vibration compaction, steam-cured concrete, shotcrete, etc. Furthermore, medium-fluidity concrete (slump value is 22-25cm) Mortar and concrete that require high fluidity, such as concrete with high fluidity (concrete with a slump value of 25 cm or more and a slump flow value of 50 to 70 cm), self-filling concrete, self-leveling material, etc. Also effective.

When the cement admixture is used in a cement composition, the blending ratio of the polymer (i), which is an essential component of the present invention, is 0 with respect to 100 mass% of the total mass of cement in terms of solid content. It is preferable to set it to be 0.01 to 10% by 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 0.02-8 mass%, More preferably, it is 0.05-6 mass%.

The cement admixture can also be used in combination with other cement additives. As another cement additive, 1 type (s) or 2 or more types, such as a cement additive (material) as shown below, can be used, for example. Among these, it is particularly preferable to use an oxyalkylene antifoaming agent or an AE agent in combination.
In addition, it is suitable for the addition ratio of a cement additive to be 0.0001-10 weight part with respect to 100 weight part of solid content of the said polymer (i).

(1) Water-soluble polymer substances: polyacrylic acid (sodium), polymethacrylic acid (sodium), polymaleic acid (sodium), unsaturated carboxylic acid polymer such as sodium salt of acrylic acid / maleic acid copolymer; polyethylene Polymers of polyoxyethylene or polyoxypropylene such as glycol and polypropylene glycol or copolymers thereof; Nonionic cellulose ethers such as methylcellulose, ethylcellulose, hydroxymethylcellulose, hydroxyethylcellulose, carboxymethylcellulose, carboxyethylcellulose, hydroxypropylcellulose, etc. Yeast glucan, xanthan gum, β-1,3 glucans (both linear and branched), for example, curdlan, paramylon, pachyman, Polyacrylamide; polyvinyl alcohol; starch; starch phosphate ester; sodium alginate; gelatin; copolymer of acrylic acid having an amino group in the molecule and its four Grade compounds and the like.

(2) Polymer emulsion.
(3) Retardant: Gluconic acid, malic acid or citric acid, and oxycarboxylic acids such as inorganic salts or organic salts such as sodium, potassium, calcium, magnesium, ammonium, triethanolamine, and salts thereof; glucose , Fructose, galactose, saccharose; sugar alcohols such as sorbitol; magnesium silicate; phosphoric acid and its salts or borate esters; aminocarboxylic acid and its salts; alkali-soluble protein; humic acid; tannic acid; Polyhydric alcohols such as aminotri (methylenephosphonic acid), 1-hydroxyethylidene-1,1-diphosphonic acid, ethylenediaminetetra (methylenephosphonic acid), diethylenetriaminepenta (methylenephosphonic acid) and alkali metal salts thereof, al Phosphonic acids and derivatives thereof such as Li earth metal salts.

(4) Early strengthening agent / accelerator: soluble calcium salt such as calcium chloride, calcium nitrite, calcium nitrate, calcium bromide, calcium iodide; alkanolamine; alumina cement; calcium aluminate silicate.
(5) Mineral oil-based antifoaming agent: cocoon oil, liquid paraffin, etc.
(6) Fat and oil-based antifoaming agents: animal and vegetable oils, sesame oil, castor oil, alkylene oxide adducts thereof and the like.
(7) Fatty acid-based antifoaming agent: oleic acid, stearic acid, and these alkylene oxide adducts.
(8) Fatty acid ester antifoaming agent: glycerin monoricinoleate, alkenyl succinic acid derivative, sorbitol monolaurate, sorbitol trioleate, natural wax and the like.

(9) Oxyalkylene antifoaming agents: polyoxyalkylenes such as (poly) oxyethylene (poly) oxypropylene adducts; diethylene glycol heptyl ether, polyoxyethylene oleyl ether, polyoxypropylene butyl ether, polyoxyethylene polyoxypropylene (Poly) oxyalkyl ethers such as 2-ethylhexyl ether and higher alcohols having 12 to 14 carbon atoms such as oxyethyleneoxypropylene adducts; (poly) oxy such as polyoxypropylene phenyl ether and polyoxyethylene nonylphenyl ether Alkylene (alkyl) aryl ethers; 2,4,7,9-tetramethyl-5-decyne-4,7-diol, 2,5-dimethyl-3-hexyne-2,5-diol, 3-methyl-1 -Bu Acetylene ethers obtained by addition polymerization of alkylene oxide to acetylene alcohol such as n-3-ol; (poly) oxyalkylene fatty acid esters such as diethylene glycol oleate, diethylene glycol laurate, ethylene glycol distearate; polyoxyethylene (Poly) oxyalkylene sorbitan fatty acid esters such as sorbitan monolaurate and polyoxyethylene sorbitan trioleate; (poly) oxyalkylene alkyl such as sodium polyoxypropylene methyl ether sulfate and sodium polyoxyethylene dodecylphenol ether sulfate ( Aryl) ether sulfate esters; (poly) oxyethylene stearyl phosphates, etc. Polyoxyalkylene alkyl phosphoric acid esters; polyoxyethylene such as polyoxyethylene lauryl amine (poly) oxyalkylene alkyl amines; polyoxyalkylene amide.

(10) Alcohol-based antifoaming agent: octyl alcohol, hexadecyl alcohol, acetylene alcohol, glycols and the like.
(11) Amide antifoaming agent: acrylate polyamine and the like.
(12) Phosphate ester antifoaming agent: tributyl phosphate, sodium octyl phosphate, etc.
(13) Metal soap type antifoaming agent: aluminum stearate, calcium oleate, etc.
(14) Silicone antifoaming agent: dimethyl silicone oil, silicone paste, silicone emulsion, organically modified polysiloxane (polyorganosiloxane such as dimethylpolysiloxane), fluorosilicone oil and the like.
(15) AE agent: resin soap, saturated or unsaturated fatty acid, sodium hydroxystearate, lauryl sulfate, ABS (alkyl benzene sulfonic acid), LAS (linear alkyl benzene sulfonic acid), alkane sulfonate, polyoxyethylene alkyl (phenyl) ether , Polyoxyethylene alkyl (phenyl) ether sulfate or a salt thereof, polyoxyethylene alkyl (phenyl) ether phosphate or a salt thereof, protein material, alkenyl sulfosuccinic acid, α-olefin sulfonate, and the like.

(16) Other surfactants: aliphatic monohydric alcohols having 6 to 30 carbon atoms in the molecule such as octadecyl alcohol and stearyl alcohol, and those having 6 to 30 carbon atoms in the molecule such as abiethyl alcohol Intramolecular such as alicyclic monohydric alcohol, dodecyl mercaptan, etc. Intramolecular such as monovalent mercaptan having 6-30 carbon atoms in the molecule, such as nonylphenol, alkylphenol having 6-30 carbon atoms in the molecule, dodecylamine, etc. 10 mol or more of an alkylene oxide such as ethylene oxide or propylene oxide was added to a carboxylic acid having 6 to 30 carbon atoms in the molecule such as an amine having 6 to 30 carbon atoms, lauric acid or stearic acid. Polyalkylene oxide derivatives; having an alkyl group or alkoxyl group as a substituent Alkyl diphenyl ether sulfonates in which two phenyl groups having a sulfone group are ether-bonded; various anionic surfactants; various cationic surfactants such as alkylamine acetate and alkyltrimethylammonium chloride; various nonions Surfactants; various amphoteric surfactants.
(17) Waterproofing agent: fatty acid (salt), fatty acid ester, oil and fat, silicon, paraffin, asphalt, wax and the like.
(18) Rust preventive: nitrite, phosphate, zinc oxide and the like.
(19) Crack reducing agent: polyoxyalkyl ethers; alkanediols such as 2-methyl-2,4-pentanediol.
(20) Expansion material: Ettlingite, coal, etc.

Other cement additives (materials) include, for example, cement wetting agents, thickeners, separation reducing agents, flocculants, drying shrinkage reducing agents, strength enhancing agents, self-leveling agents, rust preventives, colorants, antifungal agents , Blast furnace slag, fly ash, cinder ash, clinker ash, husk ash, silica fume, silica powder, gypsum and the like.

Since the polyalkylene glycol polymer of the present invention has the above-described configuration and can exhibit extremely excellent dispersion performance and slump retention performance, it is useful for various applications, particularly cement admixture applications.

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, “%” means “mass%” and “part” means “part by weight”. “Wt%” means “mass%”.
First, as an analysis method for polyalkylene glycol chain-containing thiol compounds, polymers thereof and comparative polymers, liquid chromatography (LC) analysis conditions / analysis conditions, and gel permeation chromatography (GPC) analysis conditions / analysis conditions Will be described. A measurement method for obtaining these solid contents will also be described.

<LC analysis method>
Device: Waters Alliance (2695)
Analysis software: Waters Empower Professional + GPC option column: Waters Atlantis dC18 guard column + column (particle size 5 μm, inner diameter 4.6 mm × 250 mm × 2)
Detector: differential refractometer (RI) detector (Waters 2414), multi-wavelength visible ultraviolet (PDA) detector (Waters 2996)
Eluent: A mixture of acetonitrile / 100 mM acetate ion exchange aqueous solution = 40/60 (mass%) adjusted to pH 4.0 by adding 30% NaOH aqueous solution Flow rate: 1.0 mL / min Column temperature: 40 ° C.
Sample solution injection amount: 100 μL (eluent solution having a sample concentration of 1 to 2% by mass)

<LC analysis conditions: consumption rate of raw material alcohol (adduct) and average number of introduced SH>
The consumption rate of alcohol (adduct) as a raw material component was estimated as follows.
According to LC analysis, no mercapto group was introduced (unreacted raw material), polyalkylene glycol chain-containing thiol compound into which one mercapto group was introduced (also referred to as “PAG thiol compound”), ..., mercapto The peak of the PAG thiol compound into which (m + p) groups have been introduced is separated. These RI (differential refractometer) area ratios (%) were S ₀ , S ₁ ,... S _{m + p,} and the consumption rate of alcohol as a raw material component was estimated by the following formula (1).

Moreover, the average number of SH introduction | transduction in a PAG thiol compound was estimated by the following formula | equation (2).

<GPC analysis method>
The weight average molecular weight, number average molecular weight, and peak top molecular weight of the polyalkylene glycol chain-containing thiol polymer and the comparative polymer were measured under the following measurement conditions.
Device: Waters Alliance (2695)
Analysis software: Waters, Empor professional + GPC option column: Tosoh Co., Ltd., TSKguardcolumns SWXL + TSKgel G4000SWXL + G3000SWXL + G2000SWXL
Detector: differential refractometer (RI) detector (Waters 2414), multi-wavelength visible ultraviolet (PDA) detector (Waters 2996)
Eluent: A solution prepared by dissolving 115.6 g of sodium acetate trihydrate in a mixed solvent of 10999 g of water and 6001 g of acetonitrile, and further adjusting the pH to 6.0 with acetic acid. Standard material for preparing a calibration curve: polyethylene glycol (peak top molecular weight (Mp ) 272500, 219300, 107000, 50000, 24000, 12600, 7100, 4250, 1470)
Calibration curve: Flow rate prepared by cubic equation based on Mp value of polyethylene glycol and elution time: 1 mL / min Column temperature: 40 ° C
Measurement time: 45 minutes Sample solution injection amount: 100 μL (PAG, PAG thiol compound is an eluent solution having a sample concentration of 0.4% by mass, and polymer is a sample concentration of 0.5% by mass)

<GPC analysis condition 1 (analysis of PAG thiol compound (monomer))>
In the RI chromatogram, the flat and stable portions in the baseline immediately before and after elution were connected with straight lines, and peaks were detected and analyzed. When a multimer or an impurity was measured partially overlapping the target peak, the molecular weight of the target product was measured by vertically dividing at the most concave portion of the overlapping portion of the peak.
Calculation of pure monomer content and multimer content;
From the ratio of the peak area by the RI detector, the calculation was performed as follows.
Monomer pure amount = (PAG thiol compound area) / (multimer peak area + PAG thiol compound area)
Multimerized product amount = (multimerized product peak area) / (multimerized product peak area + PAG thiol compound area)

<GPC analysis condition 2 (analysis of polymer)>
In the obtained RI chromatogram, the portions that were flat and stable in the baseline immediately before and after elution of the polymer were connected with a straight line, and the polymer was detected and analyzed. However, when the peak of the monomer or monomer-derived impurity is measured partially overlapping the polymer peak, the polymer part and the monomer are divided vertically at the most concave part of the overlapping part of the polymer and the polymer peak. The molecular weight and molecular weight distribution of only the polymer part were measured. When the polymer part and other parts could not be completely overlapped and separated, they were calculated together.
Calculation of polymer purity:
From the ratio of the peak area by the RI detector, the calculation was performed as follows.
Polymer pure content = (polymer peak area) / (polymer peak area + monomer or impurity peak area)

<Measurement of solid content (analysis of PAG thiol compound and polymer)>
About 0.5 g of the sample was weighed on an aluminum dish and diluted with about 1 g of water to spread it uniformly. The sample was dried at 130 ° C. for 1 hour in a nitrogen atmosphere, allowed to cool in a desiccator, and then weighed after drying. The solid content (nonvolatile content) concentration was calculated from the difference in mass before and after drying.
As the concentration of the aqueous solution of the PAG thiol compound or polymer, the solid content measured by the above procedure was used unless otherwise specified.

<Polyalkylene glycol chain-containing thiol compound (PAG thiol compound)>
Production Example 1
(1) Dehydration esterification reaction process In a glass reactor equipped with a Dean-Stark device with a Dimroth condenser, a Teflon (R) stirring blade and a stirring seal, and a temperature sensor with a glass protective tube, Polyalkylene glycol (PEG-100, manufactured by Nippon Shokubai Co., Ltd., 1500.00 g), 3-mercaptopropionic acid (3-MPA, manufactured by Wako Pure Chemical Industries, Ltd., 80.34 g), p-toluene Sulfonic acid-hydrate (PTS, Wako Pure Chemical Industries, 31.61 g), phenothiazine (PTZ, Wako Pure Chemical Industries, 0.7902 g), and cyclohexane (79.02 g) were charged. After the Dean-Stark apparatus was filled with cyclohexane, the reaction system was heated to reflux while stirring. The temperature of the heating oil bath was 120 ± 5 ° C. The reaction was completed by heating and refluxing for 40.0 hours while adding cyclohexane in the middle so that the temperature in the reaction system became 110 ± 5 ° C.

(2) Solvent removal step After completion of the reaction, the mixture was allowed to cool to 60 ° C. with stirring so as not to solidify, and then rapidly reacted with an aqueous solution obtained by adding water (1507.51 g) to a 30% aqueous NaOH solution (21.05 g). It was put into the vessel. Subsequently, the temperature was gradually raised to about 100 ° C., and cyclohexane was distilled off. The heating was stopped and nitrogen was bubbled at 30 mL / min for 90 minutes while cooling to remove residual cyclohexane to obtain an aqueous solution of the target compound (PAG thiol compound (1)).
As a result of LC analysis of the obtained target compound, the consumption rate of PEG-100 was 100.0%, and the average number of SH introduced per molecule of PEG-100 was 1.95. As a result of GPC analysis, the monomer amount was 94.2%, and the remainder was a multimer.

Production Example 2
An aqueous solution of the target compound (PAG thiol compound (2)) was obtained in the same manner as in Production Example 1 except that the raw material compounds and reaction conditions in Production Example 1 were changed as shown in Tables 1 and 2.
The results of LC analysis and GPC analysis are shown in Table 2.

Abbreviations in Tables 1 and 2 are as follows.
T-51: PAG thiol compound (1)
T-34: PAG thiol compound (2)
PEG-100: Polyethylene glycol (average EO addition mole number 100)
PEG-43: Polyethylene glycol (average EO addition moles 43)
3-MPA: 3-mercaptopropionic acid PTS · 1H ₂ O: p-toluenesulfonic acid monohydrate PTZ: phenothiazine

<Polyalkylene glycol chain-containing thiol polymer>
Example 1
As a monomer solution, sodium methacrylate (SMAA, manufactured by Nippon Shokubai Co., Ltd., 4.33 g), methacrylic acid (MAA, manufactured by Nippon Shokubai Co., Ltd., 31.07 g), methoxypolyalkylene glycol methacrylate (10 mol of ethylene oxide of methanol, propylene) 2 mol of oxide, 13 mol of ethylene oxide ABA block adduct methacrylate, ME23P2E, 173.35 g), PAG thiol compound (1) obtained in Production Example 1 (T-51, 16.25 g), hydroxylation A solution of sodium (NaOH, 1.44 g) and ion-exchanged water (86.06 g) was prepared.
As an initiator solution, a solution of 2,2′-azobis (2-methylpropionamidine) dihydrochloride (V-50, manufactured by Wako Pure Chemical Industries, Ltd., 0.29 g) and ion-exchanged water (49.71 g) was prepared.
Dimroth condenser, Teflon (R) stirrer and stirrer with stir seal, nitrogen introduction tube, glass reaction vessel equipped with temperature sensor, charged with ion exchange water (137.50 g), with stirring at 250 rpm, The mixture was heated to 80 ° C. while introducing nitrogen at 200 mL / min.
Subsequently, the monomer solution was dropped into the reaction vessel over 4 hours and the initiator solution over 5 hours. The polymerization reaction was completed by maintaining at 80 ° C. for 1 hour after completion of the dropping. After cooling to room temperature, a 30% aqueous NaOH solution was added to adjust the pH to 6.0 to obtain an aqueous solution of the target polymer (polymer (1)).
As a result of GPC analysis, the polymer was Mw = 54200, Mp = 47400, and Mn = 25600. The pure polymer content was 89.8%.

Examples 2 to 4 and Comparative Examples 1 to 4
In Example 1, the target polymer (polymer (2) to An aqueous solution of (4) and polymers (c1) to (c4)) was obtained. Table 4 shows the GPC analysis results.

Abbreviations in Tables 3 and 4 are as follows.
SMAA: sodium methacrylate MAA: methacrylic acid ME23P2E: methoxy polyalkylene glycol methacrylate (methacrylate of ABA block adduct of 10 mol of methanol, 2 mol of propylene oxide, 13 mol of ethylene oxide)
ME9P1E: Methoxypolyalkylene glycol methacrylate (methacrylate of ABA block adduct of 6 mol of methanol, 1 mol of propylene oxide, 3 mol of ethylene oxide)
ME25E: Methoxypolyethylene glycol methacrylate (average number of moles of ethylene oxide addition 25)
ME10E: Methoxypolyethylene glycol methacrylate (average number of moles of ethylene oxide added 10)
T-51: PAG thiol compound (1)
T-34: PAG thiol compound (2)

<Method for evaluating cement dispersion performance: mortar test>
Mortar Examples 1 to 3 and Mortar Comparative Examples 1 to 3
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 = 550/1350/220 (g). However,
C: Ordinary Portland cement (manufactured by Sumitomo Osaka Cement)
S: Standard sand for cement strength test (Cement Association)
W: As the ion exchange aqueous solution W of the polymer of the present invention or the comparative polymer and the antifoaming agent, the addition amount of the polymer aqueous solution shown in Table 5 was weighed, and the antifoaming agent MA-404 (Pozoris product) was used. In solid form, 10% 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 5, 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 container to a 1 L polyethylene container, stirred with a spatula 20 times, and then immediately packed in a half of the 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 5 shows the 15-stroke flow value immediately after mortar preparation (initial), 15 minutes and 30 minutes.
The 0-stroke flow value and the 15-stroke flow value are more excellent in dispersion performance as the numerical value is larger.

<Method of measuring the amount of mortar air>
About 200 mL of mortar was packed in a 500 mL glass graduated cylinder, struck with a round bar having a diameter of 8 mm, and gently bubbled by hand to remove coarse bubbles. Further, about 200 mL of mortar was added and air bubbles were similarly removed. Then, the volume and mass of the mortar were measured, and the amount of air was calculated from the density of each material. The results are shown in Table 5.

<Evaluation of mortar state>
The state of the prepared mortar was visually observed and evaluated according to the following criteria. The results are shown in Table 5.
○: Cement paste and sand are well integrated, and the mortar surface is smooth and uniform.
Δ: Coarse bubbles are seen on the mortar surface or sand is floating.
X: Remarkably coarse bubbles are conspicuous on the mortar surface, or sand is remarkably floated.

From the above Examples and Comparative Examples, the following was found.
In each mortar example using the polyalkylene glycol polymer of the present invention, the corresponding comparative polymer (the polyalkylene glycol chain of the unsaturated polyalkylene glycol monomer does not contain an oxyalkylene group having 3 or more carbon atoms) It was found that the state of the mortar was improved as compared with each of the mortar comparative examples using. The improvement of mortar condition is thought to contribute to the improvement of pumpability and workability of concrete.
Thus, it was confirmed that there is a technical significance in using the polyalkylene glycol polymer of the present invention in terms of improving the mortar state and workability.

Claims (9)

A polymer having a structural unit derived from a vinyl monomer and a polyalkylene glycol chain in the main chain,
The polymer has a structure in which a terminal oxygen atom at at least one terminal of the polyalkylene glycol chain is bonded to a main chain terminal of a constituent unit derived from the vinyl monomer directly or through an organic residue. Have
The vinyl monomer essentially contains an unsaturated polyalkylene glycol monomer having a polyalkylene glycol chain having an oxyalkylene group having 3 or more carbon atoms as an essential component. . A polymer containing a polyalkylene glycol chain and having a multi-branched structure,
In the polymer, 3 or more polyalkylene glycol chains are bonded to the residue of a compound having 3 or more active hydrogens, and the terminal oxygen atom at at least one other end of the polyalkylene glycol chain is directly or organically bonded. It has a structure bonded to the main chain end of a structural unit derived from a vinyl monomer via a residue,
The vinyl monomer essentially contains an unsaturated polyalkylene glycol monomer having a polyalkylene glycol chain having an oxyalkylene group having 3 or more carbon atoms as an essential component. . The unsaturated polyalkylene glycol monomer having a polyalkylene glycol chain essentially comprising an oxyalkylene group having 3 or more carbon atoms is 100 mol% of all oxyalkylene groups constituting the polyalkylene glycol chain of the monomer. The polyalkylene glycol polymer according to claim 1, wherein the polyalkylene glycol polymer contains 5 mol% or more of the oxyalkylene group having 3 or more carbon atoms. The polyalkylene glycol polymer according to any one of claims 1 to 3, wherein the vinyl monomer essentially contains an unsaturated carboxylic acid monomer. The polyalkylene glycol polymer according to any one of claims 1 to 4, wherein the organic residue contains a sulfur atom. The polyalkylene glycol chain according to any one of claims 1 to 5, wherein the polyalkylene glycol chain has an average number of alkylene oxide repeats of 5 to 1000. The polyalkylene glycol polymer has the following general formula (5):

(In the formula, X ′ represents a residue of a compound having one or more active hydrogens, a group represented by ZY ¹ — or a hydrogen atom. AO is the same or different and has 2 to 2 carbon atoms. 18 represents an oxyalkylene group, Y ¹ is the same or different, and represents a direct bond or an organic residue, Z is the same or different, and a polyalkylene glycol chain essentially having an oxyalkylene group having 3 or more carbon atoms. Represents a polymer that forms a structural unit derived from a vinyl-based monomer that essentially contains an unsaturated polyalkylene glycol-based monomer having n, wherein n is the same or different and represents the average number of moles of oxyalkylene groups added The polyalkylene glycol polymer according to any one of claims 1 to 6, wherein m is an integer of 1 to 50. . A cement admixture comprising the polyalkylene glycol polymer according to any one of claims 1 to 7. A cement composition comprising the cement admixture according to claim 8.