JP2013249237A - Polyalkylene glycol-based polymer, inorganic particle dispersant, inorganic particle admixture, and inorganic particle composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a polyalkylene glycol-based polymer capable of showing especially excellent retentivity, and useful for various applications, especially for application to a dispersant or an admixture of inorganic particles such as cement, and to provide a dispersant (inorganic particle dispersant), an admixture (inorganic particle admixture) and an inorganic particle composition using the same.SOLUTION: In a polyalkylene glycol-based polymer, which is a polymer having a structural unit derived from a vinyl monomer and a polyalkylene glycol chain in a main chain, the polymer has a structure in which a terminal oxygen atom on at least one terminal of a polyalkylene glycol chain is bonded to a main chain terminal of the structural unit derived from the vinyl monomer directly or through an organic residue, wherein the vinyl monomer contains a 1-99 mol% monomer having a hydrolyzable group with respect to the 100 mol% total amount of the vinyl monomer, and contains a 1-99 mol% unsaturated polyalkylene glycol-based polymer.

Description

The present invention relates to a polyalkylene glycol polymer, an inorganic particle dispersant, an inorganic particle admixture, and an inorganic particle composition. More specifically, a polyalkylene glycol polymer used for various applications such as an inorganic particle admixture such as a cement admixture or a detergent builder, an inorganic particle dispersant, an inorganic particle admixture and an inorganic particle obtained using the same. Relates to the composition.

A polymer containing a polyalkylene glycol chain (hereinafter also referred to as a polyalkylene glycol-based polymer) can have hydrophilicity, hydrophobicity, flexibility, steric repulsion, etc. by appropriately adjusting the chain length and the constituent alkylene oxide. It has characteristics and is widely used in various applications. In recent years, the use of inorganic particles as a dispersant has been studied. Conventional dispersants include sulfonic acid group-containing polymers such as lignin sulfonic acid and naphthalene sulfonic acid, carboxylic acid group-containing polymers such as poly (meth) acrylic acid, and amide group-containing heavy polymers such as poly (meth) acrylamide. Polymers, phosphoric acid group-containing polymers such as polyphosphoric acid and hexametaphosphoric acid, hydroxyl group-containing compounds such as gluconic acid, surfactants and the like have been used. These are generally adsorbed on inorganic particles by interactions such as ionicity and hydrophobicity and hydrogen bonds, imparting ionicity to the particle powder surface to impart electrostatic repulsion, and hydrophilicity on the inorganic particle surface It is considered that the inorganic particles are dispersed by imparting.

In addition, as a dispersant for dispersing inorganic particles by steric repulsion, a polycarboxylic acid polymer containing a polyalkylene glycol chain (hereinafter also referred to as polycarboxylic acid) has been newly proposed as one that exhibits a high dispersing action, Recently, it has been used a lot. This polymer mainly disperses particles with the steric repulsive force of the polyalkylene glycol chain. Compared with conventional dispersants that disperse powder only with electrostatic repulsive force or hydrophilicity, this polymer has a stronger dispersing power. Have

In recent years, among these inorganic particle dispersant applications, cement dispersants added to cement compositions such as cement pastes, mortars, concrete, etc., and cement admixtures containing cement dispersants, where the inorganic particles to be dispersed are cement. The use of the drug is being studied energetically. These dispersants and admixtures are also called water-reducing agents, and are hardened by increasing the fluidity of the cement composition to improve workability and formability, and reducing the amount of water required for kneading. It is used for the purpose of improving the strength and durability of objects.

Conventionally, lignin-based, naphthalene-based, gluconic acid and the like have been used as cement dispersants, but a polycarboxylic acid-based material containing a polyalkylene glycol chain having a steric repulsive force has been newly proposed. Compared with conventional ones, polycarboxylic acid-based cement dispersants have high dispersibility and water-reducing properties derived from steric repulsion, and have recently been used as high-performance AE water-reducing agents. Yes.

For a conventional polycarboxylic acid polymer containing a polyalkylene glycol chain, for example, it is obtained by adding a thiocarboxylic acid to a polyether having double bonds at both ends or one end and then decomposing the resulting thioester group. As a biodegradable water-soluble polymer for use in detergent builders, a compound having a mercapto group is esterified to a polyether compound as a polyether having a mercapto group at both ends or one end. A polymer obtained by subjecting a modified polyether compound introduced by a reaction 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). Moreover, a concrete admixture containing a copolymer obtained by polymerizing a polyalkylene glycol monoester monomer and a (meth) acrylic acid ester monomer at a specific ratio is disclosed (for example, , See Patent Document 4).

Japanese Patent Publication No. 7-13141 JP-A-7-109487 JP 2007-119736 A JP-A-10-81549

As described above, in recent years, studies have been made to apply polyalkylene glycol polymers to inorganic particle dispersants and inorganic particle admixtures.
By the way, as a performance that has been increasing in demand in recent years, for example, in concrete admixture applications, it is possible to exhibit higher retainability. Since the time from concrete production to transportation and construction may vary, the fluidity of the concrete differs greatly during production and construction, and design performance may not be demonstrated during construction. In general, concrete tends to lose its fluidity at higher temperatures. This is probably because the hydration reaction of cement is accelerated at high temperatures. For this reason, under high temperature conditions such as summer, the conventional admixture cannot obtain sufficient retention, and the design performance may not be exhibited during construction. In order to satisfy such a demand, a dispersant having particularly excellent retention is effective.

Here, in the prior art, in order to impart high retainability to the concrete, the amount of the dispersant used is increased to increase the fluidity in the first place, and the retainer is improved by devising the molecular structure of the dispersant. Studies such as delaying the hydration reaction of cement by using a setting retarder have been made. However, it is not economical to increase fluidity by increasing the amount used, and there is also a problem in that it causes separation of cement paste and aggregate by giving excessive fluidity to concrete, resulting in poor performance. The structure of the dispersant has been devised in various ways, but the current situation is that it has not been able to meet the recent demands. The use of a setting retarder increases the work period by delaying the hardening of the concrete, and in the worst case, the concrete does not harden and does not reach the design strength.

Therefore, it can be said that a dispersant capable of exhibiting excellent retainability is useful in more fields. Although it has been described using cement as an example of inorganic particles, since cement is a composite of various inorganic oxides such as calcium, aluminum, iron, silicon, sulfur and the like, it is the same in many inorganic particle dispersion applications. I guess.
As described above, in order to exhibit excellent retainability, there has been room for improvement in order to make the structure of the polymer used as the dispersant more suitable.

The present invention has been made in view of the above-described situation, and can exhibit particularly excellent retainability, and is useful for various uses, particularly for inorganic particle dispersants and admixtures such as cement. An object of the present invention is to provide a polymer, a dispersant (inorganic particle dispersant), an admixture (inorganic particle admixture) and an inorganic particle composition using the polymer.

The inventor has made various studies on a polymer containing a polyalkylene glycol chain. As a result, the polymer has a polyalkylene glycol chain and a structural unit derived from a vinyl monomer, and the polymer has a terminal end of the polyalkylene glycol chain. When the terminal oxygen atom in at least one has a structure bonded to the main chain terminal of the structural unit derived from the vinyl monomer, directly or through an organic residue, the inorganic particle composition such as a cement composition 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 it has a structure 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 steric repulsion causes an inorganic particle composition such as a cement composition to And found that it can exhibit higher water reduction performance. Furthermore, when the bonding part of the polyalkylene glycol chain in the polymer as described above and the structural unit derived from the vinyl monomer is a hydrolyzable group, the retention property of the inorganic particle composition using the polymer Has been found to improve further.

Further, in the polymer as described above, if the vinyl monomer essentially contains a monomer having a hydrolyzable group and an unsaturated polyalkylene glycol monomer, inorganic particles using the polymer are used. It has been found that the retentivity and state of the composition and the like are improved or improved, and the performance of dispersing inorganic particles (dispersibility) has been dramatically improved, and in particular, the content ratio of the monomer having a hydrolyzable group It has been found that the retention of the inorganic particle composition using the polymer is particularly improved when the amount is 20 mol% or more with respect to the total amount of vinyl monomers of 100 mol%. If the vinyl monomer further contains an unsaturated carboxylic acid monomer, the content of the unsaturated carboxylic acid monomer is, in particular, the molar content of the monomer having a hydrolyzable group. It has also been found that when the molar content is less than or equal to, higher fluidity and retention can be imparted by an inorganic particle composition using the polymer. And the inorganic particle dispersant represented by the inorganic particle admixture such as cement admixture obtained by using the polymer of the present invention can exhibit unprecedented performance (dispersibility, slump retention, etc.). The present inventors have found that an inorganic particle composition such as a cement composition comprising the same is particularly useful in the field, and has reached the present invention.

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, the polymer comprising a terminal oxygen at at least one of the terminals of the polyalkylene glycol chain. An atom has a structure bonded to the main chain terminal of a constituent unit derived from the vinyl monomer directly or through an organic residue, and the vinyl monomer has a total amount of vinyl monomers of 100. A polyalkylene glycol polymer containing 1 to 99 mol% of a monomer having a hydrolyzable group and 1 to 99 mol% of an unsaturated polyalkylene glycol monomer relative to mol%.

The present invention also includes a polymer having a polyalkylene glycol chain and having a multi-branched structure, wherein the polymer has three or more polyalkylene glycol chains bonded to a residue of a compound having three 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 via an organic residue, The vinyl monomer contains 1 to 99 mol% of a monomer having a hydrolyzable group with respect to 100 mol% of the total amount of vinyl monomers, and 1 unsaturated polyalkylene glycol monomer. It is also a polyalkylene glycol polymer containing ˜99 mol%.

The present invention is also an inorganic particle dispersant containing the polyalkylene glycol polymer.
The present invention is also an inorganic particle admixture containing the above polyalkylene glycol polymer.
The present invention is also an inorganic particle composition containing the above inorganic particle admixture.
The present invention is described in detail below. In addition, the form which combined each preferable form of this invention described below 2 or 3 or more is also a preferable form of this invention.

<Polyalkylene glycol polymer>
The polyalkylene glycol polymer of the present invention is a polymer having a structural unit derived from a vinyl monomer and a polyalkylene glycol chain in its main chain, and the terminal at at least one of the terminals of the polyalkylene glycol chain. The oxygen atom 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, and the vinyl monomer is a monomer having a hydrolyzable group. And an unsaturated polyalkylene glycol monomer. Details of the structure of the polyalkylene glycol polymer will be described later.
In the following, the terminal oxygen atom in at least one of the terminals of the polyalkylene glycol chain of the present invention has a structure in which the main chain terminal of the structural unit derived from the vinyl monomer is bonded directly or through an organic residue. A polyalkylene glycol polymer is referred to as “polymer (i)”, and a polymer that forms a structural unit derived from a vinyl monomer in which the polyalkylene glycol chain is bonded directly or via an organic residue (heavy polymer). The combined portion) is also referred to as “polymer (ii)”.

-Polymer (i)-
In the polyalkylene glycol polymer (i), the vinyl monomer for forming the polymer (ii) is a monomer having a hydrolyzable group and an unsaturated polyalkylene glycol monomer. Essentially included. That is, the polyalkylene glycol polymer (i) of the present invention includes a structural unit derived from a monomer having a hydrolyzable group and a structural unit derived from an unsaturated polyalkylene glycol monomer.
Each structural unit may be a structural unit derived from one type of monomer, or may be a structural unit derived from two or more types of monomers.

Although it will not specifically limit if it is a group which can be hydrolyzed as said hydrolysable group, It is preferable that it is a functional group which produces | generates a carboxyl group by hydrolysis. When such a polyalkylene glycol polymer containing a structural unit derived from a monomer having a hydrolyzable group is applied to, for example, an inorganic particle admixture which is one of the preferred uses, the inorganic particle admixture is used. In the inorganic particle composition containing, the said hydrolysable group will hydrolyze with time and a carboxyl group will be produced | generated. Therefore, the adsorption function of the polyalkylene glycol polymer to inorganic particles (cement particles, etc.) increases with time due to the carboxy anion generated from the carboxyl group. As a result, good inorganic particle dispersibility can be maintained over a long period of time, and the slump retention of the inorganic particle composition can be improved.
As a functional group which produces | generates a carboxyl group by the said hydrolysis, an ester group, an amide group, a nitrile group etc. can be mentioned, for example. An ester group is preferred.
Specific examples of the monomer having a hydrolyzable group will be described later.

Next, the structure of the polyalkylene glycol polymer (i) of the present invention will be described.
The polymer (i) has a polyalkylene glycol chain and a structural unit derived from a vinyl monomer in the main chain of the polymer, and a terminal oxygen atom at at least one terminal of the polyalkylene glycol chain (PAG). However, it has the structure couple | bonded with the principal chain terminal of the structural unit (BL) derived from a vinyl-type monomer through a direct bond or an organic residue.
The polyalkylene glycol polymer is composed of a polyalkylene glycol chain (PAG) and a structural unit (BL) derived from a vinyl monomer that is bonded directly or via an organic residue to the polyalkylene glycol chain. As long as it has, it may have 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 three structural sites of the polyalkylene glycol chain (PAG), the vinyl monomer-derived structural unit (BL), and Y are as follows: There is a thing of structure.

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 the polymers represented by the general formulas (a) to (d), when the polyalkylene glycol chain (PAG) is located at the end of the polymer structure, the polyalkylene glycol chain (PAG) Have hydrogen atoms. 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 derived from the unsaturated polyalkylene glycol monomer in the derived structural site is also referred to as “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 the production of the inorganic particle admixture component, it is mainly composed of a relatively short chain alkylene oxide (oxyalkylene group) having about 2 to 8 carbon atoms from the viewpoint of affinity with cement particles. Is preferred. 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 expressing “dominate” 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 an admixture or dispersing agent for inorganic particles such as a cement admixture, the inorganic particles exhibit a light hydrophobic interaction between polyalkylene glycol chains in an aqueous solution. This is because the viscosity of the composition is adjusted and 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. 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 usually used may be used. 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 n of alkylene oxide repeats (average number of added moles of oxyalkylene group) in the polyalkylene glycol chain (I) is preferably 1-1000. 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 preferably 5, 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 added oxyalkylene groups) is the number of moles of alkylene oxide added in 1 mole of the polyalkylene glycol chain (I) of the polymer (i). Mean value of

The structural site represented by Y is a direct bond or an organic residue, but can facilitate the bond between the polyalkylene glycol chain (PAG) and the structural unit (BL) derived from the vinyl monomer. In this respect, an organic residue is preferable. 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 to couple | bond with the principal chain terminal of the said polymer (ii) 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. Moreover, since a carbonyl group and an amide group have hydrolyzability, such a form can improve retention, when the said polymer is used as a dispersing agent. This form may be appropriately adjusted according to the required performance, but a carbonyl group having high hydrolyzability is more preferable because the performance can be easily adjusted. That is, among the organic residues containing a sulfur atom, those containing a carbonyl group are more preferable.

Further, when the organic residue containing a sulfur atom is in a form containing a carbonyl group or an amide group, a carbonyl group (including a —CO group in the amide group) at the bonding site between the organic residue and the polyalkylene glycol chain. ) And the terminal oxygen atom of the polyalkylene glycol chain are preferably adjacent to each other. That is, the polymer (i) is preferably a polyalkylene glycol chain and Y ² bonded via an ester bond or an amide bond, and more preferably bonded via an ester bond. .

-Polymer (ii)-
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-based monomer forming it essentially contains a monomer having a hydrolyzable group (hereinafter also simply referred to as “monomer (A)”). That is, the polymer (ii) includes a structural unit derived from the monomer (A).
The monomer (A) may be one type or two or more types.
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 a vinyl monomer and may have at least one hydrolyzable group as described above. When two or more hydrolyzable groups are contained in one molecule, the hydrolyzable groups may be the same type or different types. The monomer (A) is a monomer having the same hydrolyzable group type (in the case where two or more hydrolyzable groups are present in one molecule, the combination is the same). Monomer) or different monomers (or combinations) of hydrolyzable groups may be used in combination.

As described above, the hydrolyzable group possessed by the monomer (A) is preferably an ester group, an amide group, a nitrile group, or the like.
Among the monomers (A), examples of the monomer (A) having an ester group as a hydrolyzable group include an esterified product of an unsaturated carboxylic acid monomer and an alcohol compound, and an unsaturated alcohol type. Examples include esterified products of monomers and carboxylic acid compounds. Among these, the former which produces | generates a carboxyl group on the said polymer (ii) by hydrolysis is preferable.

Examples of the unsaturated carboxylic acid monomer include unsaturated monocarboxylic acid monomers and unsaturated dicarboxylic acid monomers. Examples of the unsaturated monocarboxylic acid monomer include (meth) acrylic acid, crotonic acid and anhydrides thereof, and acrylic acid is preferable. Examples of unsaturated dicarboxylic acid monomers include maleic acid, fumaric acid, itaconic acid, citraconic acid and anhydrides thereof, and maleic acid and maleic anhydride are preferred.

Examples of the alcohol compound include monoalcohol having 1 to 30 carbon atoms; alkyl (poly) alkylene glycol obtained by adding 1 to 500 moles of alkylene oxide having 2 to 18 carbon atoms to monoalcohol having 1 to 30 carbon atoms; A diol having 1 to 30 carbon atoms; a hydroxy (poly) alkylene glycol obtained by adding 1 to 500 moles of an alkylene oxide having 2 to 18 carbon atoms to a diol having 1 to 30 carbon atoms; a polyol having 1 to 30 carbon atoms A polyol (poly) alkylene oxide adduct obtained by adding 1 to 500 moles of an alkylene oxide having 2 to 18 carbon atoms to a polyol having 1 to 30 carbon atoms;
Among them, monoalcohol having 1 to 8 carbon atoms; alkyl (poly) alkylene glycol obtained by adding 1 to 200 moles of alkylene oxide having 2 to 8 carbon atoms to monoalcohol having 1 to 8 carbon atoms; A diol having ˜8; a hydroxy (poly) alkylene glycol obtained by adding 1 to 200 moles of an alkylene oxide having 2 to 8 carbon atoms to a diol having 1 to 8 carbon atoms; a polyol having 1 to 15 carbon atoms; A polyol (poly) alkylene oxide adduct obtained by adding 1 to 200 moles of an alkylene oxide having 2 to 8 carbon atoms to a 1 to 15 polyol is preferable,
An alkyl (poly) alkylene glycol obtained by adding 1 to 50 moles of an alkylene oxide having 2 to 4 carbon atoms to a monoalcohol having 1 to 4 carbon atoms; a diol having 1 to 4 carbon atoms; More preferred is a hydroxy (poly) alkylene glycol obtained by adding 1 to 50 moles of an alkylene oxide having 2 to 4 carbon atoms to a diol,
Methoxy (poly) alkylene glycol obtained by adding 1 to 25 moles of alkylene oxide having 2 to 3 carbon atoms to methanol; ethylene glycol, propylene glycol; alkylene oxide having 2 to 3 carbon atoms to diol having 2 to 3 carbon atoms More preferably, 1 to 25 mol of hydroxy (poly) alkylene glycol is added,
Most preferred are methoxy (poly) ethylene glycol obtained by adding 1 to 10 mol of ethylene oxide to methanol; ethylene glycol; hydroxy (poly) ethylene glycol obtained by adding 1 to 10 mol of ethylene oxide to ethylene glycol.

Examples of the esterified product of the unsaturated carboxylic acid monomer and the alcohol compound may include a monoester, a diester, a polyester, and a half ester. Of these, diesters and polyesters act as cross-linking agents during polymerization, making it difficult to adjust the molecular weight of the polymer or generating an insoluble gel. Monoesters and half esters are preferred.

Examples of the unsaturated alcohol monomer include vinyl alcohol, hydroxyalkyl vinyl ether, (meth) allyl alcohol, 3-buten-1-ol, 3-methyl-3-buten-1-ol, and 3-methyl- 2-buten-1-ol, 2-methyl-3-buten-2-ol, 2-methyl-2-buten-1-ol, 2-methyl-3-buten-1-ol and the like are preferable, Vinyl alcohol.
Examples of the carboxylic acid compound include formic acid and carboxylic acids having 1 to 8 carbon atoms, preferably acetic acid.

Among the monomers (A), examples of the monomer (A) having an amide group as a hydrolyzable group include, for example, an unsaturated dicarboxylic acid monomer and an amine having 1 to 30 carbon atoms. Half amides, diamides; half amides of maleamic acid and glycols having 2 to 18 carbon atoms or polyalkylene glycols having an addition mole number of these glycols of 2 to 500; unsaturated monocarboxylic acids such as methyl (meth) acrylamide Amides of acids and amines having 1 to 30 carbon atoms; unsaturated amides such as (meth) acrylamide, (meth) acrylalkylamide, N-methylol (meth) acrylamide, N, N-dimethyl (meth) acrylamide Etc. Of these, acrylamide is preferred.

Among the monomers (A), examples of the monomer (A) having a nitrile group as a hydrolyzable group include unsaturated cyanides such as (meth) acrylonitrile and α-chloroacrylonitrile. Of these, acrylonitrile is preferred.

Content of the said monomer (A) is 1-99 mol% with respect to 100 mol% of the total amount of the said vinylic monomer. That is, in the range of 1 to 99 mol%, it may be appropriately adjusted according to the required performance, but in order to sufficiently exhibit the performance derived from the monomer (A), the total amount of vinyl monomers is 100. 5 mol% or more is preferable with respect to mol%. More preferably, it is 20 mol% or more, and this makes it possible to further improve the retention of an inorganic particle composition or the like using the polymer. Thus, the form in which the content of the monomer (A) having the hydrolyzable group is 20 mol% or more with respect to 100 mol% of the total amount of the vinyl monomer is also suitable for the present invention. One of the forms. More preferably, it is 30 mol% or more, 40 mol% or more is still more preferable, 50 mol% or more is especially preferable, and 60 mol% or more is the most preferable. Further, from the viewpoint of sufficiently exhibiting the performance of other vinyl monomers, the content of the monomer (A) is preferably 95 mol% or less. 80 mol% or less is more preferred, 75 mol% or less is more preferred, 70% mol% or less is even more preferred, 60 mol% or less is particularly preferred, and 55 mol% or less is most preferred.

The vinyl monomer also contains an unsaturated polyalkylene glycol monomer (hereinafter also simply referred to as “monomer (B)”). That is, the polymer (ii) includes a structural unit derived from the monomer (B) in addition to the structural unit derived from the monomer (A). As a result, the polyalkylene glycol polymer of the present invention is superior in dispersion performance. This is due to the steric repulsion of the polyalkylene glycol chain derived from the monomer (B), resulting in inorganic particles such as cement particles. This is thought to be due to the dramatic improvement in the performance of dispersing the slag.
The monomer (B) may be one type or two or more types.
The structural unit derived from the monomer (B) is a structure in which a polymerizable double bond of the monomer (B) is opened by a polymerization reaction (a double bond (C = C) is a single bond (- This corresponds to the structure (CC-).

Examples of the unsaturated polyalkylene glycol monomer (B) include the following formula (1);

(.AO ^wherein, R 1, ^{R 2} and ^{R 3} are the same or different, .R ⁴ 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 more of oxyalkylene groups having 2 to 18 carbon atoms, and when there are two or more oxyalkylene groups represented by AO, these groups are introduced in a block form. And y is an integer of 0 to 2. z is 0 or 1. r represents the average number of moles added of the oxyalkylene group. A number of 300.) is preferred.

In the general formula (1), of the terminal group represented by ^{R 4,} examples of the hydrocarbon group having 1 to 20 carbon atoms, aliphatic alkyl group having 1 to 20 carbon atoms, alicyclic of 3 to 20 carbon atoms Examples thereof include an alkyl group having 2 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, an alkynyl group having 2 to 20 carbon atoms, and an aryl group having 6 to 20 carbon atoms.
The terminal group represented by R ⁴ is preferably a hydrophilic group from the viewpoint of dispersibility of cement particles when used for an inorganic particle admixture such as a cement admixture. Is preferably a hydrogen atom or a hydrocarbon group having 1 to 8 carbon atoms. 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), the polyalkylene glycol chain (II) represented by (AO) _r is 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 (II) 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 (II) 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 (II) represented by the above (AO) _r may also include a part of the oxyalkylene group having 3 or more carbon atoms having higher hydrophobicity. When such a hydrophobic group is introduced, when used as an admixture or dispersing agent for inorganic particles such as a cement admixture, the inorganic particles exhibit a light hydrophobic interaction between polyalkylene glycol chains in an aqueous solution. This is because the viscosity of the composition is adjusted and 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 (ii), the aspect which does not contain C3 or more alkylene oxide may be preferable.

When the polyalkylene glycol chain (II) 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).

In the general formula (1), r is a number of 1 to 300, but if it exceeds 300, there is a risk of production failure, and when used as an inorganic particle admixture such as a cement admixture. There is a possibility that the viscosity of the inorganic particle composition becomes high and the workability is not sufficient. 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.

Specific examples of the unsaturated polyalkylene glycol monomer represented by the general formula (1) include unsaturated alcohol polyalkylene glycol adducts and polyalkylene glycol ester monomers.

The unsaturated alcohol polyalkylene glycol adduct may be a compound having a structure in which a polyalkylene glycol chain is added to an alcohol having an unsaturated group. Specifically, for example, 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-buten-1-ol alkylene Oxide adducts, 2-methyl-3-buten-1-ol alkylene oxide adducts are preferred. From the viewpoints of reactivity during polymerization and economy, (meth) allyl alcohol alkylene oxide adducts and 3-methyl-3-buten-1-ol alkylene oxide adducts are preferred.

The polyalkylene glycol ester monomer may be a monomer having a structure in which an unsaturated group and a polyalkylene glycol chain are bonded via an ester bond. Specifically, unsaturated carboxylic acid polyalkylene glycol ester compounds are preferred. However, from the viewpoint of distinguishing from the hydrolyzable monomer (A) regardless of the performance, the polyalkylene glycol ester monomer in the present invention has a relatively low hydrolyzability. Since it is necessary, R ¹ in the general formula (1) is a methyl group. Of these, (alkoxy) polyalkylene glycol monomethacrylate is preferred.

Content of the said monomer (B) is 1-99 mol% with respect to 100 mol% of total amounts of the said vinyl-type monomer. That is, in the range of 1 to 99 mol%, it may be appropriately adjusted according to the required performance, but from the viewpoint of sufficiently exhibiting the performance derived from the monomer (B), the total amount of vinyl monomers is 100. 3 mol% or more is preferable with respect to mol%. 5 mol% or more is more preferable, 10 mol% or more is still more preferable, 15 mol% or more is still more preferable, 20 mol% or more is especially preferable, and 25 mol% or more is the most preferable. Further, from the viewpoint of sufficiently exhibiting the performance of other vinyl monomers, the content of the monomer (B) is preferably 80 mol% or less. 50 mol% or less is more preferable, 40 mol% or less is still more preferable, 30% or less is still more preferable, 25 mol% or less is especially preferable, and 20 mol% or less is the most preferable.

The vinyl monomer preferably further contains an unsaturated carboxylic acid monomer (hereinafter also simply referred to as “monomer (C)”). That is, the polymer (ii) is a structural unit derived from a monomer (A) having a hydrolyzable group, a structural unit derived from an unsaturated polyalkylene glycol monomer (B), and an unsaturated carboxylic acid. A form containing a structural unit derived from the system monomer (C) is preferred. Thereby, the hydrophilicity of a polymer is improved and it becomes possible to make it useful by various uses. Thus, the form in which the vinyl monomer further contains an unsaturated carboxylic acid monomer is also one of the preferred forms of the present invention.
The monomer (C) may be one type or two or more types.
The structural unit derived from the monomer (C) is a structure in which a polymerizable double bond of the monomer (C) is opened by a polymerization reaction (a double bond (C = C) is a single bond (- This corresponds to the structure (CC-).

Examples of the unsaturated carboxylic acid monomer (C) include the following formula (2);

(In the formula, R ⁵ , R ⁶ and R ⁷ are the same or different and each represents a hydrogen atom, a methyl group or (CH ₂ ) _x COOM ^2. Note that — (CH ₂ ) _x COOM ² represents —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.

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 / or salts thereof are preferable from the viewpoint of polymerizability, and acrylic acid, methacrylic acid and / or salts thereof are more preferable.

The content of the monomer (C) is preferably 1 to 98 mol% with respect to 100 mol% of the total amount of the vinyl monomer. That is, in the range of 1 to 98 mol%, it is preferable to adjust appropriately according to the required performance. From the viewpoint of sufficiently exhibiting the performance derived from the monomer (C), the vinyl monomer 5 mol% or more is preferable with respect to the total amount of 100 mol%. 10 mol% or more is more preferable, 20 mol% or more is still more preferable, 25 mol% or more is still more preferable, 30 mol% or more is especially preferable, and 35 mol% or more is the most preferable. Further, from the viewpoint of sufficiently exhibiting the performance of other vinyl monomers, the content of the monomer (C) is preferably 80 mol% or less. 60 mol% or less is more preferable, 50 mol% or less is still more preferable, 40% or less is still more preferable, 35 mol% or less is especially preferable, and 30 mol% or less is the most preferable.

Further, from the molar content of the monomer (A) (content of the monomer (A) with respect to the total amount of vinyl monomers of 100 mol%), the molar content of the monomer (C) (single vinyl monomer) The difference obtained by subtracting the monomer (C) content relative to the total amount of 100 mol% of the body is preferably in the range of −97 to 97 mol%. That is, within this range, it is preferable to appropriately adjust the difference according to the required performance, but the performance derived from the monomer (A) and the performance derived from the monomer (C) From the viewpoint of exerting a good balance, it is preferably −50 mol% or more. It is more preferably −25 mol% or more, more preferably 0 mol% or more, that is, the molar content of the monomer (C) is more preferably less than or equal to the molar content of the monomer (A). Thereby, higher fluidity and retention can be imparted to the inorganic particle composition using the polymer of the present invention. Even more preferably, it is at least 5 mol%, particularly preferably at least 10 mol%, most preferably at least 15 mol%. Further, it is preferably 70 mol% or less, more preferably 50 mol% or less, still more preferably 40 mol% or less, still more preferably 30 mol% or less, particularly preferably 20 mol% or less, and 15 mol% or less. Most preferred.

The vinyl monomer is also a monomer other than the above-mentioned monomer (A) having a hydrolyzable group, unsaturated polyalkylene glycol monomer (B) and unsaturated carboxylic acid monomer (C). Other copolymerizable monomers (hereinafter also referred to as “monomer (D)”) may be further included. In this case, the polymer (ii) further includes a structural unit derived from the monomer (D). The structural unit derived from the monomer (D) is a monomer obtained by a polymerization reaction. (D) corresponds to a structure in which a polymerizable double bond is open (a structure in which a double bond (C═C) is a single bond (—C—C—)).
When using the said monomer (D), it is suitable to set it as 30 mol% or less with respect to 100 mol% of total amounts of a vinyl-type monomer as the content. More preferably, it is 25 mol% or less, More preferably, it is 20 mol% or less.

Specific examples of the monomer (D) include the following compounds, and one or more of these can be used.
Vinyl sulfonate, (meth) allyl sulfonate, 2- (meth) acryloxyethyl sulfonate, 3- (meth) acryloxypropyl sulfonate, 3- (meth) acryloxy-2-hydroxypropyl sulfonate, 3- (meth) acryloxy-2 -Hydroxypropylsulfophenyl ether, 3- (meth) acryloxy-2-hydroxypropyloxysulfobenzoate, 4- (meth) acryloxybutylsulfonate, (meth) acrylamidomethylsulfonic acid, (meth) acrylamidoethylsulfonic acid, 2- Unsaturated sulfonic acids such as methylpropanesulfonic acid (meth) acrylamide and styrenesulfonic acid, and monovalent metal salts, divalent metal salts, ammonium salts and organic amine salts thereof; styrene, α-methylstyrene, Vinyl aromatics such as nyltoluene and p-methylstyrene; dienes such as butadiene, isoprene, 2-methyl-1,3-butadiene and 2-chloro-1,3-butadiene; and non-polymers such as vinyl acetate and vinyl propionate Saturated esters.

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 the same or different polymer that forms a structural unit derived from a vinyl monomer having a hydrolyzable group, and n is the same or different, The average added mole number of an oxyalkylene group is a number from 1 to 1000. m is an integer from 1 to 50).

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 having a hydrolyzable group represented by Z, respectively, above Y and, This is the same as the polymer (ii) that forms the structural unit (BL) derived from the vinyl monomer. M is a polyalkylene glycol 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 chains.

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 above-mentioned multi-branched polyalkylene glycol polymer has a multi-branched structure. As described above, the multi-branched structure is a structure that branches 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 inorganic particle dispersion performance such as cement dispersion performance and the 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, As the vinyl monomer, a polyalkylene glycol-based polymer including a monomer having a hydrolyzable group and an unsaturated polyalkylene glycol-based monomer is one preferred embodiment of the present invention.
The “main chain” in the polyalkylene glycol polymer having a multi-branched structure includes a polyalkylene glycol chain 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 of the number of active hydrogens is preferably 4, more preferably 5, and the upper limit is more preferably 20, and even 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 the compound having one or more active hydrogens include alcohol residues having a structure in which active hydrogen is removed from the hydroxyl group of a monovalent or polyhydric alcohol, monovalent or polyvalent amines. An amine residue having a structure obtained by removing active hydrogen from an amino group, an imine residue having a structure obtained by removing active hydrogen from an imino group of a monovalent or polyvalent imine, an active hydrogen from an amide group of a monovalent or polyvalent amide compound An amide residue having a structure excluding is preferred. 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, etc. These polyamines usually have a third in the structure. 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, such as ethyleneimine, propyleneimine, 1,2-butyleneimine, 2,3-butyleneimine, 1 A homopolymer or a copolymer obtained by polymerizing one or more alkylene imines 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 fully exhibit the effect resulting from the structure of the polyalkylene glycol polymer. For example, the inorganic particle admixture and the like exhibit inorganic particle dispersion performance. It can be suitable for the application. 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.

The number average molecular weight of the polyvalent amine and polyalkyleneimine is preferably 100 to 100,000, more preferably 300 to 50,000, still more preferably 600 to 10,000, and particularly preferably 800 to 5,000.

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. As a result, it is possible to provide an inorganic particle admixture that can exhibit further excellent dispersion performance, and thus it can be a compound applicable to various uses.

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 non-multi-branched (straight chain) structure polyalkylene glycol polymer 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.

In the general formula (4), 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、加水分解性基を有するビニル系単量体由来の構成単位を形成する重合体である。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。

(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, and Z is the same or different and represents a structural unit derived from a vinyl monomer having a hydrolyzable group. N is the same or different and represents the average number of moles added of the oxyalkylene group and is a number from 1 to 1000. m is an integer from 1 to 50. The form which has a structure can be mentioned.

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). The form in which 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 has a weight average molecular weight (Mw) in consideration of its handleability and retention of inorganic particle composition when used for inorganic particle admixture such as cement admixture. It is preferable that it is 1 million or less. 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. In addition, when used for admixtures of inorganic particles such as cement admixtures, Mw is considered to be more effective when adsorbed to inorganic particles (cement particles, etc.) to some extent, and the larger the Mw, the greater the adsorbing power. It is preferable that it is 1000 or more. More preferably, it is 5000 or more, More preferably, it is 10,000 or more, Still more preferably, it is 20,000 or more, Especially 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.
The polyalkylene glycol polymer of the present invention is, for example, the vinyl-based polymer 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 the monomer component. By using the above polymer initiator and / or polymer chain transfer agent, the polyalkylene glycol chain (I) is introduced into the polyalkylene glycol polymer in the present invention.

In the polymerization reaction, the amount of the polyalkylene glycol chain used is preferably within a certain range from the viewpoint of sufficiently exerting the performance derived from the polyalkylene glycol chain and the performance derived from the vinyl monomer. .
The use amount of the polyalkylene glycol chain is the sum of the use amounts of the monomer (A), monomer (B), monomer (C) and monomer (D) of the vinyl monomer component. When the monomer (B) (unsaturated polyalkylene glycol monomer) is 50% by mass or more with respect to 100% by mass of the total vinyl monomer, 0.1 mass% or more is preferable. 0.5 mass% or more is more preferable, 1 mass% or more is still more preferable, 2.5 mass% or more is further more preferable, 5 mass% or more is especially preferable, and 7.5 mass% or more is the most preferable. Moreover, 50 mass% or less is preferable from a viewpoint of fully exhibiting the performance of a vinyl-type monomer. It is more preferably 40% by mass or less, further preferably 30% by mass or less, still more preferably 20% by mass or less, particularly preferably 15% by mass or less, and most preferably 10% by mass or less.
On the other hand, when the monomer (B) (unsaturated polyalkylene glycol monomer) is less than 50% by mass, 10% by mass or more is preferable with respect to 100% by mass of the total vinyl monomer. 100 mass% or more is more preferable, 200 mass% or more is still more preferable, 300 mass% or more is still more preferable, 400 mass% or more is especially preferable, and 500 mass% or more is the most preferable. Moreover, 2000 mass% or less is preferable from a viewpoint of fully exhibiting the performance of a vinyl-type monomer. 1500 mass% or less is more preferable, 1200 mass% or less is still more preferable, 1000 mass% or less is still more preferable, 800 mass% or less is especially preferable, and 700 mass% or less is the most preferable.

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.
In addition, 1 type (s) or 2 or more types can each be used for a polymeric initiator and a polymeric azo initiator.

First, a method for producing the polymer (i-1), that is, a polyalkylene glycol chain (PAG), a structural unit (BL) derived from a vinyl-based monomer, and three structural sites of Y 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 the polymer azo initiators represented by the general formulas (e) to (f), when the polyalkylene glycol chain (PAG) is located at the end of the structure, the polyalkylene glycol chain (PAG) Have hydrogen atoms. 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.

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 2000, m = 45), VPE-0401 (number average molecular weight about 2.5 to 40,000, molecular weight of polyethylene oxide part about 4000, m = 90), VPE-0601 (number average molecular weight about 2.5 to 40,000, molecular weight of polyethylene oxide part about 6000) M = 135) and the like.

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 addition mole number of an alkylene group is a number of 1-1000.) The high molecular azo initiator represented by this is mentioned.

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 a method of obtaining a polymer azo initiator by subjecting polyalkylene glycol to dehydration condensation using dicyclohexylcarbodiimide (DCC) and, if necessary, 4-dimethylaminopyridine.

In the polymerization reaction, the polymer azo initiator having the repeating unit represented by the general formula (6) or the polymer azo initiator represented by the general formula (9) is used in an amount of the polymer. From the viewpoint of sufficiently exhibiting the performance derived from the azo initiator and the performance derived from the vinyl monomer, it is preferably within a certain range.
The amount of the polymeric azo initiator used is the amount of the monomer (A), monomer (B), monomer (C) and monomer (D) used in the vinyl monomer component. When the total is 100% by mass and expressed as an external percentage, when the monomer (B) (unsaturated polyalkylene glycol monomer) is 50% by mass or more, the total vinyl monomer is 100% by mass. 0.1 mass% or more is preferable. 0.5 mass% or more is more preferable, 1 mass% or more is still more preferable, 2.5 mass% or more is further more preferable, 5 mass% or more is especially preferable, and 7.5 mass% or more is the most preferable. Moreover, from a viewpoint of fully exhibiting the performance of a vinyl-type monomer, 50 mass% or less is preferable. It is more preferably 40% by mass or less, further preferably 30% by mass or less, still more preferably 20% by mass or less, particularly preferably 15% by mass or less, and most preferably 10% by mass or less.
On the other hand, when the monomer (B) (unsaturated polyalkylene glycol monomer) is less than 50% by mass, 10% by mass or more is preferable with respect to 100% by mass of the total vinyl monomer. 100 mass% or more is more preferable, 200 mass% or more is still more preferable, 300 mass% or more is still more preferable, 400 mass% or more is especially preferable, and 500 mass% or more is the most preferable. Moreover, 2000 mass% or less is preferable from a viewpoint of fully exhibiting the performance of a vinyl-type monomer. 1500 mass% or less is more preferable, 1200 mass% or less is still more preferable, 1000 mass% or less is still more preferable, 800 mass% or less is especially preferable, and 700 mass% or less is the most preferable.

Next, in addition to the polymer (i-2), that is, the polyalkylene glycol chain (PAG), the vinyl monomer derived structural unit (BL), and the three structural sites Y, other than hydrogen atoms As a method for producing one having other structural sites of 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 addition, 1 type (s) or 2 or more types can each be used for a polymer chain transfer agent and a polyalkylene glycol chain containing compound.

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 above production method is the polymer (i-1), that is, the polyalkylene glycol chain (PAG), the structural unit derived from the vinyl monomer (BL), and When the polymer is composed of three structural sites of Y, 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 polyalkylene The 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” or “PAG-SH”). 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 (BL) derived from the vinyl monomer, and the three structural sites Y In the case of producing a polyalkylene glycol 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 condensation.

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, and one or more of these can be used. 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, it is preferable to carry out the 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.
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 (B), a monomer (C), and a polymer having a structural unit derived from one or more monomers among the monomers (D) may be formed 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, a polyalkylene glycol chain ( PAG), a vinyl monomer-derived structural unit (BL), and in addition to the three structural sites of Y, when producing a polyalkylene glycol polymer having another structural site other than a hydrogen atom, 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 Differently represents an organic residue, 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 an integer from 1 to 50. It is preferable to include 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 compound represented by Y ¹ The average addition mole number of the residue 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; As described above.

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, sodium hydride or the like.

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 “adduct”).

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.

<Uses of polyalkylene glycol polymers>
The polyalkylene glycol polymer (i) of the present invention can exhibit good performance as, for example, an inorganic or organic dispersant that is sparingly soluble in water. In addition, adhesives; sealing agents; various polymers It can be suitably used for various applications such as a flexibility imparting component. Among them, as described above, since extremely high inorganic particle dispersion performance and slump retention performance can be exhibited, it is particularly suitable as a dispersant for dispersing inorganic particles such as cement particles. Thus, the inorganic particle dispersant containing the polyalkylene glycol polymer is also one aspect of the present invention. As the inorganic particle dispersant, an inorganic particle admixture such as a cement admixture is particularly suitable, and thus the inorganic particle admixture containing the polyalkylene glycol polymer is also one aspect of the present invention. Furthermore, the form in which the polyalkylene glycol polymer is a polymer for an inorganic particle dispersant or a polymer for an inorganic particle admixture is a preferred form of the present invention.

The said inorganic particle admixture can be used in addition to the inorganic particle composition represented by cement compositions, such as cement paste, mortar, concrete, for example. Thus, the inorganic particle composition comprising the inorganic particle admixture is also one aspect of the present invention. Particularly preferred as the inorganic particle composition is a cement composition.
Below, a cement admixture is demonstrated as a typical inorganic particle admixture.

As the cement composition to which the cement admixture is applied, those containing cement, water, fine aggregate, coarse aggregate and the like are suitable, and as the cement, Portland cement (ordinary, early strength, very early strength, Medium heat, sulfate resistant and low alkali type); 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) Hard 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, cement containing high belite); ultra high strength cement; cement solidification Material: Ecocement (At least one of municipal waste incineration ash and sewage sludge incineration ash Cement produced as a raw material), etc., and blast furnace slag, fly ash, cinder ash, clinker ash, husk ash, silica fume, silica powder, limestone powder and the like added with fine powder and gypsum .
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 precast concrete), centrifugal concrete, vibration compaction concrete, steam-cured concrete, shotcrete, etc., and 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.

The polyalkylene glycol-based polymer of the present invention has the above-described configuration, and can exhibit extremely excellent dispersion performance and slump retention performance. Therefore, the polyalkylene glycol-based polymer is useful for various applications, particularly for inorganic particle admixtures such as cement admixture. is there.

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 alcohol consumption rate of the raw material components was estimated by the following equation (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, TSKguardcolumns SWXL + TSKgel G4000SWXL + G3000SWXL + G2000SWXL
Detector: differential refractometer (RI) detector (Waters 2414), multi-wavelength visible ultraviolet (PDA) detector (Waters 2996)
Eluent: A solution obtained by dissolving 115.6 g of sodium acetate trihydrate in a mixed solvent of 10999 g of water and 6001 g of acetonitrile, and adjusting the pH to 6.0 with acetic acid.
Standard substance for preparing calibration curve: polyethylene glycol (peak top molecular weight (Mp) 272500, 219300, 107000, 50000, 24000, 12600, 7100, 4250, 1470)
Calibration curve: Prepared by a cubic equation based on the Mp value and elution time of the polyethylene glycol.
Flow rate: 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)>
PAG thiol 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, Polyethylene glycol (PEG-100, manufactured by Nippon Shokubai Co., Ltd., addition number of ethylene glycol 100 mol, 1500.00 g), 3-mercaptopropionic acid (3-MPA, manufactured by Wako Pure Chemical Industries, 79.19 g), p-toluene Sulfonic acid monohydrate (PTS, Wako Pure Chemical Industries, 31.58 g), phenothiazine (PTZ, Wako Pure Chemical Industries, 0.79 g), and cyclohexane (78.96 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 45 hours while adding cyclohexane in the middle so that the temperature in the reaction system became 110 ± 5 ° C.

(2) Desolvation step After completion of the reaction, the mixture was allowed to cool to 60 ° C. with stirring so as not to solidify, and then an aqueous solution in which water (1498.69 g) was added to 30% NaOH aqueous solution (21.03 g) was reacted rapidly. It was put into the vessel. Subsequently, the temperature was gradually raised to about 100 ° C., and cyclohexane was distilled off. After distilling off, 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 99.9%, and the average number of SH introduced per PEG-100 molecule was 1.95. As a result of GPC analysis, the monomer amount was 94.2%, and the remainder was a multimer. Hereinafter, the molecular weight of the PAG thiol compound (1) is treated as 4600 which is the molecular weight of the PAG thiol monomer at the time of 100% reaction.

PAG thiol production example 2
(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, Trimethylolpropane ethylene oxide 75 mol adduct (TMP-75, manufactured by Nippon Shokubai Co., Ltd., 1500.00 g), 3-mercaptoisobutyric acid (3-MiBA, manufactured by Tokyo Chemical Industry Co., Ltd., 173.02 g), p-toluenesulfonic acid A monohydrate (PTS, manufactured by Wako Pure Chemical Industries, 33.46 g), phenothiazine (PTZ, manufactured by Wako Pure Chemical Industries, 0.84 g), and cyclohexane (83.65 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 70 hours while adding cyclohexane in the middle so that the temperature in the reaction system became 110 ± 5 ° C.

(2) Desolvation step After completion of the reaction, the mixture was allowed to cool to 60 ° C. with stirring so as not to solidify, and then an aqueous solution in which water (156.90 g) was added to 30% NaOH aqueous solution (22.28 g) was quickly reacted. It was put into the vessel. Subsequently, the temperature was gradually raised to about 100 ° C., and cyclohexane was distilled off. After distilling off, 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 (2)). As a result of LC analysis of the obtained target compound, the consumption rate of TMP-75 was 100%, and the average number of SH introduced per molecule of TMP-75 was 2.77. As a result of GPC analysis, the monomer amount was 88.1%, and the remainder was a multimer. Hereinafter, the molecular weight of the PAG thiol compound (2) is treated as 3744, which is the molecular weight of the PAG thiol monomer at the time of 100% reaction.

PAG thiol production example 3
(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, Propylene oxide 18 mol adduct of sorbitol ethylene oxide 450 mol adduct (SB-450-P18, Nippon Shokubai, 1500.00 g), 3-mercaptopropionic acid (3-MPA, Wako Pure Chemical Industries, 49.92 g) ), P-toluenesulfonic acid monohydrate (PTS, manufactured by Wako Pure Chemical Industries, Ltd., 31.00 g), phenothiazine (PTZ, manufactured by Wako Pure Chemical Industries, Ltd., 0.77 g), cyclohexane (154.99 g) Was 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 110 ± 5 ° C. The temperature in the reaction system was 90 to 95 ° C. The reaction was terminated by heating to reflux for 80 hours.

(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 quickly reacted with an aqueous solution in which water (1480.26 g) was added to 30% NaOH aqueous solution (20.64 g). It was put into the vessel. Subsequently, the temperature was gradually raised to about 100 ° C., and cyclohexane was distilled off. After distilling off, 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 (3)). As a result of LC analysis of the obtained target compound, the consumption rate of SB-450-P18 was 100%, and the average number of SH introduced per molecule of SB-450-P18 was 5.05. As a result of GPC analysis, the monomer amount was 58.3%, and the remainder was a multimer. Hereinafter, the molecular weight of the PAG thiol compound (3) is treated as 21579, which is the molecular weight of the PAG thiol monomer at the time of 100% reaction.

<Polyalkylene glycol chain-containing thiol polymer>
Polymer Example 1
Equipment: A Dimroth condenser, a Teflon (R) stirring blade and a stirrer with a stirring seal, a nitrogen inlet tube, and a glass reaction vessel equipped with a temperature sensor were used.
Preparation of raw material solution 1: Acrylic acid (AA, manufactured by Nippon Shokubai Co., Ltd., 0.78 g) as monomer (C), and ethylene oxide adduct of 3-methyl-3-buten-1-ol as monomer (B) (MB-E50, average EO addition mole number 50, 429.29 g) and ion-exchanged water (270.04 g) were charged into the reaction vessel.
Preparation of raw material solution 2: acrylic acid (30.12 g) as monomer (C), hydroxyethyl acrylate (HEA, Nippon Shokubai Co., Ltd., 52.89 g) as monomer (A), polyalkylene glycol chain (I ) A solution of the PAG thiol compound obtained in Production Example 1 (36.93 g in terms of solid content) and ion-exchanged water (79.96 g) as raw materials was prepared.
Preparation of initiator solution: As an initiator solution, 2,2′-azobis (2-methylpropionamidine) dihydrochloride (V-50, manufactured by Wako Pure Chemical Industries, Ltd., 1.45 g), ion-exchanged water (98. 55 g) of the solution was prepared.
Synthesis procedure: The raw material solution 1 charged in the reaction vessel was heated to 70 ° C. while introducing nitrogen at 200 mL / min with stirring at 200 pm. Subsequently, the raw material solution 2 was dropped into the reaction vessel over 3 hours and the initiator solution over 3.5 hours. The polymerization reaction was completed by maintaining at 70 ° 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 weight average molecular weight (Mw) was 51000.

Polymer Examples 2-4, 6-16 and Polymer Comparative Examples 1-2
The target polymer (polymers 2-4, 6) was used in the same manner as in Polymer Example 1 except that the types of raw materials used, the amounts used, the reaction temperature, etc. were as described in Tables 1-1 and 1-2. To 16, aqueous solutions of comparative polymers 1-2) were obtained. The results of GPC analysis are shown in Table 1-2.

Polymer Comparative Examples 3-4
Instead of using polyalkylene glycol chain (I) raw material, 3-mercaptopropionic acid (MPA) was used instead, and the type and amount of raw material used were as shown in Tables 1-1 and 1-2. Others were obtained in the same manner as in Polymer Example 1 to obtain an aqueous solution of the target polymer (Comparative Polymers 3 to 4). The results of GPC analysis are shown in Table 1-2.

Polymer Example 5
Equipment: A Dimroth condenser, a Teflon (R) stirring blade and a stirrer with a stirring seal, a nitrogen inlet tube, and a glass reaction vessel equipped with a temperature sensor were used.
Preparation of raw material solution 1: Methacrylic acid (MAA, Nippon Shokubai Co., Ltd., 66.47 g), sodium methacrylate (SMAA, MAA neutralized with sodium hydroxide, 9.27 g) as monomer (C), As a monomer (B), a methacrylic acid ester (MEPE-613E, manufactured by Nippon Shokubai Co., Ltd., 208.19 g) obtained by adding 6 mol of ethylene oxide, 1 mol of propylene oxide and 3 mol of ethylene oxide in this order to methanol, HEA (105.84 g) as A), PAG thiol compound (60.23 g in terms of solid content) obtained in Production Example 2 as a polyalkylene glycol chain (I) raw material, and ion-exchanged water (175.00 g) in the reaction vessel Was charged.
Preparation of initiator solution: As an initiator solution, a solution of V-50 (2.91 g) and ion-exchanged water (97.09 g) was prepared.
Synthesis procedure: Ion exchange water (275.00 g) was charged into a reaction vessel, and the mixture was heated to 70 ° C. while introducing nitrogen at 200 mL / min while stirring at 200 pm. Subsequently, the raw material solution 1 was dropped into the reaction vessel over 4 hours and the initiator solution over 5 hours. The polymerization reaction was completed by maintaining at 70 ° 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 5). As a result of GPC analysis, the weight average molecular weight (Mw) was 44000.

Abbreviations in Tables 1-1 and 1-2 are as follows.
Monomer (A): Monomer (A) having a hydrolyzable group
Monomer (B): Unsaturated polyalkylene glycol monomer (B)
Monomer (C): Unsaturated carboxylic acid monomer (C)
Monomer (C) Na salt: Unsaturated carboxylic acid monomer (C) sodium salt AA: Acrylic acid MAA: Methacrylic acid MB-E50: Ethylene oxide 50 of 3-methyl-3-buten-1-ol Mole adduct MEPE-613E: methacrylic acid ester ML-E150: ethylene oxide 150 mol adduct of methallyl alcohol HEA: hydroxyethyl acrylate HPA : Hydroxypropyl acrylate MEA: Methoxyethyl acrylate MPEG-10AE: Acrylic acid ester PAG-SH obtained by adding 10 mol of ethylene oxide to methanol: Polyalkylene glycol chain-containing thiol compound “(1)”: P PAG thiol compound (1) obtained in AG Thiol Production Example 1
“(2)”: PAG thiol compound obtained in PAG thiol production example 2 (2)
“(3)”: PAG thiol compound obtained in PAG thiol production example 3 (3)
MPA: 3-mercaptopropionic acid V-50: 2,2′-azobis (2-methylpropionamidine) dihydrochloride

<Concrete test>
Next, the result of the performance evaluation by the concrete test of the polymer and the comparative polymer will be described.
(1) Concrete mix:
Concrete was mixed and kneaded according to the formulation shown in Table 2. As the cement, ordinary Portland cement (manufactured by Taiheiyo Cement) was used. As the concrete admixture, the polymer obtained in the polymer example or the polymer comparative example was used. The compounding amount of the admixture was calculated as the solid content of the admixture, and is shown in Tables 3 to 5 in terms of mass% with respect to the cement. Further, an antifoaming agent (MA-404, manufactured by BASF Pozzolith Co., Ltd.) was added to adjust the amount of air in the concrete to 1 to 2%.
(2) Concrete kneading method (W / C = 30%):
Cement (C) and sand (S) were charged into a 50 L forced-kneading bread mixer, and after kneading for 10 seconds, water and cement admixture (W) were added and kneaded until the mortar was uniform. . Here, the number of seconds required for homogenizing the mortar was defined as “kneading time”. However, the maximum kneading time was 120 seconds. After homogenizing the mortar, stone (G) was added and kneaded for 90 seconds to prepare concrete.
(3) Concrete kneading method (W / C = 36%):
Sand (S), stone (G), and cement (C) are charged into a 50-liter forced-kneading bread mixer, kneaded for 10 seconds, water and cement admixture (W) are added, and kneaded for 120 seconds. And concrete was prepared.

(4) Evaluation method:
In accordance with Japanese Industrial Standards (JIS A1101-2005, A1128-2005, A6204-2006), the slump flow value of the concrete obtained by each concrete mix was measured.
The greater the slump flow value, the higher the fluidity of the concrete.
Regarding the cement dispersion performance of the admixture, if the addition amount is constant, the larger the slump flow value, the higher the cement dispersion performance of the admixture. The cement dispersibility is high and the water reduction performance is good.
Regarding the retention of the admixture, if the initial slump flow value immediately after kneading is equivalent, the higher the slump flow value after the lapse of a certain time, the better the admixture retention. Hereinafter, the retention rate may be obtained by dividing the slump flow value after a lapse of a certain time by the initial slump flow value. The retention rate is a measure of retention, and the larger the retention, the better the retention.

Table 3 shows the results of concrete examples 1 to 6 and concrete comparative examples 1 and 2.

In Table 3, the water cement ratio (W / C) is 30% and the target slump flow value is 600 mm. The polymers used in the concrete examples 1 to 4 and the concrete comparative examples 1 and 2 were changed in their molar contents using HEA as the monomer (A) having a hydrolyzable group (polymer 1). To 4) and those not using the monomer (A) (comparative polymers 1 and 2).

First, in order to clarify the effect of the monomer (A), concrete example 1 and concrete comparative examples 1 and 2 are compared. A polymer corresponding to the molar content of the monomer (A) of the polymer 1 used in the concrete example 1 is replaced with the monomer (C) is a comparative polymer 1 (concrete comparative example 1). The thing replaced with the monomer (B) is the comparative polymer 2 (concrete comparative example 2).
In the concrete example 1 using the polymer 1 having the monomer (A), the amount of admixture added to achieve a flow value of about 600 mm is 0.18%. Further, the retention rate after 60 minutes is 103%, and excellent retention properties capable of maintaining the initial fluidity are exhibited even after 60 minutes. On the other hand, in the concrete comparative example 1 using the comparative polymer 1 having no monomer (A), the amount of admixture required to achieve a flow value of about 600 mm is slightly increased to 0.19%, Dispersibility is slightly reduced. Moreover, the retention after 60 minutes is 34%, and it can be seen that the retention after 60 minutes is significantly inferior to that of Concrete Example 1. Moreover, in the concrete comparative example 2 using the comparative polymer 2 which does not have a monomer (A), even if it increases the addition amount of a polymer to 0.3%, the fluidity | liquidity of concrete cannot be obtained.
From the above, it can be seen that the polymer 1 having the monomer (A) imparts high fluidity and high retainability to the concrete.

Next, in order to clarify the effect of the monomer (A), comparing concrete examples 1 to 4, the comparison improves the retention rate as the content of the monomer (A) increases. It is clear. In particular, the concrete examples 1 and 2 have good retainability.

Moreover, the example at the time of changing the structure of a polymer (i) as concrete Examples 5-6 is shown.
The polymers 5 to 6 used in these are the same in composition and monomer (A) as the polymer 1, but the other monomers and the structure of the main chain polyalkylene glycol are changed. The retention after 60 minutes is very good at 119% and 94%, respectively, indicating high retention. From these results, it can be seen that the hydrolyzable monomer (A) is effective in improving retention.

Table 4 shows the results of Concrete Examples 7 to 8 and Concrete Comparative Examples 3 to 4.

In Table 4, the water cement ratio (W / C) is 30% and the target slump flow value is 600 mm. The polymers used in the concrete examples 7 to 8 and the concrete comparative examples 3 to 4 use HEA as the monomer (A) having a hydrolyzable group, but use a main chain polyalkylene glycol raw material. The polymers used in different amounts (polymers 7 to 8) and the main chain polyalkylene glycol raw materials were used instead of the corresponding amount of 3-mercaptopropionic acid (comparative polymers 3 to 4) It is.
When Concrete Example 7 and Concrete Comparative Example 3 are compared, and Concrete Example 8 and Concrete Comparative Example 4 are compared, the amount of addition necessary to obtain the target flow value is 13 to 29 when the polymer 7 or 8 is used. % Can be reduced. Since the structure of the polymer (ii) is common, it is presumed that this is an effect of the polyalkylene glycol chain in the main chain. Further, the retention after 60 minutes is slightly higher in the Example, which is presumed to be because the bonding portion between the polyalkylene glycol chain and the polymer (ii) in the main chain is a hydrolysable ester bond. Is done.

Table 5 shows the results of Concrete Examples 9-25.

In Table 5, the water cement ratio (W / C) is 36%. The polymers used in the concrete examples 9 to 12 have a constant composition and are different in the type of the monomer (A) having a hydrolyzable group. The polymers used in the concrete examples 13 to 16 Are the same monomer species but different compositions.
In any concrete, although the initial flow value is about 200 mm and the fluidity is low, the concrete exhibits a “rear elongation type” behavior that exhibits high fluidity after a certain period of time. Moreover, the fluidity of the concrete is maintained even after a long time such as 120 minutes or 180 minutes. From these results, by changing the composition of the monomer used in the polymer and the type of the monomer (A), the time for developing the fluidity can be adjusted, and the higher retention and longer retention can be achieved. It can be seen that sex can be achieved.

Concrete examples 18-25 use what mixed 2 types of polymers 3 and the polymer 9-16 of a "back elongation type | mold" 9-16 as an admixture in the ratio of 60/40 by weight ratio. Manufactured. These concretes maintain a retention rate of about 80% for 90 to 120 minutes, and there is little fluctuation in the retention rate during that period. From these results, it can be understood that the holding time can be adjusted or the fluidity can be kept constant for a long time by mixing plural kinds of polymers as required. It is presumed that the same effect can be obtained even when the polymer of the present invention is mixed with other general admixtures.
As described above, from Tables 3 to 5, the technical significance of using the polyalkylene glycol polymer of the present invention was confirmed in terms of improving various performances such as retention performance of inorganic particle compositions such as concrete. .

Claims (11)

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 contains 1 to 99 mol% of a monomer having a hydrolyzable group with respect to 100 mol% of the total amount of vinyl monomers, and 1 unsaturated polyalkylene glycol monomer. A polyalkylene glycol polymer characterized by containing ~ 99 mol%. 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 contains 1 to 99 mol% of a monomer having a hydrolyzable group with respect to 100 mol% of the total amount of vinyl monomers, and 1 unsaturated polyalkylene glycol monomer. A polyalkylene glycol polymer characterized by containing ~ 99 mol%. The polyalkylene according to claim 1 or 2, wherein the content of the monomer having a hydrolyzable group is 20 mol% or more with respect to 100 mol% of the total amount of the vinyl monomers. Glycol polymer. The polyalkylene glycol polymer according to any one of claims 1 to 3, wherein the hydrolyzable group includes a functional group that generates a carboxyl group by hydrolysis. The polyalkylene glycol polymer according to any one of claims 1 to 4, wherein the vinyl monomer further contains an unsaturated carboxylic acid monomer. The polyalkylene glycol polymer according to any one of claims 1 to 5, wherein the organic residue contains a sulfur atom. The polyalkylene glycol chain according to any one of claims 1 to 6, wherein the polyalkylene glycol chain has an average number of repeating alkylene oxides of 5 to 1,000. 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 carbon atoms. Represents an oxyalkylene group of ˜18, Y ¹ is the same or different and represents a direct bond or an organic residue, and Z is the same or different and is a structural unit derived from a vinyl monomer having a hydrolyzable group. N 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. m is an integer from 1 to 50. The polyalkylene glycol polymer according to any one of claims 1 to 7, wherein the polyalkylene glycol polymer has the following structure. An inorganic particle dispersant comprising the polyalkylene glycol polymer according to any one of claims 1 to 8. An inorganic particle admixture comprising the polyalkylene glycol polymer according to any one of claims 1 to 8. An inorganic particle composition comprising the inorganic particle admixture according to claim 10.