JP2012232873A - Polyalkylene glycol-based polymer - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a polyalkylene glycol-based polymer which exhibits performances such as cement dispersibility or slump retention property at a higher level, and is thereby useful for various applications, especially for the application of cement admixture, and to provide a cement admixture and a cement composition using the same.SOLUTION: The polyalkylene glycol-based polymer has such a structure that a terminal oxygen atom at at least one terminal of a polyalkylene glycol chain is bonded directly or via an organic residue to the terminal of the main chain of a polymer including a constituent unit derived from a vinyl-based monomer component. The polyalkylene glycol-based polymer has a structure of the formula (1), and the vinyl-based monomer component indispensably includes an unsaturated polyalkylene glycol-based monomer. In the unsaturated polyalkylene glycol-based monomer, the average added mole number r is 50 or more.

Description

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

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

With respect to a polymer containing a conventional polyalkylene glycol chain, for example, both ends obtained by decomposing a thioester group formed after adding a thiocarboxylic acid to a polyether having a double bond at both ends or one end A polyether having a mercapto group at one end (for example, see Patent Document 1) or a compound having a mercapto group as a biodegradable water-soluble polymer used in a detergent builder is introduced into a polyether compound by an ester reaction. A polymer obtained by subjecting a modified polyether compound to block or graft polymerization of a monoethylenically unsaturated monomer component is disclosed (for example, see Patent Document 2). Further, it is disclosed that a novel polymer having a polymer unit comprising a polyalkylene glycol chain and a constituent unit derived from an unsaturated monomer bonded to at least one end of the chain is particularly useful as a cement admixture. (For example, refer to Patent Document 3). Also, radical polymerization of esters of mercapto fatty acids and polyoxyalkylene compounds used as antioxidants and raw materials for synthetic resins, and their production methods, and vinyl polymerizable monomers such as (meth) acrylic acid esters, etc. The block copolymer obtained by making it do is disclosed (for example, refer patent document 4).

Japanese Patent Publication No. 7-13141 JP-A-7-109487 JP 2007-119736 A JP 2002-128889 A

Thus, what has various structures as a polymer containing a polyalkylene glycol chain is proposed. However, a polymer containing a conventional polyalkylene glycol chain has not yet reached a level where the extremely high performance (cement dispersibility (water-reducing property) and slump retention property) demanded recently can be sufficiently exhibited. Therefore, there has been room for improvement to make the compound useful in more fields by making it suitable for use as a cement admixture.
The present invention has been made in view of the above-mentioned present situation, and can exhibit performance such as cement dispersibility and slump retention at a higher level, and is useful for various applications, particularly cement admixture applications. It is an object of the present invention to provide a polymer, a cement admixture and a cement composition using the same.

The present inventor has made various studies on polymers containing a polyalkylene glycol chain, and a polymer in which at least one terminal oxygen atom at the terminal of the polyalkylene glycol chain contains a constituent unit derived from a vinyl monomer component. It has been found that if the structure is bonded directly to the main chain end of the polymer or via an organic residue, high water-reducing performance can be exhibited only by adding a small amount to the cement composition or the like. In addition, as the vinyl monomer component, a component that essentially contains an unsaturated polyalkylene glycol monomer is used, and the average addition mole number of the oxyalkylene group in the unsaturated polyalkylene glycol monomer is specified. It was found that within the range, the cement dispersibility of the polyalkylene glycol polymer and the slump retention of the cement composition containing the polymer were improved. And it discovered that the cement admixture obtained using the polymer of this invention can exhibit outstanding performance (dispersibility, slump retention property, etc.), and the cement composition containing this is especially in the cement field. It has been found useful and has reached the present invention.

That is, in the present invention, the terminal oxygen atom at at least one of the terminal ends of the polyalkylene glycol chain is bonded directly or via an organic residue to the main chain terminal of the polymer containing the structural unit derived from the vinyl monomer component. A polyalkylene glycol-based polymer having a structure, wherein the polymer has the following general formula (1):

(In the formula, X represents an oxygen atom or a residue of a compound having two or more active hydrogens. AO is the same or different and represents an oxyalkylene group having 2 to 18 carbon atoms. N and n ′ Are the same or different and each represents the average number of added moles of the oxyalkylene group and is a number from 50 to 1000. Y ¹ and Y ² are the same or different and each represents a direct bond or an organic residue. Are the same or different and the residue of the polymer containing the structural unit derived from the vinyl monomer component Q ¹ is the same or different and is a hydrogen atom, an alkyl group having 1 to 10 carbon atoms or an alkylene group. And a residue of a compound having one or more active hydrogens, or Z. m and p are integers of 1 to 50.) Ingredients are unsaturated polyalkylene glycol monomers A polyalkylene glycol-based polymer that is essential and has an average addition mole number r of oxyalkylene groups in the unsaturated polyalkylene glycol-based monomer of greater than 50.

In the present invention, the terminal oxygen atom in at least one of the terminals of the polyalkylene glycol chain is bonded to the main chain terminal of the polymer containing the structural unit derived from the vinyl monomer component directly or through an organic residue. A method for producing a polyalkylene glycol polymer having a structure, wherein the production method comprises the following general formula (2):

(In the formula, X represents an oxygen atom or a residue of a compound having two or more active hydrogens. AO is the same or different and represents an oxyalkylene group having 2 to 18 carbon atoms. N and n ′ Are the same or different and each represents the average number of moles of the oxyalkylene group, and is a number from 50 to 1000. Y ¹ and Y ² are the same or different and each represents a direct bond or an organic residue. ² is the same or different and represents a hydrogen atom, an alkyl or alkylene group having 1 to 10 carbon atoms, or a residue of a compound having one or more active hydrogens, and m and p are 1 to 50. The vinyl monomer component is polymerized in the presence of a polyalkylene glycol chain-containing compound represented by the formula: wherein the vinyl monomer component is an unsaturated polyalkylene glycol monomer. Is included The average addition mole number r of the oxyalkylene group in the unsaturated polyalkylene glycol monomer is more than 50, which is also a method for producing a polyalkylene glycol polymer.

The present invention is also a cement dispersant containing the above polyalkylene glycol polymer.
The present invention is also a cement admixture containing the polyalkylene glycol polymer.
The present invention is also a cement composition containing the above cement admixture.
The present invention is described in detail below.

<Polyalkylene glycol polymer>
The polyalkylene glycol polymer of the present invention will be described.
Hereinafter, the polyalkylene glycol polymer of the present invention is referred to as “polyalkylene glycol polymer (i)” or “polymer (i)”, and the polyalkylene glycol chain of the polyalkylene glycol polymer of the present invention is directly Alternatively, a polymer containing a structural unit derived from a vinyl-based monomer component that is bonded via an organic residue (a polymer that forms a residue represented by Z in the general formula (1)) is referred to as “ Also referred to as “polymer (ii)”.

In the polyalkylene glycol polymer (i), the vinyl monomer component for forming the polymer (ii) is an unsaturated polyalkylene glycol system in which the average addition mole number r of oxyalkylene groups is greater than 50. A monomer (hereinafter, also referred to as “unsaturated polyalkylene glycol monomer (A)” or simply “monomer (A)”) is essential. That is, the polyalkylene glycol polymer (i) of the present invention includes a structural unit derived from the monomer (A). When the polyalkylene glycol polymer (i) is used as a dispersant such as cement, the polymer (i) is an unsaturated polyalkylene glycol monomer (average added mole number r of oxyalkylene group greater than 50). When the structural unit is derived from A), the ability to disperse the polymer (i) cement particles can be remarkably improved by the steric repulsion of the polyalkylene glycol chain of the monomer (A). Furthermore, the setting speed of the cement composition is improved, and the relatively initial strength of about 24 hours after water injection is improved. The average addition mole number of the oxyalkylene group (average repeat number of alkylene oxide) is the alkylene added in 1 mole of the polyalkylene glycol chain of the unsaturated polyalkylene glycol monomer (A). Means the average number of moles of oxide. The average addition mole number r of the oxyalkylene group is not particularly limited as long as it is a number larger than 50, but is preferably 75 or more, more preferably 100 or more, and still more preferably from the viewpoint of strongly dispersing cement particles. Is 150 or more. The average addition mole number r of the oxyalkylene group is also a viewpoint of ensuring sufficient workability by making the viscosity of the cement composition moderate when the polyalkylene glycol polymer (i) is used as a cement admixture. Therefore, 300 or less is preferable. More preferably it is 250 or less, and still more preferably 200 or less.
Details of the unsaturated polyalkylene glycol monomer (A) will be described later.

Next, the structure of the polyalkylene glycol polymer (polymer (i)) in the present invention will be described.
The polymer (i) has the following general formula (1):

(In the formula, X represents an oxygen atom or a residue of a compound having two or more active hydrogens. AO is the same or different and represents an oxyalkylene group having 2 to 18 carbon atoms. N and n ′ Are the same or different and each represents the average number of added moles of the oxyalkylene group and is a number from 50 to 1000. Y ¹ and Y ² are the same or different and each represents a direct bond or an organic residue. Are the same or different and the residue of the polymer containing the structural unit derived from the vinyl monomer component Q ¹ is the same or different and is a hydrogen atom, an alkyl group having 1 to 10 carbon atoms or an alkylene group. Represents a residue of a compound having 1 or 2 or more active hydrogens, or Z. m and p are integers of 1 to 50).

The polymer having the structure represented by the general formula (1) includes a polyalkylene glycol-based polymer having a multi-branched structure and a polyalkylene glycol-based non-multi-branched (straight chain) structure having no multi-branched structure. Polymer.
In the above general formula (1), when m = 1 and p = 1, the polymer (i) is a non-multi-branched (straight chain) polyalkylene glycol polymer having no multi-branched structure. When m + p ≧ 3, the polymer (i) is a polyalkylene glycol polymer having a multi-branched structure.
The polyalkylene glycol polymer having a multi-branched structure as used herein means that a polymer chain containing a polyalkylene glycol chain is bonded to at least three or more sites having active hydrogen of a compound having three or more active hydrogens. In addition, it means a structure in which the polymer chain is branched radially from the residue of a compound having 3 or more active hydrogens. On the other hand, a polyalkylene glycol polymer having a non-multi-branched (straight chain) structure is a structure that does not have the above-mentioned polymer chain branched radially from the residue of a compound having three or more active hydrogens. Means.
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 polymer (ii) containing a structural unit derived from a vinyl monomer component is branched from the main chain as in the case where the polymer is formed using an unsaturated monomer having a polyalkylene glycol chain as a raw material. It may have a branched structure.

When m = 1 and p = 1, that is, when the polymer (i) is a non-multi-branched (straight chain) polyalkylene glycol polymer having no multi-branched structure, the above general formula ( When X in 1) is an oxygen atom, the above polymer (i) is bonded to polymer (ii) containing a structural unit derived from a vinyl monomer component directly or via an organic residue. It becomes a polymer having a polyalkylene glycol chain (hereinafter also referred to as polymer (ia)). On the other hand, if X in the general formula (1) is a residue of a compound having two or more active hydrogens, the polymer (i) binds to a residue of a compound having two or more active hydrogens. A polymer having one polyalkylene glycol chain (hereinafter also referred to as polymer (ib)) is obtained.

When the polyalkylene glycol chain is represented by “PAG”, the structure of the polymer (ia) has the following general formula (a):
^{Q 1 -Y 2 - (PAG)} -Y 1 -Z (a)
(Wherein Y ¹ , Y ² , Z and Q ¹ are the same as those in the general formula (1)).
Moreover, when Q < ¹ > -Y < ² >-in the said general formula (a) represents a hydrogen atom as a whole, the structure of the said polymer (ia) has the following general formula (b):
^{(PAG) -Y 1 -Z (b} )
(Y ¹ and Z in the formula are the same as those in the general formula (a)).

When the residue of a compound having two or more active hydrogens is represented by “X ′”, the structure of the polymer (ib) is represented by the following general formula (c):
^{Q 1 -Y 2 - (PAG)} -X '- (PAG) -Y 1 -Z (c)
(Wherein Y ¹ , Y ² , Z and Q ¹ are the same as those in the general formula (1)).
Moreover, when Q < ¹ > -Y < ² >-in the said general formula (c) represents a hydrogen atom as a whole, the structure of the said polymer (ib) has the following general formula (d):
^{(PAG) -X '- (PAG} ) -Y 1 -Z (d)
(Y ¹ and Z in the formula are the same as those in the general formula (c)).

When m + p ≧ 3, the polymer (i) is a polyalkylene glycol polymer having a multi-branched structure (hereinafter also referred to as polymer (ic)). In this case, X in the general formula (1) is a residue of a compound having 3 or more active hydrogens. Examples of the polymer (ic) include three or more active hydrogens in the residue of a compound having three or more active hydrogens as represented by the following formula (A) or (B). A compound having a structure in which a number of polyalkylene glycol chains equal to the number of active hydrogens in the compound are bonded can be exemplified.

In the 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.
In the above formula (B), the residue of the compound having 3 or more active hydrogens is a sorbitol residue (polyhydric alcohol residue), and all the active hydrogens possessed by sorbitol contain a polyalkylene glycol chain and a sulfur atom. FIG. 2 schematically shows a structure in which an organic residue contained is bonded, and further, a structural unit derived from a vinyl monomer component is bonded to some sulfur atoms.

The polymer (ic) is also a polyalkylene glycol having 3 or more residues in the compound having 4 or more active hydrogens and less than the number of active hydrogens in the compound having 4 or more active hydrogens. The thing which has the structure where the chain | strand couple | bonded can also be mentioned.

In the general formula (1), X represents an oxygen atom or a residue of a compound having two or more active hydrogens.
When m = 1 and p = 1, that is, when the polymer (i) is a polyalkylene glycol polymer having a non-multi-branched (straight chain) structure that does not have a multi-branched structure, X is , An oxygen atom, and a residue of a compound having two or more active hydrogens.
On the other hand, when m + p ≧ 3, that is, when the polymer (i) is a polyalkylene glycol polymer having a multi-branched structure, X is a residue of a compound having 3 or more active hydrogens. It is necessary to be.

In the present specification, the residue of a 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. .
When the compound having active hydrogen is used to form the structural moiety represented by X in the general formula (1) in the production of the polyalkylene glycol polymer (i) of the present invention, the active hydrogen The number of active hydrogens in the compound having suffices to be not less than the number of polyalkylene glycol chains bonded to the residue of the compound having active hydrogen represented by X. That is, the number of active hydrogens should just be more than the total value of m and p in the said General formula (1).
For example, in the production of a polyalkylene glycol polymer (i) having a non-multi-branched (straight chain) structure that does not have a multi-branched structure, the compound having active hydrogen is represented by X in the general formula (1). The number of active hydrogens in a compound having active hydrogens should be two.
Further, the compound having active hydrogen is used to form a structural portion represented by X in the general formula (1) in the production of a polyalkylene glycol polymer (i) having a multi-branched structure. In this case, the number of active hydrogens of the compound having active hydrogens needs to be 3 or more. Moreover, it is suitable that it is 50 or less from a polymeric viewpoint at the time of superposing | polymerizing using the polyalkylene glycol chain containing thiol compound mentioned later. When the polyalkylene glycol polymer (i) having a multi-branched structure is produced, the lower limit value of the number of active hydrogens is preferably 4 and more preferably 5. Moreover, as an upper limit, More preferably, it is 20 pieces, More preferably, it is 10.

Specific examples of the residue of the compound having two or more active hydrogens include, for example, polyhydric alcohol residues having a structure in which active hydrogen is removed from the hydroxyl group of the polyhydric alcohol, and active from the amino group of the polyvalent amine. A polyvalent amine residue having a structure excluding hydrogen, a polyvalent imine residue having a structure in which active hydrogen is removed from an imino group of a polyvalent imine, and a structure in which active hydrogen is removed from an amide group of a polyvalent amide compound Multivalent amide residues and the like are preferred. Of these, polyvalent amine residues, polyalkyleneimine residues and polyhydric alcohol residues are preferred. That is, the residue of the compound having two or more active hydrogens is at least one polyvalent compound residue selected from the group consisting of a polyvalent amine residue, a polyalkyleneimine residue and a polyhydric alcohol residue. Preferably it is.
In addition, the structure of the compound residue having active hydrogen may be any of a chain, a branched structure, and a three-dimensionally crosslinked structure.

Among the preferred specific examples of the residue of the compound having two or more active hydrogens, the polyvalent amine (polyamine) may be a compound having an average of two or more amino groups in one molecule. Preferred are alkylamines such as amines; alkylene amines such as allylamine; aromatic amines such as aniline; homopolymers and copolymers obtained by polymerizing one or more monoamine compounds such as ammonia by a conventional method. It is. Such a compound forms a polyvalent amine residue of the polyalkylene glycol polymer.
Furthermore, it may be a diamine or higher amine compound such as ethylenediamine, diethylenetriamine, triethylenetetramine, or a polyamine obtained by polymerizing one or more of them. Such a polyamine usually has a primary amino group having an active hydrogen atom or a secondary amino group (imino group) in addition to a tertiary amino group in the structure.

The polyalkyleneimine may be a compound having an average of two or more imino groups in one molecule. For example, one or two kinds of alkyleneimines having 2 to 8 carbon atoms such as ethyleneimine and propyleneimine. A homopolymer or copolymer obtained by polymerizing the above by a conventional method is preferred. By such a compound, the polyalkyleneimine residue of the polyalkylene glycol polymer is formed. 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, ethyleneimine is more preferable from the viewpoint of performance exhibited by the polyalkylene glycol polymer.

As a number average molecular weight of the said polyvalent amine and polyalkyleneimine, 100-100000 are preferable, More preferably, it is 300-50000, More preferably, it is 600-10000, Most preferably, it is 800-5000.

The polyhydric alcohol may be a compound containing an average of two 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, Suitable are sugars such as adonitol, arabitol, xylitol, mannitol, glucose, sugar alcohols such as glucite, and sugar acids such as gluconic acid. By such a compound, the polyhydric alcohol residue of the polyalkylene glycol polymer is formed.
Among these, glycerin, polyglycerin, trimethylolpropane, erythritol, pentaerythritol, dipentaerythritol, sorbitol, and sorbitan are more preferable from the viewpoint of industrial production efficiency.

The number of the polyalkylene glycol chains to which the compound having two or more active hydrogens is bonded is preferably equal to the number of active hydrogens in the compound having two 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 two or more active hydrogens. This makes it possible to provide a cement admixture that can exhibit even better dispersion performance.
The number of the polyalkylene glycol chains to which the compound having two or more active hydrogens is bonded corresponds to the total value of m and p in the general formula (1). Accordingly, the total value of m and p is preferably equal to the number of active hydrogens in the compound having two or more active hydrogens.

In the general formula (1), (AO) _n and (AO) _{n ′} each represent a polyalkylene glycol chain composed of an oxyalkylene group having 2 to 18 carbon atoms (alkylene oxide, AO).
In the following, a polyalkylene glycol chain bonded directly or via an organic residue to the main chain terminal of the polymer (ii) containing a structural unit derived from a vinyl monomer component, that is, in the general formula (1) The polyalkylene glycol chain represented by (AO) _n or (AO) _{n ′} is also referred to as “polyalkylene glycol chain (I)”. In addition, the polyalkylene glycol chain of the unsaturated polyalkylene glycol monomer contained in the vinyl monomer component in the polymer (ii) containing the structural unit derived from the vinyl monomer component is referred to as “polyalkylene glycol chain”. (II) ". The polyalkylene glycol chains (I) and (II) are preferably substantially linear.

When the polymer (i) is used as a dispersant such as cement, the polyalkylene glycol chain (I) has an effect of imparting hydrophilicity and steric repulsion to the dispersoid and stably dispersing it. In addition, as a characteristic effect, it greatly affects the rheological properties of the dispersion system, such as separation resistance and yield stress. By adjusting the structure and amount of the polyalkylene glycol chain (I) according to the purpose, the polymer (i) having very good dispersibility and rheological properties can be obtained.

The alkylene oxide constituting the polyalkylene glycol chain (I) may be an oxyalkylene group having 2 to 18 carbon atoms (alkylene oxide, AO), but the polyalkylene glycol polymer (i) of the present invention may be used. It is preferable to select appropriately according to the required use. For example, when used for the production of cement admixture components, a relatively short chain alkylene oxide (oxyalkylene group) having about 2 to 8 carbon atoms is mainly used from the viewpoint of affinity with cement particles. 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. Thereby, the obtained polyalkylene glycol polymer (i) becomes sufficiently hydrophilic, and sufficient water solubility and cement particle dispersion performance are imparted to the polymer (i).

The “main body” as used herein means that when the polyalkylene glycol chain (I) is composed of two or more types of alkylene oxides, it accounts for the majority of the total number of alkylene oxides present. When “dominating” is expressed in terms of mol% of ethylene oxide in 100 mol% of all alkylene oxides, 50 to 100 mol% is preferable. Thereby, the polymer (i) has higher hydrophilicity. More preferably, it is 60 mol% or more, More preferably, it is 70 mol% or more, Especially preferably, it is 80 mol% or more, Most preferably, it is 90 mol% or more.

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. Good. When the block arrangement is used, the hydrophilicity of the hydrophilic block is expressed more strongly than the random arrangement, and the hydrophobicity of the hydrophobic block seems to be expressed more strongly. This is preferable because workability is 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).

N and n ′ in the general formula (1) are the same or different and represent the average number of added moles of the oxyalkylene group, that is, the average number of repeating alkylene oxides in the polyalkylene glycol chain (I). A number of 1000. By setting the average number of repetitions to 50 or more, the polymer (i) can sufficiently exhibit performance based on the polyalkylene glycol chain. In addition, when the average number of repetitions exceeds 1000, the viscosity of the raw material compound used for producing the polymer (i) increases, the reactivity is not sufficient, and so on in terms of workability. It may not be suitable.
The sum of n and n ′ can be regarded as the diameter of the polyalkylene glycol chain (I) for convenience. From the viewpoint of sufficiently exhibiting the dispersion performance of the cement particles of the polymer (i), the total of n and n ′ is preferably 100 to 1500. The lower limit of the sum of n and n ′ is more preferably 200, still more preferably 250, particularly preferably 300, most preferably 350, and the upper limit is more preferably 1000, still more preferably 800, Particularly preferred is 600, and most preferred is 400.
The total of n and n ′ is preferably at least half of the average added mole number r of the oxyalkylene group in the unsaturated polyalkylene glycol monomer (A). That is, n and n ′ preferably satisfy n + n ′ ≧ 0.5r. When n, n ′ and r satisfy the above relationship, the effect of steric repulsion caused by the polyalkylene glycol chain (I) and the effect of steric repulsion caused by the polyalkylene glycol chain (II) are exhibited in a balanced manner. As a result, the polyalkylene glycol polymer (i) of the present invention exhibits extremely good cement dispersibility. More preferably, n + n ′ ≧ 1r is satisfied, further preferably n + n ′ ≧ 1.5r, particularly preferably n + n ′ ≧ 2r, and most preferably n + n ′ ≧ 3r. n and n ′ also preferably satisfy 10r ≧ n + n ′. More preferably, 8r ≧ n + n ′ is satisfied, and further preferably 6r ≧ n + n ′.
When m + p ≧ 3, that is, when the polymer (i) is a polyalkylene glycol polymer having a multi-branched structure, (AO) _{n is} included in the structure of the polymer (i). At least one of the polyalkylene glycol chain represented by (II) and the polyalkylene glycol chain represented by (AO) _{n ′} is present in plural types. In this case, it is preferable that at least one combination of n and n ′ whose total value satisfies the above condition exists.
The average number of repeating alkylene oxides (average number of moles of oxyalkylene group added) is the average number of moles of alkylene oxide added in 1 mole of the polyalkylene glycol chain of the polymer (i). Means.

The structural site represented by Y ¹ or Y ² in the general formula (1) is a direct bond or an organic residue, and Y ¹ and Y ² may be different from each other or the same. . Y ¹ and Y ² are organic residues in that the bond between the polyalkylene glycol chain (I) and the polymer (ii) containing a structural unit derived from a vinyl monomer component can be facilitated. It 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.

Examples of the organic residue, is preferred to be those containing sulfur atoms, specifically, for ^{example, -S-Y 3 -COO -,} - S-Y 3 -CO -, - S-Y 3 - CO—NH—, —S—Y ³ —CO—NH—CH ₂ —CH ₂ —, —S—Y ³ —, —S—Y ³ —O—, —S—Y ³ —N—, —S— Y ³ —S— or the like is preferable. Here, Y ³ 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 this case, as described later, during the production of the polyalkylene glycol polymer of the present invention, monomers are successively added to the polyalkylene glycol chain-containing thiol compound via the sulfur atom due to the reactivity of the sulfur atom. In addition, a residue of the polymer (ii), that is, a site represented by Z in the general formula (1) is formed, which is advantageous for production.

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 It is also one preferred form of the present invention that the organic residue containing an atom contains a carbonyl group or an amide group. In this case, since the production of the polyalkylene glycol polymer of the present invention is easy and can be produced at low cost, it is useful for industrial production.
In this case, the carbon atom contained in the carbonyl group (including the —CO group in the amide group) is adjacent to the terminal oxygen atom of the polyalkylene glycol chain at the bonding site between the organic residue and the polyalkylene glycol chain. It is preferable to do. That is, the polymer (i) is preferably one in which a polyalkylene glycol chain and Y ³ are bonded via an ester bond or an amide bond.

Z in the said General formula (1) represents the residue of the polymer containing the structural unit derived from a vinyl-type monomer component. The polymer containing a structural unit derived from the vinyl monomer component (polymer (ii)) may be one type of polymer or a mixture of two or more types of polymers. However, the vinyl-type monomer component which forms it contains the said unsaturated polyalkylene glycol-type monomer (A) essential. That is, the polymer (ii) includes a structural unit derived from the monomer (A). The structural unit derived from the monomer (A) is a structure in which a polymerizable double bond of the monomer (A) is opened by a polymerization reaction (a double bond (C = C) is a single bond ( -C-C-).
The monomer (A) is a vinyl monomer, and has at least one polyalkylene glycol chain (II) having an average addition mole number r of oxyalkylene group larger than 50 in the molecule. Good. When having two or more polyalkylene glycol chains (II) in one molecule, the polyalkylene glycol chains may be the same or different. The unsaturated polyalkylene glycol monomer (A) is a monomer having the same polyalkylene glycol chain (II) type (two or more polyalkylene glycol chains (II) in one molecule). May be used only in combination, or monomers having different types (or combinations) of polyalkylene glycol chains (II) may be used in combination.
When the unsaturated polyalkylene glycol monomer (A) has two or more polyalkylene glycol chains (II) in one molecule, the average added mole number r of oxyalkylene groups in at least one of them. Should be larger than 50.

The vinyl monomer component is also referred to as an unsaturated carboxylic acid monomer (hereinafter referred to as “unsaturated carboxylic acid monomer (a)” or simply “monomer (a)”). ) As an essential component. Thereby, the hydrophilicity of the polyalkylene glycol polymer is improved, and it can be made useful for various applications. In this case, the vinyl monomer component includes the unsaturated carboxylic acid monomer (a) and the unsaturated polyalkylene glycol monomer (A). Thus, it is considered that the cement particles can be extremely effectively dispersed by these synergistic effects. That is, the structural unit derived from the vinyl monomer component includes a structural unit derived from the unsaturated carboxylic acid monomer (a) and a structural unit derived from the unsaturated polyalkylene glycol monomer (A). It is suitable that it is a form including.
Thus, it is one of the preferred embodiments in the present invention that the vinyl monomer component essentially contains the unsaturated carboxylic acid monomer (a).

Examples of the unsaturated carboxylic acid monomer (a) include the following general formula (3);

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

In the general formula (3), 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 (3) include monocarboxylic acid monomers such as acrylic acid, methacrylic acid, and crotonic acid; maleic acid, itaconic acid, fumaric acid, and the like. Dicarboxylic acid monomers such as acids; anhydrides or salts of these carboxylic acids (for example, alkali metal salts, alkaline earth metal salts, trivalent metal salts, ammonium salts, organic amine salts) and the like. Among these, acrylic acid, methacrylic acid, maleic acid, maleic anhydride and salts thereof are preferable from the viewpoint of polymerizability, and acrylic acid, methacrylic acid and salts thereof are more preferable. As the monomer (a), one or more of these can be used.

The vinyl monomer component further includes an unsaturated polyalkylene glycol monomer other than the unsaturated polyalkylene glycol monomer (A) in which the average addition mole number r of the oxyalkylene group is greater than 50. May be. Hereinafter, the monomer (A) and the unsaturated polyalkylene glycol monomer other than the monomer (A) are combined to produce an unsaturated polyalkylene glycol monomer (b) (or simply “Monomer (b)”).

Examples of the unsaturated polyalkylene glycol monomer (b) include the following general formula (4);

(.AO ^wherein, R 4, ^{R 5} and ^{R 6} are the same or different, .R ⁷ represents a hydrogen atom or a methyl group, represents a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms are the same Or, differently, it represents one or 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 added moles of the oxyalkylene group, 1 Is a number of ˜300.). However, the monomer (b) contains at least the unsaturated polyalkylene glycol monomer (A) having the structure described above.
In addition, when the said vinyl-type monomer component contains the said monomer (b), the said polymer (ii) will contain the structural unit derived from a monomer (b). The structural unit derived from the monomer (b) is a structure (double bond (C = C)) in which the polymerizable double bond of the monomer (b) represented by the general formula (4) is opened by a polymerization reaction. , A structure formed as a single bond (—C—C—)).

In the general formula (4), of the terminal group represented by ^{R 7,} examples of the hydrocarbon group having 1 to 20 carbon atoms, aliphatic alkyl group having 1 to 20 carbon atoms, 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 ⁷ is preferably a hydrophilic group from the viewpoint of dispersibility of cement particles when used for cement admixture, specifically, a hydrogen atom or carbon. The hydrocarbon group of number 1-8 is preferable. A hydrogen atom or a hydrocarbon group having 1 to 6 carbon atoms is more preferable, a hydrogen atom or a hydrocarbon group having 1 to 3 carbon atoms is still more preferable, and a hydrogen atom or a methyl group is particularly preferable.

In the general formula (4), the preferred structure of the polyalkylene glycol chain (II) represented by (AO) _{r ′} is the same as described for the polyalkylene glycol chain (I).

In the general formula (4), r ′, that is, the average number of alkylene oxide repeats in the polyalkylene glycol chain (II) is such that the monomer (b) is an unsaturated polyalkylene glycol monomer (A). In some cases, r is as described above. However, although the monomer (b) is different from the unsaturated polyalkylene glycol monomer (A), the unsaturated polyalkylene glycol monomer having the structure represented by the general formula (4) is used. In the case of the isomer, the average addition mole number r ′ of the oxyalkylene group in the unsaturated polyalkylene glycol monomer is a number of 1 to 300. If r 'exceeds 300, production problems may occur, and when used as a cement admixture, the viscosity of the cement composition may increase and workability may not be 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 (b) represented by the general formula (4) include an unsaturated alcohol polyalkylene glycol adduct and a polyalkylene glycol ester monomer.
The unsaturated alcohol polyalkylene glycol adduct may be a compound having a structure in which a polyalkylene glycol chain is added to an alcohol having an unsaturated group.
The polyalkylene glycol ester monomer may be any monomer having a structure in which an unsaturated group and a polyalkylene glycol chain are bonded via an ester bond. An unsaturated carboxylic acid polyalkylene glycol ester monomer may be used. Compounds are preferred, among which (alkoxy) polyalkylene glycol mono (meth) acrylate and (hydroxy) polyalkylene glycol mono (meth) acrylate are preferred, and methoxy polyalkylene glycol mono (meth) acrylate is most preferred. .

Examples of the unsaturated alcohol polyalkylene glycol adduct include vinyl alcohol alkylene oxide adduct, (meth) allyl alcohol alkylene oxide adduct, 3-buten-1-ol alkylene oxide adduct, isoprene alcohol (3-methyl- 3-buten-1-ol) alkylene oxide adduct, 3-methyl-2-buten-1-ol alkylene oxide adduct, 2-methyl-3-buten-2-ol alkylene oxide adduct, 2-methyl-2 -Butene-1-ol alkylene oxide adducts and 2-methyl-3-buten-1-ol alkylene oxide adducts are preferred. 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 vinyl monomer component used to obtain the polymer (ii) also includes the unsaturated carboxylic acid monomer (a) and the unsaturated polyalkylene glycol monomer (b) (described above). Other copolymerizable monomers (hereinafter also referred to as “monomer (c)”) other than the unsaturated polyalkylene glycol monomer (A) may be included.
In this case, the polymer (ii) further contains a structural unit derived from the monomer (c), and the structural unit derived from the monomer (c) is a monomer by polymerization reaction. It corresponds to a structure (a structure in which a double bond (C = C) is converted to a single bond (-C-C-)) having a polymerizable double bond in (c).

The preferable content of the unsaturated polyalkylene glycol monomer (A) in which the average addition mole number r of the oxyalkylene group in the polymer (ii) is greater than 50 is appropriately adjusted according to the required performance. That's fine. Examples of preferable contents of the monomer (A), the monomer (a), the monomer (b), the monomer (c) and the polyalkylene glycol chain (I) are shown below. In the above, the mass of the monomer (a) was that of the corresponding sodium salt. The total amount of the monomer components is 100% by mass and 100% by mol, respectively, and the polyalkylene glycol chain (I) is not included in this total amount.
From the viewpoint of sufficiently exerting the performance derived from the unsaturated polyalkylene glycol monomer (A), 50% by mass or more is preferable with respect to 100% by mass of all vinyl monomer components, and 70% by mass or more is preferable. More preferably, 80% by mass or more is further preferable, and 85% by mass or more is most preferable. Further, from the viewpoint of sufficiently exhibiting the performance of other vinyl monomers, it is preferably 97% by mass or less, more preferably 95% by mass or less, still more preferably 93% by mass or less, and most preferably 91% by mass or less.
From the viewpoint of sufficiently exhibiting the performance derived from the unsaturated carboxylic acid monomer (a), the content is preferably 1% by mass or more, more preferably 2% by mass or more, based on 100% by mass of all vinyl monomer components. 5 mass% or more is still more preferable, and 7.5 mass% or more is the most preferable. Moreover, from a viewpoint which fully exhibits the performance of another vinyl-type monomer component, 30 mass% or less is preferable, 20 mass% or less is more preferable, 15 mass% or less is further more preferable, and 10 mass% or less is the most preferable.
70 mass% or more is preferable with respect to 100 mass% of all vinyl-type monomer components from a viewpoint which fully exhibits the performance derived from the said unsaturated polyalkylene glycol monomer (b), and 80 mass% or more is preferable. More preferably, 85% by mass or more is further preferable, and 90% by mass or more is most preferable. Further, from the viewpoint of sufficiently exhibiting the performance of other vinyl monomers, 99% by mass or less is preferable, 97% by mass or less is more preferable, 95% by mass or less is further preferable, and 93% by mass or less is most preferable. Among these, the preferable content of the monomer (A) is as described above.
When using the said monomer (c), it is suitable to set it as 30 mass% or less with respect to 100 mass% of all the vinyl-type monomer components. More preferably, it is 20 mass% or less, More preferably, it is 10 mass% or less.
The content for fully exhibiting the features of the polyalkylene glycol chain (I) is preferably 1% by mass or more, more preferably 3% by mass or more, as a mass ratio to 100% by mass of the total vinyl monomer component. 5 mass% or more is further more preferable, and 7 mass% or more is the most preferable. Moreover, 50 mass% or less is preferable, 30 mass% or less is more preferable, 20 mass% or less is more preferable, and 15 mass% or less is the most preferable.

Q ¹ in the general formula (1) is the same or different and is a hydrogen atom, an alkyl group or alkylene group having 1 to 10 carbon atoms, a residue of a compound having one or more active hydrogens, or Z (vinyl Represents a residue of a polymer containing a structural unit derived from a system monomer component.
The polyalkylene glycol polymer (i) of the present invention has a polymer (ii) in which all of the structural sites represented by Q ¹ include a structural unit derived from a vinyl monomer component represented by Z. When it is a residue, all of the polyalkylene glycol chain (polyalkylene glycol chain represented by (AO) _n or (AO) _{n ′} in the general formula (1)) of the polymer (i) is It is bonded to the polymer (ii) (for example, see the above formula (A)).
On the other hand, residue of the polymer (i) has, at least one of the structural moiety represented by Q ^1, a polymer containing a constitutional unit derived from the vinyl monomer component represented by Z (ii) In the case where the polymer (i) has a polyalkylene glycol chain (polyalkylene glycol chain represented by (AO) _n or (AO) _{n ′} in the general formula (1)). At least one of them is not bonded to the polymer (ii) (for example, see the above formula (B)).
Thus, the polyalkylene glycol polymer (i) of the present invention may have a polyalkylene glycol chain that is not bonded to the polymer (ii) containing a structural unit derived from a vinyl monomer component.

As the residue of the compound having 1 or 2 or more active hydrogens, in addition to those described above as the residue of the compound having 2 or more active hydrogens with respect to the structural site represented by X, Residues can also be mentioned. The residue of a compound having one active hydrogen is an alcohol residue having a structure obtained by removing active hydrogen from the hydroxyl group of a monovalent alcohol, or an amine residue having a structure obtained by removing active hydrogen from the amino group of a monovalent amine. An imine residue having a structure obtained by removing active hydrogen from an imino group of a monovalent imine, an amide residue having a structure obtained by removing active hydrogen from an amide group of a monovalent amide compound, and the like are preferable.
The residue of the polymer containing a structural unit derived from a vinyl monomer component represented by Z is as described above.

As described above, the polyalkylene glycol polymer (i) in the present invention is a polymer chain containing a polyalkylene glycol chain in at least three or more sites having active hydrogen of a compound having three or more active hydrogens. And a polyalkylene glycol polymer (polymer (ic)) having a multi-branched structure in which the polymer chain is branched radially starting from the residue of the compound having 3 or more active hydrogens , A polyalkylene glycol polymer (polymer (i) having no non-branched (straight chain) structure having the above polymer chain radially branched starting from the residue of a compound having three or more active hydrogens. -A) and polymers (ib)). Among these, the polyalkylene glycol polymer (i) is preferably a polyalkylene glycol polymer having the above multi-branched structure. Due to the synergistic effect of the steric repulsion due to the multi-branched structure and the steric repulsion due to the polyalkylene glycol chain of the monomer (A), the ability to disperse the cement particles of the polymer (i) has jumped. It is because it improves.
Thus, the polymer (i) is a polyalkylene glycol-based polymer having a multi-branched structure, that is, in the general formula (1), m + p ≧ 3 and X is 3 active hydrogens. It is one of the preferred embodiments of the present invention that it is a residue of the compound having the above.

The polyalkylene glycol polymer of the present invention may have a weight average molecular weight (Mw) of 1 million or less in consideration of its handleability and retention of cement composition when used for cement admixture. Is preferred. More preferably, it is 500,000 or less, more preferably 300,000 or less, still more preferably 200,000 or less, and particularly preferably 150,000 or less. Further, when used for cement admixture, it is preferable that Mw is 1000 or more from the viewpoint that performance is better when adsorbed to cement particles to some extent, and the adsorption power increases as Mw increases. More preferably, it is 5000 or more, More preferably, it is 10,000 or more, 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.
In the present invention, the polyalkylene glycol polymer is a vinyl monomer in the presence of a polymer initiator having a polyalkylene glycol chain and a radical generating site and / or a polymer chain transfer agent having a polyalkylene glycol chain. It can be produced by polymerizing body components. By using the polymer initiator and / or polymer chain transfer agent, a polyalkylene glycol chain is introduced into the polyalkylene glycol polymer in the present invention.

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

First, a polyalkylene glycol polymer having one polyalkylene glycol chain bonded to the above polymer (ia), that is, a polymer (ii) containing a structural unit derived from a vinyl monomer component is produced. 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 above general formulas (e) to (f), “PAG” represents a polyalkylene glycol chain, and “Y” represents a direct or organic residue.
In these polymeric azo initiators (e) to (f), when the polyalkylene glycol chain (PAG) is located at the end of the polymer structure, the polyalkylene glycol chain (PAG) Or a residue of a compound having 1 or 2 or more hydrogen atoms, an alkyl group or alkylene group having 1 to 10 carbon atoms, or an active hydrogen atom, directly or at the end opposite to the end bonded to Y. It has a structure linked through an organic residue.
As a preferable form of the polymer azo initiator having a repeating unit represented by the general formula (e), the following general formula (5);

(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 represents a group in which an alkylene group having 1 to 20 is 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, n is the same or different and represents the average number of moles added of the oxyalkylene group, That.) Polymeric azo initiator having a repeating unit represented by the like.

Examples of the substituent for R ⁸ in the general formula (5) 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.

Among the polymeric azo initiators having a repeating unit represented by the general formula (5), a polymeric azo initiator having a repeating unit in which A ¹ O is an oxyethylene group is particularly suitable. Is a polymer azo initiator VPE series commercially available from Wako Pure Chemical Industries, Ltd., for example, VPE-0201 (number average molecular weight about 1.5 to 30,000, molecular weight of polyethylene oxide part about 2,000, m = 45), VPE-0401 (number average molecular weight of about 2.5 to 40,000, polyethylene oxide part molecular weight of about 4,000, m = 90), VPE-0601 (number average molecular weight of about 2.5 to 40,000, polyethylene oxide) The molecular weight of the portion is about 6,000, and m = 135).

As a preferable form of the polymeric azo initiator represented by the general formula (f), the following general formula (6):

(In formula, R <^11> 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 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 added moles of the oxyalkylene group, In a.) A polymer azo initiator represented by like.

Examples of the substituent for R ¹¹ in the general formula (6) 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.

The polymer azo initiator represented by the general formula (6) includes, for example, an azo initiator having a carboxyl group at both ends of the azo group (V-501 or the like, manufactured by Wako Pure Chemical Industries, Ltd.), and polyalkylene glycol. Can be obtained by esterification. As a method of esterification, since a azo initiator will decompose | disassemble when a heating process is performed, the manufacturing method which does not include a heating process is required. As such a production method, (1) a method in which an azo initiator is reacted with thionyl chloride to synthesize an acid chloride, and then a polyalkylene glycol is reacted to obtain a polymer azo initiator; (2) an azo initiator And polyalkylene glycol are subjected to dehydration condensation using dicyclohexylcarbodiimide (DCC) and 4-dimethylaminopyridine as required, to obtain a polymer azo initiator.

Next, the polymer (ib), that is, a polyalkylene glycol-based polymer having two polyalkylene glycol chains bonded to the residue of a compound having two or more active hydrogens, and the polymer (i -C), that is, as a method for producing a polyalkylene glycol polymer having a multi-branched structure, the following general formula (7);

(In the formula, X ¹ represents a residue of a compound having two or more active hydrogens. R ¹⁴ represents a hydrocarbon group having 1 to 20 carbon atoms. Y ⁴ 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 of 50 to 1,000. Q is an integer of 2 to 50.) A method of polymerizing a vinyl monomer component in the presence of a polymer azo initiator represented by

In the general formula (7), the residue of the compound having two or more active hydrogens represented by X ¹ is the same as the residue described for X in the general formula (1). The organic residue represented by Y ⁴ is the same as the organic residue described for Y ¹ and Y ^{2 in} the general formula (1). The oxyalkylene group having 2 to 18 carbon atoms represented by A ² O is the same as AO in the general formula (1). The average added mole number of the oxyalkylene group represented by k is the same as n in the general formula (1).

R ¹⁴ in the general formula (7) 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.
Moreover, q represents the number of the polyalkylene glycol chains couple | bonded with the residue of the compound which has 2 or more of active hydrogens, and is an integer of 2-50. By using a polymer azo initiator with q = 2, the above-mentioned non-multi-branched polyalkylene glycol polymer can be produced. Further, a residue of a compound in which X ¹ has three or more active hydrogen atoms, and in the case of using a polymeric azo initiator which is q ≧ 3, producing a polyalkylene glycol polymer having the multi-branched structure can do. The preferred range of q is the same as described for the total value of m and p in the general formula (1).

In the polymerization reaction, a polymer azo initiator having a repeating unit represented by the general formula (5) or a polymer azo initiator represented by the general formula (6) 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 (2):

(In the formula, X represents an oxygen atom or a residue of a compound having two or more active hydrogens. AO is the same or different and represents an oxyalkylene group having 2 to 18 carbon atoms. N and n ′ Are the same or different and each represents the average number of moles of the oxyalkylene group, and is a number from 50 to 1000. Y ¹ and Y ² are the same or different and each represents a direct bond or an organic residue. ² is the same or different and represents a hydrogen atom, an alkyl or alkylene group having 1 to 10 carbon atoms, or a residue of a compound having one or more active hydrogens, and m and p are 1 to 50. And a step of polymerizing a vinyl monomer component in the presence of a polyalkylene glycol chain-containing compound represented by the formula: wherein the vinyl monomer component is an unsaturated polyalkylene glycol monomer. Is essential, and the It is preferable to employ a production method in which the average addition mole number r of the oxyalkylene group in the unsaturated polyalkylene glycol monomer is greater than 50.

In the method for producing the polyalkylene glycol polymer, the polyalkylene glycol chain-containing compound may be any compound having the structure represented by the general formula (2).
X, AO, n, n ′, Y ¹ , Y ² , m, and p in the general formula (2) are the same as those in the general formula (1). Also, the structural moiety represented by Q ^2, the groups described for Q ¹ in the general formula (1), a polymer based non-radical Z of a structural unit derived from the vinyl monomer component It is the same.

In the general formula (2), the organic residue represented by Y ¹ or Y ² is preferably a group containing a sulfur atom as described above, but in this case, the sulfur atom and the general formula ( It is preferable that the hydrogen atom existing at the terminal of 2) is bonded. That is, the polyalkylene glycol chain-containing compound represented by the general formula (2) is preferably a compound having a mercapto group (thiol group, SH group) (hereinafter, such a compound is referred to as “polyalkylene”). Also referred to as “glycol chain-containing thiol compound”). This makes it possible to carry out the polymerization utilizing the unique reactivity of the mercapto group, and to produce the polyalkylene glycol polymer of the present invention more efficiently and simply at a low cost. Become.

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

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

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

In the polymerization reaction, the amount of the polymer azo initiator having the repeating unit represented by the general formula (5) or the polymer azo initiator represented by the general formula (6), or the polyalkylene glycol Use amount of chain-containing compound (preferably polyalkylene glycol chain-containing thiol compound), monomer (A), monomer (a), monomer (b) and single amount of vinyl monomer component The relationship with the usage-amount of a body (c) is the same as the preferable content for fully exhibiting the characteristic of the said polyalkylene glycol chain (I) mentioned above.

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- 1 or 2 of 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 More than seeds can be used. Among them, it is preferable to use an amphiphilic radical polymerization initiator because it is not necessary to remove insoluble components after polymerization, and an amphiphilic azo initiator is most preferable. 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.

The above polymer (ib), that is, a compound having two or more active hydrogens by the above production method (a production method including a step of polymerizing a vinyl monomer component in the presence of a polyalkylene glycol chain-containing compound). In the case of producing a polyalkylene glycol polymer having two polyalkylene glycol chains bonded to the residue of the above, and the polymer (ic), that is, a polyalkylene glycol polymer having a multi-branched structure, The polyalkylene glycol chain-containing thiol compound is obtained by a production method including a step of dehydrating and condensing a compound obtained by adding alkylene oxide to a compound having active hydrogen and a thiol compound having a carboxyl group. Is preferred.
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.

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 (ib) and (ic) can be obtained. The polymerization reaction of the vinyl monomer component is as described above.

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

As the above-mentioned cement composition, those containing cement, water, fine aggregate, coarse aggregate, and the like are suitable. Various mixed cements (blast furnace cement, silica cement, fly ash cement); white Portland cement; alumina cement; super fast cement (1 clinker fast cement, 2 clinker fast cement, magnesium phosphate cement) ); Grout cement; oil well cement; low exothermic cement (low exothermic blast furnace cement, fly ash mixed low exothermic blast furnace cement, high content of belite); ultra high strength cement; cement-based solidified material; Cement produced from one or more of incineration ash and sewage sludge incineration ash G) other such, these blast furnace slag, fly ash, cinder ash, clinker ash, husk ash, silica fume, silica powder, and a film obtained by adding a fine powder and gypsum limestone powder.
As the above aggregate, in addition to gravel, crushed stone, granulated slag, recycled aggregate, etc., siliceous, clay, zircon, high alumina, silicon carbide, graphite, chrome, chromic, magnesia, etc. Refractory aggregate and the like.

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

The cement admixture can also be used in combination with other known cement additives. Among them, it is particularly preferable to use an antifoaming agent or an AE agent in combination.

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

The present invention will be described in more detail with reference to the following examples. However, the present invention is not limited to these examples. Unless otherwise specified, “%” means “mass%” and “part” means “part by weight”. “Wt%” means “mass%”.
First, as an analysis method for polyalkylene glycol chain-containing thiol compounds, polymers thereof and comparative polymers, liquid chromatography (LC) analysis conditions / analysis conditions, and gel permeation chromatography (GPC) analysis conditions / analysis conditions Will be described. A measurement method for obtaining these solid contents will also be described.

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

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

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

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

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

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

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

<Polyalkylene glycol chain-containing thiol compound (PAG thiol compound)>
Production Example 1
(1) Dehydration esterification reaction process In a glass reactor equipped with a Dean-Stark device with a Dimroth condenser, a Teflon (registered trademark) stirring blade and a stirring seal, and a temperature sensor with a glass protective tube , Polyalkylene glycol (PEG-100, manufactured by Nippon Shokubai Co., Ltd., 1500.00 g), 3-mercaptopropionic acid (3-MPA, manufactured by Wako Pure Chemical Industries, Ltd., 80.34 g), p- Toluenesulfonic acid monohydrate (PTS · 1H ₂ O, Wako Pure Chemical Industries, 31.61 g), phenothiazine (PTZ, Wako Pure Chemical Industries, 0.7902 g), cyclohexane (CyH, 79. 02g) 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 120 ± 5 ° C. The reaction was completed by heating and refluxing for 40.0 hours while adding cyclohexane in the middle so that the temperature in the reaction system became 110 ± 5 ° C.
(2) Solvent removal step After completion of the reaction, the mixture was allowed to cool to 60 ° C. with stirring so as not to solidify, and then rapidly reacted with an aqueous solution obtained by adding water (1507.51 g) to a 30% aqueous NaOH solution (21.05 g). It was put into the vessel. Subsequently, the temperature was gradually raised to about 100 ° C., and cyclohexane was distilled off. The heating was stopped and nitrogen was bubbled at 30 mL / min for 90 minutes while cooling to remove residual cyclohexane to obtain an aqueous solution of the target compound (PAG thiol compound (1)).
As a result of LC analysis of the obtained target compound, the consumption rate of PEG-100 was 100.0%, and the average number of SH introduced per molecule of PEG-100 was 1.95. From this, the molecular weight was 4532. As a result of GPC analysis, the monomer amount was 94.2%, and the remainder was a multimer.

Production Example 2
(1) Dehydration esterification reaction process In a glass reactor equipped with a Dean-Stark device with a Dimroth condenser, a Teflon (registered trademark) stirring blade and a stirring seal, and a temperature sensor with a glass protective tube , Polyalkylene glycol chain-containing hexaol obtained by adding 450 mol of ethylene oxide to 1 mol of sorbitol (SB-450, manufactured by Nippon Shokubai Co., Ltd., 1500.00 g), 3-mercaptopropionic acid (3-MPA, 52.53 g), p- Toluenesulfonic acid monohydrate (PTS · 1H ₂ O, 31.05 g), phenothiazine (PTZ, 0.7763 g), and cyclohexane (CyH, 77.63 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 42.0 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 rapidly reacted with an aqueous solution obtained by adding water (1487.45 g) to 30% NaOH aqueous solution (20.68 g). It was put into the vessel. Subsequently, the temperature was gradually raised to about 100 ° C., and cyclohexane was distilled 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 SB-450 consumption rate was 100%, and the average number of SH introduced per molecule of SB-450 was 5.05. From this, the molecular weight was 20450. As a result of GPC analysis, the monomer amount was 84.2%, and the remainder was a multimer.

<Polyalkylene glycol chain-containing thiol polymer (Polymer Examples 1-1 to 1-2, 2-1 to 2-3, 3-1, 3-2, Polymer Comparative Examples 1-1 to 1-2, 2-1 to 2-3, 3-1 to 3-3)>
<Polymer Example 1-1>
As monomer solution, methacrylic acid (MAA, 4.06 g), methoxypolyethylene glycol methacrylate (average number of ethylene oxide additions: 90 mol: NOF Blenmer PME-4000, 58.66 g), PAG thiol compound obtained in Production Example 1 (2) A solution was prepared by adding ion-exchanged water to (4.78 g) to a total of 112.5 g.
As an initiator solution, 2,2′-azobis (2-methylpropionamidine) dihydrochloride (V-50, 0.17 g, manufactured by Wako Pure Chemical Industries, Ltd.) was added with ion-exchanged water to prepare a total solution of 37.5 g.
Dimroth cooling tube, Teflon (registered trademark) stirring blade and stirrer with stirring seal, nitrogen introduction tube, and glass reaction vessel equipped with temperature sensor were charged with 100 g of ion-exchanged water, and nitrogen was stirred at 300 rpm with 200 mL of nitrogen. The mixture was heated to 80 ° C. while introducing at a rate of / min.
Subsequently, the monomer solution was dropped into the reaction vessel over 3 hours and the initiator solution over 4 hours. The polymerization reaction was completed by maintaining at 80 ° C. for 1 hour after completion of the dropping. It cooled to room temperature and obtained the aqueous solution of the target polymer (polymer 1-1).
As a result of GPC analysis, the polymer was Mw = 105100, Mp = 105300, and Mn = 53200. The pure polymer content was 80.7%.

<Polymer Example 1-2>
Synthesis was performed in the same manner as in Polymer Example 1-1 except that the raw material compounds and amounts used in Polymer Example 1-1 were changed as shown in Tables 1 and 2, and the target polymer (polymer 1) was prepared. -2) aqueous solution was obtained.
Table 2 shows the GPC analysis results of the obtained polymer.
<Polymer Comparative Examples 1-1 to 1-2>
Synthesis was performed in the same manner as in Polymer Example 1-1 except that the raw material compounds and the amounts used in Polymer Example 1-1 were changed as shown in Tables 1 and 2, and the target polymer (comparative polymer) was prepared. An aqueous solution of 1-1 to 1-2) was obtained.
Table 2 shows the GPC analysis results of the obtained polymer. In addition, the monomer (b) used for the polymer comparative examples 1-1 to 1-2 has 23 repeating units of ethylene oxide and does not exceed 50.

<Polymer Example 2-1>
Ion exchange water (9.15 g) was added to acrylic acid (AA, 4.69 g) as a monomer solution and the PAG thiol compound (1) (7.95 g) obtained in Production Example 1 to prepare a solution.
As an initiator solution, 2,2′-azobis (2-methylpropionamidine) dihydrochloride (V-50, 0.22 g, manufactured by Wako Pure Chemical Industries, Ltd.) was added with ion-exchanged water to prepare a total solution of 37.5 g.
Dimroth condenser, Teflon (registered trademark) stirrer blade and stirrer with stir seal, nitrogen inlet tube, ethylene oxide adduct of 2-methyl-2-propen-1-ol in a glass reaction vessel equipped with a temperature sensor (ML-E150, average addition number of ethylene oxide 150 mol, 99.67 g), neutralizing acrylic acid (AA, 0.18 g), ion-exchanged water (90.85 g) are charged, and nitrogen is 200 mL with stirring at 300 rpm. The mixture was heated to 80 ° C. while introducing at a rate of / min.
Subsequently, the monomer solution 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 80 ° C. for 1 hour after completion of the dropping. After cooling to room temperature, an aqueous solution of the target compound was obtained.
As a result of GPC analysis, the polymer was Mw = 32000, Mp = 30300, and Mn = 2500. The pure polymer content was 76.8%.

<Polymer Examples 2-2 to 2-3, 3-1 to 3-2>
Synthesis was performed in the same manner as in Polymer Example 2-1, except that the raw material compounds and amounts used in Polymer Example 2-1 were changed as shown in Tables 1 and 2, and the target polymer (polymer 2) was prepared. The aqueous solution of 2-2 to 2-3 and 3-1 to 3-2) was obtained.
Table 2 shows the GPC analysis results of the obtained polymer.
<Polymer Comparative Examples 2-1 to 2-3, 3-1 to 3-3>
Synthesis was performed in the same manner as in Polymer Example 2-1, except that the raw material compounds and the amounts used were changed as shown in Tables 1 and 2 in Polymer Example 2-1, and the target polymer (comparative polymer) was prepared. The aqueous solutions of 2-1 to 2-3 and 3-1 to 3-3) were obtained.
Table 2 shows the GPC analysis results of the obtained polymer. In addition, the monomer (b) used for polymer comparative examples 2-1 to 2-3 and 3-1 to 3-3 has 50 repeating units of ethylene oxide and does not exceed 50.

Abbreviations in Tables 1 and 2 are as follows.
AA: acrylic acid MAA: methacrylic acid ME90E: methoxypolyethylene glycol methacrylate (average ethylene oxide addition number 90 mol)
ML-E150: Ethylene oxide adduct of 2-methyl-2-propen-1-ol (average number of ethylene oxide additions of 150 mol)
ME23E: Methoxypolyethylene glycol methacrylate (average ethylene oxide addition number 23 mol)
MB-E50: Ethylene oxide adduct of 3-methyl-3-buten-1-ol (average number of ethylene oxide additions of 50 mol)
ML-E50: Ethylene oxide adduct of 2-methyl-2-propen-1-ol (average number of ethylene oxide additions of 50 mol)
PAG-SH: PAG thiol compound P100S2: PAG thiol compound (1)
S450S6: PAG thiol compound (2)
V-50: 2,2′-azobis (2-methylpropionamidine) dihydrochloride In Table 2, since the blending ratio of the PAG thiol compound is taken into account as an extra percentage, the total is not 100%. .

<Method for evaluating cement dispersion performance: mortar test>
The mortar test was performed in an environment where the temperature was 20 ° C. ± 1 ° C. and the relative humidity was 60% ± 10%.
The mortar formulation was C / S / W = 600/1350/210 (g). However,
C: Ordinary Portland cement (manufactured by Sumitomo Osaka Cement)
S: Standard sand for cement strength test (Cement Association)
W: An ion exchange aqueous solution of the polymer of the present invention or a comparative polymer and an antifoaming agent.
As W, the polymer aqueous solution having the addition amount shown in Tables 3-1 and 3-2 was weighed, and 10% by mass of the antifoaming agent MA-404 (manufactured by Pozoris) was added to the solid content of the polymer. Further, ion exchange water was added to make a predetermined amount to obtain a sufficiently uniform solution. In Tables 3-1 and 3-2, the addition amount of the polymer is represented by mass% of the polymer solid content with respect to the cement mass.
A stainless beater (stirring blade) was attached to a Hobart mortar mixer (model number N-50; manufactured by Hobart), C and W were added, and kneaded at a first speed for 30 seconds. Further, S was added over 30 seconds while kneading at a first speed. After the completion of S addition, after kneading for 30 seconds at the second speed, the mixer was stopped, the mortar was scraped off for 15 seconds, and then allowed to stand for 75 seconds. The mixture was allowed to stand for 75 seconds and then kneaded at a second speed for 60 seconds to prepare a mortar.

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

<Method of measuring the amount of mortar air>
About 200 mL of mortar was packed in a 500 mL glass graduated cylinder, struck with a round bar having a diameter of 8 mm, and gently bubbled by hand to remove coarse bubbles. Further, about 200 mL of mortar was added and air bubbles were similarly removed. Then, the volume and mass of the mortar were measured, and the amount of air was calculated from the density of each material. The results are shown in Tables 3-1 and 3-2.

<Measurement of compressive strength (strength after 12 hours)>
The mortar prepared by the above method is packed in a cylindrical formwork (diameter 5 cm, height 10 cm) placed on a horizontal table to one third of the formwork capacity, and struck 20 times with a stick, then the mold The frame container was vibrated to remove coarse bubbles. Next, fill the mortar to 2/3 of the formwork, poke it 20 times with a stick, then add vibration to the formwork container, and then pack the mortar until the formwork is filled, and use the stick After piercing 20 times, the formwork container was vibrated. In order to prevent drying, the specimen was covered with a PET film and cured for 12 hours in an environment at room temperature of 20 ° C.
Using the specimen prepared by the above method, the strength was measured according to the compressive strength measuring method of JIS-A-1108 (revised in 2006).

<Mortar Examples 1-1 to 1-7, Mortar Comparative Examples 1-1 to 1-9>
Polymers 1-1 to 1-2, polymers 2-1 to 2-3, and polymers having a polyalkylene glycol monomer (A) having an average alkylene oxide repeating unit number exceeding 50, Performance evaluation was performed by a mortar test using the combined materials 3-1 to 3-2. As comparative examples, comparative polymers 1-1 to 1-2, 2-1 to 2-3, which are polymers having no polyalkylene glycol monomer (A) having an average alkylene oxide repeating unit number exceeding 50, 3-1 to 3-3 were used. As a comparative example, a plain (no polymer added) mortar test was performed. The results are shown in Table 3-1.
First, mortar examples 1-1 and 1-4, and mortar comparative examples 1-1, 1-4, 1-7, and a polymer, in which polymers having the same weight composition were used in the same addition amount, were used. The mortar comparative example 1-9 using the plain mortar which does not do is compared. The mortar comparative examples 1-1, 1-4, and 1-7 have substantially the same 15-throw flow value as that of plain mortar. Shows almost no cement dispersibility. On the other hand, the 15 flow values of mortar Examples 1-1 and 1-4 are remarkably higher than those of plain mortar, and it can be seen that the polymers 1-1 and 2-2 used show excellent cement dispersibility.
Similarly, the mortar Examples 1-2 and 1-5, the mortar comparative examples 1-2, 1-5, 1-8, and the polymer in which the same composition of the weight composition was used in the same addition amount were used. Similar results were obtained when mortar comparative examples 1-9 using plain mortar not used were compared.
Similarly, mortars using mortar Examples 1-3, mortar comparative examples 1-3, 1-6, and plain mortar without using a polymer having the same weight composition in the same addition amount Similar results were obtained when Comparative Examples 1-9 were compared.
From the above results, the polymer (i) having a polyalkylene glycol monomer (A) having an average alkylene oxide repeating unit number exceeding 50 is compared with the polymer not having the monomer (A), Even with the exact same weight composition, it is clear that high cement dispersibility is exhibited.
Further, the polymers 1-1 to 1-2 and the comparative polymers 1-1 to 1-2 are the average polyalkylene glycol chain lengths of the monomer (A) and the monomer (b) used, respectively. The structure of PAG-SH, which is a raw material for the monomer (a) and the polyalkylene glycol chain (I), and the weight composition of each raw material are exactly the same. The same applies to the polymers 2-1 to 2-3 and the comparative polymers 3-1 to 3-3. Comparative polymers 2-1 to 2-3 were slightly different from comparative polymers 3-1 to 3-3 in the structure of the main chain portion, but there was no significant difference in performance.
From this, it is presumed that high cement dispersibility is exhibited when the polymer (i) has a structure derived from the polyalkylene glycol monomer (A) having an average alkylene oxide repeating unit number exceeding 50. The

<Mortar Examples 2-1 to 2-7, Mortar Comparative Examples 2-1 to 2-8>
Polymers 1-1 to 1-2, polymers 2-1 to 2-3, and polymers having a polyalkylene glycol monomer (A) having an average alkylene oxide repeating unit number exceeding 50, Performance evaluation was performed by a mortar test using the combined materials 3-1 to 3-2. As comparative examples, comparative polymers 1-1 to 1-2, 2-1 to 2-3, and 3-1 to 3-3, which are polymers having no monomer (A), were used.
First, using each polymer, the addition amount was adjusted so that the 15-stroke flow value was 200 ± 5 mm. Subsequently, a specimen was prepared and cured according to the procedure described above, and the strength after 12 hours from the injection of water into the cement was measured. The results are shown in Table 3-2. However, with respect to Comparative Polymers 1-1 and 1-2, even when the addition amount was increased to 0.2%, the predetermined 15-stroke flow value was not reached, and it was determined that the dispersibility was poor, and the strength test was not performed.
As shown in Table 3-2, mortar examples 2-1 to 2-7 after 12 hours the intensity is 16.6~18.1N / mm ^2, the mortar Comparative Example 2-3～2-8 The value was 16.9% -33.1% higher than 13.6-14.2 N / mm ² .
From the above results, the mortar using the polymer (i) having the polyalkylene glycol monomer (A) having an average alkylene oxide repeating unit number exceeding 50 is a polymer having no monomer (A). It is clear that even with the same degree of fluidity as compared to the mortar used, it shows a high 12 hour strength. In addition, the mortar Examples 2-3 to 2-5 using the polymer (i) having a larger average alkylene oxide repeating unit number show slightly higher strength than the mortar Examples 2-1 to 2-2. It is.
From this, it is presumed that the high initial mortar strength is exhibited by the polymer (i) having a structure derived from the polyalkylene glycol monomer (A) having an average alkylene oxide repeating unit number exceeding 50. .

Claims (8)

A polyalkylene having a structure in which a terminal oxygen atom at at least one terminal of a polyalkylene glycol chain is bonded to a main chain terminal of a polymer containing a structural unit derived from a vinyl-based monomer component directly or via an organic residue A glycol-based polymer,
The polymer has the following general formula (1):

(In the formula, X represents an oxygen atom or a residue of a compound having two or more active hydrogens. AO is the same or different and represents an oxyalkylene group having 2 to 18 carbon atoms. N and n ′ Are the same or different and each represents the average number of added moles of the oxyalkylene group and is a number from 50 to 1000. Y ¹ and Y ² are the same or different and each represents a direct bond or an organic residue. Are the same or different and the residue of the polymer containing the structural unit derived from the vinyl monomer component Q ¹ is the same or different and is a hydrogen atom, an alkyl group having 1 to 10 carbon atoms or an alkylene group. And a residue of a compound having 1 or 2 or more active hydrogens, or Z. m and p are integers of 1 to 50.)
The vinyl monomer component essentially contains an unsaturated polyalkylene glycol monomer,
The polyalkylene glycol polymer, wherein an average addition mole number r of oxyalkylene groups in the unsaturated polyalkylene glycol monomer is greater than 50. 2. The polyalkylene glycol polymer according to claim 1, wherein an average addition mole number r of the oxyalkylene group in the unsaturated polyalkylene glycol monomer is 75 or more. The polyalkylene glycol polymer according to claim 1 or 2, wherein the vinyl monomer essentially contains an unsaturated carboxylic acid monomer. A polyalkylene having a structure in which a terminal oxygen atom at at least one terminal of a polyalkylene glycol chain is bonded to a main chain terminal of a polymer containing a structural unit derived from a vinyl-based monomer component directly or via an organic residue A method for producing a glycol polymer comprising:
The production method comprises the following general formula (2):

(In the formula, X represents an oxygen atom or a residue of a compound having two or more active hydrogens. AO is the same or different and represents an oxyalkylene group having 2 to 18 carbon atoms. N and n ′ Are the same or different and each represents the average number of moles of the oxyalkylene group, and is a number from 50 to 1000. Y ¹ and Y ² are the same or different and each represents a direct bond or an organic residue. ² is the same or different and represents a hydrogen atom, an alkyl or alkylene group having 1 to 10 carbon atoms, or a residue of a compound having one or more active hydrogens, and m and p are 1 to 50. A step of polymerizing a vinyl monomer component in the presence of a polyalkylene glycol chain-containing compound represented by:
The vinyl monomer component essentially contains an unsaturated polyalkylene glycol monomer,
The method for producing a polyalkylene glycol polymer, wherein an average addition mole number r of oxyalkylene groups in the unsaturated polyalkylene glycol monomer is greater than 50. A polyalkylene glycol polymer obtained by the production method according to claim 4. A cement dispersant comprising the polyalkylene glycol polymer according to claim 1. A cement admixture comprising the polyalkylene glycol polymer according to claim 1. A cement composition comprising the cement admixture according to claim 7.