JP2014065665A - Unsaturated polyalkylene glycol derivatives, and production methods and intermediates thereof - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide unsaturated polyalkylene glycol derivatives which are significantly excellent in various properties, particularly in early strength development and dispersibility and may provide compositions useful for various applications such as dispersants and cement admixtures; production methods thereof; and intermediates of the unsaturated polyalkylene glycol derivatives.SOLUTION: The unsaturated polyalkylene glycol derivatives are represented by the specified general formula (1).

Description

The present invention relates to an unsaturated polyalkylene glycol derivative, a production method thereof and an intermediate. More specifically, the present invention relates to an unsaturated polyalkylene glycol derivative that is an unsaturated compound having a polyalkylene glycol chain, a method for producing the same, and an intermediate of the unsaturated polyalkylene glycol derivative.

An unsaturated compound having a polyalkylene glycol chain can impart properties such as hydrophilicity, hydrophobicity, and steric repulsion by appropriately adjusting the chain length and the constituent alkylene oxide. As a monomer component to be used, it is widely used in various applications such as adhesives and sealants, dispersants, flexibility-imparting components, and detergent builder applications. Recently, the use of cement admixtures added to cement compositions such as cement paste with water added to cement, mortar with fine aggregate mixed with cement paste, and concrete with coarse aggregate mixed with mortar has been studied. ing. The cement admixture is usually used as a water reducing agent, etc., and aims to exert the effect of improving the strength and durability of the cured product by increasing the fluidity of the cement composition to reduce the water content of the cement composition. It is used as

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

Regarding unsaturated compounds having a conventional polyalkylene glycol chain, for example, Patent Documents 1 and 2 include structural units derived from an unsaturated polyether monomer having a branched polyalkylene glycol chain, and an unsaturated carboxylic acid monomer. A polycarboxylic acid-based dispersant containing a structural unit having Patent Document 3 discloses an unsaturated polyether having a branched polyethylene glycol chain, and Patent Document 4 discloses a polyoxyethylene ether having a branched polyalkylene glycol chain. Furthermore, Patent Document 5 discloses polyhydroxy functional polysiloxanes obtained by adding a branched polyhydroxy functional allyl polyether to a Si-H functional alkyl polysiloxane. Branched polyglycols are disclosed for use in making polyether functional organopolysiloxanes.

Chinese Patent Application No. 102060465 Specification Chinese Patent Application No. 102030496 Chinese Patent Application No. 101955555 Chinese Patent Application No. 102140167 Special table 2011-527351 gazette Special table 2009-521574

As described above, unsaturated compounds having various polyalkylene glycol chains have been studied, and Patent Documents 1 to 6 disclose unsaturated compounds having branched polyalkylene glycol chains. However, when a polymer is obtained using these unsaturated compounds, the polymer has a dispersibility equivalent to or lower than that of a polymer having a linear polyalkylene glycol chain in the side chain, and the early strength is also reduced. There was no improvement. From such a point of view, there is room for devising a compound capable of providing a useful component that can exhibit excellent early strength development and dispersibility in various uses such as a dispersant and a cement admixture.

The present invention has been made in view of the above-mentioned present situation. Unsaturated polymers that are remarkably excellent in various performances, particularly early strength development and dispersibility, and can provide useful components for various uses such as dispersants and cement admixtures. An object of the present invention is to provide an alkylene glycol derivative, a production method thereof, and an intermediate of an unsaturated polyalkylene glycol derivative.

The inventors of the present invention have studied various types of polymers having a polyalkylene glycol chain. Assuming that the side chain of the polymer has a branched polyalkylene glycol chain (branched polyalkylene glycol chain), the branched side chain It is thought that the main chain can be shortened while maintaining the dispersibility due to the water, that is, the hydration area can be increased by reducing the adsorption area (polymer coating area) to the inorganic or organic matter, thereby condensing We thought that the delay was suppressed and the improvement of the early strength could be expected. However, as a monomer component, only by using a compound obtained by simply branching a polyalkylene glycol chain such as the compounds disclosed in Patent Documents 1 to 6, the dispersibility of the obtained polymer is linear in the side chain. It has been found that it is less than or equal to the polymer having a polyalkylene glycol chain, and no significant improvement is observed in terms of early strength. Therefore, an unsaturated polyalkylene glycol derivative having a structure in which an unsaturated bond (carbon-carbon double bond) and a branched polyalkylene glycol chain are bonded via another polyalkylene glycol chain is used as the monomer component. And the obtained polymer was found to be remarkably excellent in both dispersibility (also referred to as water reduction or fluidity) and early strength development. This is because the polymer main chain formed from the unsaturated bond and the polymer side chain formed from the branched polyalkylene glycol chain due to the presence of the intervening polyalkylene glycol chain (length) Therefore, the main chain can be shortened and the side chain can be made more bulky, that is, the adsorption area (polymer coating area) on the inorganic or organic matter can be reduced and the hydration area can be increased. It is speculated that this is possible.

It has also been found that an unsaturated polyalkylene glycol derivative having such a structure is an unprecedented novel compound. Furthermore, as a method for obtaining such an unsaturated polyalkylene glycol derivative, a step of reacting an epoxy alcohol and / or a polyhydric alcohol with an unsaturated polyalkylene glycol compound having a specific structure having an unsaturated bond and a polyalkylene glycol chain. It has been found that an unsaturated polyalkylene glycol derivative can be easily and efficiently obtained by employing a production method including In addition, as an intermediate of an unsaturated polyalkylene glycol derivative, a compound having a specific structure having a polyalkylene glycol chain between an unsaturated bond (carbon-carbon double bond) and a compound residue having two or more active groups It has been found that the unsaturated polyalkylene glycol derivative of the present invention that exhibits excellent performance can be suitably obtained by further introducing a polyalkylene glycol chain into this compound, and The inventors have arrived at the present invention by conceiving that the problem can be solved.

That is, the present invention is an unsaturated polyalkylene glycol derivative represented by the following general formula (1).

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

The present invention is also a method for producing the unsaturated polyalkylene glycol derivative, wherein the production method comprises an unsaturated polyalkylene glycol compound represented by the following general formula (3) with epoxy alcohol and / or polyvalent It is also a method for producing an unsaturated polyalkylene glycol derivative comprising the step 1 of reacting an alcohol.

(.P ^wherein, R 1, ^{R 2} and ^{R 3} are the same or different, .A ¹ O represents a hydrogen atom or a methyl group, the same or different and each represents an oxyalkylene group having 2 to 18 carbon atoms Is 0, 1 or 2. q is 0 or 1. t represents the average number of moles added of the oxyalkylene group represented by A ¹ O, and is a number from 2 to 300.)

The present invention is also an intermediate of an unsaturated polyalkylene glycol derivative represented by the following general formula (4).

^(Wherein, R 1, ^{R 2} and ^{R 3} are the same or different, .R ⁴ represents a hydrogen atom or a methyl group are the same or different, represent a hydrogen atom or a hydrocarbon group having 1 to 30 carbon atoms A ¹ O is the same or different and represents an oxyalkylene group having 2 to 18 carbon atoms, Y ′ represents — (C ₃ H ₆ O ₂ ) _r —, and _r represents C ₃ H ₆ O _{2. .} in a mean addition number of moles of glyceryl group represented by the number of _{1~300 (C 3 H 6 O 2} ) glyceryl group represented by the same or different, the following formula:

It consists of the structure represented by. p is 0, 1 or 2. q is 0 or 1. t represents the average addition mole number of the oxyalkylene group represented by A ¹ O, and is a number of 2 to 300. m is an integer of 2 or more, and is a number whose maximum number is determined depending on the number of — (C ₃ H ₆ O ₂ ) _r — active groups represented by Y ′. )
The present invention is described in detail below. A form in which two or more individual preferred forms of the present invention described below are combined is also a preferred form of the present invention.
In the present specification, (poly) glycidol means polyglycidol or glycidol, and (poly) alkylene glycol means polyalkylene glycol or alkylene glycol.

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

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

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

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

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

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

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

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

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

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

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

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

It consists of the structure represented by. )
When the unsaturated polyalkylene glycol derivative represented by the general formula (1) has a structure represented by the general formula (2) as Y, the effects of the present invention can be more fully exhibited. It becomes. Thus, the form in which Y in the general formula (1) is represented by the general formula (2) is also one of the preferred forms of the present invention.

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

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

The m is preferably equal to the number of active groups in the compound having two or more active groups. That is, the unsaturated polyalkylene glycol derivative has a polyalkylene glycol chain- (A in all active groups in the compound having two or more active groups (more specifically, active hydrogen atoms constituting the active groups). It is preferable to have a structure in which ² O) _n − is bonded. This makes it possible to provide a dispersant and a cement admixture that can exhibit further superior dispersion performance and early strength, and thus can be a compound useful for various applications.

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

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

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

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

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

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

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

R ⁴ constituting the terminal group of the unsaturated polyalkylene glycol derivative represented by the general formula (1), that is, the polyalkylene glycol chain-containing group (Z; — (A ² O) _n —R ⁴ ) is a hydrogen atom Or a C1-C30 hydrocarbon group is represented. From the viewpoint of improving dispersibility, it is preferable that the hydrophobicity does not become too strong. Therefore, R ⁴ is preferably a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms. More preferably, they are a hydrogen atom or a C1-C5 hydrocarbon group, More preferably, they are a hydrogen atom or a C1-C3 hydrocarbon group.
When R ⁴ represents a hydrocarbon group, it is preferably a saturated alkyl group or an unsaturated alkyl group, and may be linear, branched, or cyclic.

In the general formula (1), the branched polyalkylene glycol chain-containing group represented by —Y— (Z) _m is bonded to the polyalkylene glycol chain represented by — (A ¹ O) _t —. . Thus, it is sufficient for an unsaturated polyalkylene glycol derivative by making it a structure formed by bonding an unsaturated bond (carbon-carbon double bond) and a branched polyalkylene glycol chain-containing group via a polyalkylene glycol chain. Since the hydrophilicity can be imparted and the length (interval) between the unsaturated bond and the branched polyalkylene glycol chain-containing group (—Y— (Z) _m ) can be made sufficient, The dispersibility and early strength of the polymer obtained using the unsaturated polyalkylene glycol derivative can be significantly improved. In addition, a polymer obtained using such an unsaturated polyalkylene glycol derivative has a molecular weight equivalent to that of the polymer and has a linear polyalkylene glycol chain in the side chain. The outstanding dispersibility and early strength can be expressed.

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

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

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

[Method for producing unsaturated polyalkylene glycol derivative]
The unsaturated polyalkylene glycol derivative of the present invention is obtained, for example, by a production method including Step 1 in which an unsaturated polyalkylene glycol compound represented by the following general formula (3) is reacted with an epoxy alcohol and / or a polyhydric alcohol. be able to. Thus, it is the method of manufacturing the said unsaturated polyalkylene glycol derivative, Comprising: The process 1 which makes epoxy alcohol and / or a polyhydric alcohol react with the unsaturated polyalkylene glycol compound represented by following General formula (3). A method for producing an unsaturated polyalkylene glycol derivative containing is also one aspect of the present invention. The manufacturing method may further include one or more other steps as necessary.

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

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

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

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

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

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

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

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

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

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

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

The unsaturated polyalkylene glycol derivative of the present invention can also be produced by a production method including the following step 1 ′, step 2 ′ and step 3 ′. Thus, a method for producing the unsaturated polyalkylene glycol derivative, which includes the following steps 1 ′, 2 ′ and 3 ′, is also suitable for the present invention. This is one of the embodiments. In addition, you may include 1 or 2 or more of another process as needed.
Step 1 ′: A step of reacting an alkylene oxide adduct of an alcohol having 1 to 30 carbon atoms with an epoxy alcohol and / or a polyhydric alcohol.
Step 2 ′: a step of reacting the compound obtained in Step 1 ′ with an alkylene oxide.
Step 3 ′: The compound obtained by Step 2 ′ is added to the following general formula (5):

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

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

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

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

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

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

As the alkylene oxide used in the above step 2 ', the same alkylene oxide used in the above step 2 is preferable.

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

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

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

In the step 3 ′, examples of the compound having a group represented by the general formula (5) include a compound having a structure in which a hydroxyl group (—OH) or a halogen element (—Q) is bonded to the group. Can be mentioned. In addition, R < ¹ >, R < ² >, R < ³ >, p and q in the said General formula (5) are the same as that of each symbol in the said General formula (1).

Specific examples of the compound having the group represented by the general formula (5) include acrylic acid, methacrylic acid, allyl alcohol, allyl chloride, allyl bromide, allyl iodide, methallyl alcohol, methallyl chloride, and meta Examples include ril bromide, methallyl iodide, isoprenol, isoprenyl chloride, isoprenyl bromide, and isoprenyl iodide.

In the step 3 ′, the reaction ratio between the compound obtained in the step 2 ′ and the compound having the group represented by the general formula (5) (molar ratio; compound obtained in the step 2 ′ / the general formula (5) ) Is preferably 1/1 to 1/2. More preferably, it is 1/1 to 1 / 1.2.

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

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

[Intermediate]
The present invention is also an intermediate of an unsaturated polyalkylene glycol derivative represented by the following general formula (4).

^(Wherein, R 1, ^{R 2} and ^{R 3} are the same or different, .R ⁴ represents a hydrogen atom or a methyl group are the same or different, represent a hydrogen atom or a hydrocarbon group having 1 to 30 carbon atoms A ¹ O is the same or different and represents an oxyalkylene group having 2 to 18 carbon atoms, Y ′ represents — (C ₃ H ₆ O ₂ ) _r —, and _r represents C ₃ H ₆ O _{2. .} in a mean addition number of moles of glyceryl group represented by the number of _{1~300 (C 3 H 6 O 2} ) glyceryl group represented by the same or different, the following formula:

It consists of the structure represented by. p is 0, 1 or 2. q is 0 or 1. t represents the average addition mole number of the oxyalkylene group represented by A ¹ O, and is a number of 2 to 300. m is an integer of 2 or more, and is a number whose maximum number is determined depending on the number of — (C ₃ H ₆ O ₂ ) _r — active groups represented by Y ′. )
In the general formula (4), R ¹ , R ² , R ³ , R ⁴ , A ¹ O, p, q, t, and m are the same as the symbols in the general formula (1).

The above intermediate is very useful as an intermediate of the unsaturated polyalkylene glycol derivative of the present invention. In order to obtain such an intermediate, for example, among the above-described methods for producing an unsaturated polyalkylene glycol derivative, the unsaturated polyalkylene glycol compound represented by the above general formula (3) is added to an epoxy alcohol and / or a polyvalent compound. In the step 1 of reacting alcohol, it can be obtained by using (poly) glycidol as epoxy alcohol and / or polyhydric alcohol.

The molecular weight of the intermediate is preferably 200 to 100,000 in terms of weight average molecular weight. Moreover, when the handling on manufacture etc. are considered, More preferably, it is 200-50000, More preferably, it is 200-30000.
The molecular weight of the intermediate can be determined in the same manner as the unsaturated polyalkylene glycol derivative described above.

[Use]
The unsaturated polyalkylene glycol derivative of the present invention can provide components that are remarkably excellent in various performances, in particular, early strength development performance and dispersion performance, and is therefore suitable for use in inorganic or organic dispersants that are hardly soluble in water. be able to. In particular, a polymer obtained by using a monomer component containing the unsaturated polyalkylene glycol derivative, that is, a polymer having a structural unit derived from the unsaturated polyalkylene glycol derivative (also referred to as a polyalkylene glycol polymer). Is suitable as a polymer for a dispersant. Among polyalkylene glycol polymers, a polycarboxylic acid copolymer further having a structural unit derived from an unsaturated carboxylic acid monomer is extremely useful because it is more excellent in early strength development performance and dispersion performance.

Specifically, as an application to which the unsaturated polyalkylene glycol derivative and the polyalkylene glycol polymer using the unsaturated polyalkylene glycol derivative are applied, dispersants for inorganic pigments such as heavy or light calcium carbonate and clay used for paper coating A dispersing agent for water slurry such as cement and coal; In addition, for example, cement admixtures; cooling water systems, boiler water systems, seawater desalination equipment, pulp digesters, black liquor concentration tanks, water treatment agents for preventing scales; scale inhibitors; It can also be suitably used for fiber treatment agents such as auxiliaries; adhesives; sealing agents; components for imparting flexibility to various polymers; Furthermore, it can be widely applied in the fields of body detergents such as shampoos, rinses, body soaps, fiber processing, building material processing, paints, ceramics and the like. Above all, it is suitable to be used for cement admixture. In this case, a cement admixture that is particularly excellent in early strength development while exhibiting cement dispersion performance equivalent to or higher than that of conventional products at lower cost is provided. it can. It is particularly useful as a cement admixture for secondary concrete products (precast). Thus, a dispersant or cement admixture using the unsaturated polyalkylene glycol derivative, a dispersant or cement admixture containing the polyalkylene glycol polymer, and the unsaturated polyalkylene glycol derivative are used as a dispersant. Forms that are compounds or cement admixture compounds are also preferred embodiments of the present invention.

Since the unsaturated polyalkylene glycol derivative of the present invention has the above-described configuration, it can give components that are remarkably excellent in various performances, particularly early strength development performance and dispersion performance. In particular, a polymer obtained by polymerizing a monomer component containing such an unsaturated polyalkylene glycol derivative, and in particular, obtained by polymerizing a monomer component further containing an unsaturated carboxylic acid monomer. Polycarboxylic acid copolymers are extremely useful for dispersants and cement admixtures because of their extremely high early strength development and dispersion performance, and further improve productivity and workability in the fields where they are handled. can do. Therefore, the cement admixture containing this greatly contributes to the civil engineering / construction field and the like that handle concrete.

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

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

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

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

Synthesis example 4
A SUS autoclave reaction vessel equipped with a thermometer, a stirrer, a raw material introduction tube and a nitrogen introduction tube was charged with 167.4 g of an ethylene oxide 8 mol adduct of methallyl alcohol and 7.6 g of potassium hydroxide as an addition reaction catalyst, and stirred. The reaction vessel was purged with nitrogen and heated to 105 ° C. Next, a pipe equipped with a glass trap was connected from the top of the reaction vessel while stirring, and the inside of the reaction vessel was depressurized to 10 Torr using a vacuum pump. Thereafter, dehydration was performed at the same temperature for 3 hours while cooling the glass trap in an ethanol dry ice bath. After dehydration, the temperature was lowered to 95 ° C. in a nitrogen atmosphere. And 210.4g of glycidol was introduce | transduced in the reactor over 4 hours, maintaining 95 degreeC under a normal pressure. Further, the reaction was completed by maintaining at 95 ° C. for 2 hours.
The obtained reaction product (A-4) had a weight average molecular weight of 1400 and a number average molecular weight of 900.

Synthesis example 5
In a SUS autoclave reaction vessel equipped with a thermometer, a stirrer, a raw material introduction tube and a nitrogen introduction tube, 93.7 g of the reaction product (A-4) obtained in Synthesis Example 4 (including 1.8 g of potassium hydroxide) The reaction vessel was purged with nitrogen while stirring, and then heated to 105 ° C. Next, a pipe equipped with a glass trap was connected from the top of the reaction vessel while stirring, and the inside of the reaction vessel was depressurized to 10 Torr using a vacuum pump. Thereafter, dehydration was performed at the same temperature for 1 hour while cooling the glass trap in an ethanol dry ice bath. After dehydration, the temperature was raised to 120 ° C. in a nitrogen atmosphere. Then, 706.3 g of ethylene oxide was introduced into the reactor while maintaining 120 ° C. under a safe pressure (the dropping time was 265 minutes), and the temperature was maintained until the alkylene oxide addition reaction was completed to complete the reaction (ripening time). 60 minutes).
The obtained reaction product (A-5) had a weight average molecular weight of 16,200 and a number average molecular weight of 8,100.

Synthesis Example 6
424.8 g of reaction product (A-5) obtained in Synthesis Example 5 (including 1.0 g of potassium hydroxide) in a SUS autoclave reaction vessel equipped with a thermometer, a stirrer, a raw material introduction tube and a nitrogen introduction tube The reaction vessel was purged with nitrogen while stirring, and then heated to 105 ° C. Next, a pipe equipped with a glass trap was connected from the top of the reaction vessel while stirring, and the inside of the reaction vessel was depressurized to 10 Torr using a vacuum pump. Thereafter, dehydration was performed at the same temperature for 1 hour while cooling the glass trap in an ethanol dry ice bath. After dehydration, the temperature was raised to 120 ° C. in a nitrogen atmosphere. Then, 375.2 g of ethylene oxide was introduced into the reactor while maintaining 120 ° C. under a safe pressure (the dropping time was 196 minutes), and the temperature was maintained until the alkylene oxide addition reaction was completed to complete the reaction (ripening time). 60 minutes).
The obtained reaction product (A-6) had a weight average molecular weight of 30,400 and a number average molecular weight of 11,200.

Synthesis example 7
A SUS autoclave reaction vessel equipped with a thermometer, a stirrer, a raw material introduction tube and a nitrogen introduction tube was charged with 243.2 g of a 20-mole ethylene oxide adduct of methallyl alcohol and 8.9 g of potassium hydroxide as an addition reaction catalyst, and stirred. The reaction vessel was purged with nitrogen and heated to 105 ° C. Next, a pipe equipped with a glass trap was connected from the top of the reaction vessel while stirring, and the inside of the reaction vessel was depressurized to 10 Torr using a vacuum pump. Thereafter, dehydration was performed at the same temperature for 3 hours while cooling the glass trap in an ethanol dry ice bath. After dehydration, the temperature was lowered to 95 ° C. in a nitrogen atmosphere. And 56.8g of glycidol was introduce | transduced in the reactor over 2 hours, maintaining 95 degreeC under a normal pressure. Further, the reaction was completed by maintaining at 95 ° C. for 2 hours.
The obtained reaction product (A-7) had a weight average molecular weight of 1500 and a number average molecular weight of 1,200.

Synthesis example 8
In a SUS autoclave reaction vessel equipped with a thermometer, stirrer, raw material introduction tube and nitrogen introduction tube, 174.6 g of reaction product (A-7) obtained in Synthesis Example 7 (including 5.0 g of potassium hydroxide) The reaction vessel was purged with nitrogen while stirring, and then heated to 105 ° C. Next, a pipe equipped with a glass trap was connected from the top of the reaction vessel while stirring, and the inside of the reaction vessel was depressurized to 10 Torr using a vacuum pump. Thereafter, dehydration was performed at the same temperature for 1 hour while cooling the glass trap in an ethanol dry ice bath. After dehydration, the temperature was lowered to 95 ° C. in a nitrogen atmosphere. Then, 525.4 g of ethylene oxide was introduced into the reactor while maintaining the temperature at 95 ° C. under a safe pressure (the dropping time was 238 minutes), and the temperature was maintained until the alkylene oxide addition reaction was completed to complete the reaction (ripening time). 60 minutes).
The obtained reaction product (A-8) had a weight average molecular weight of 9,100 and a number average molecular weight of 4,800.

Synthesis Example 9
523.2 g of reaction product (A-8) obtained in Synthesis Example 8 (including 3.8 g of potassium hydroxide) in a SUS autoclave reaction vessel equipped with a thermometer, a stirrer, a raw material introduction tube and a nitrogen introduction tube The reaction vessel was purged with nitrogen while stirring, and then heated to 105 ° C. Next, a pipe equipped with a glass trap was connected from the top of the reaction vessel while stirring, and the inside of the reaction vessel was depressurized to 10 Torr using a vacuum pump. Thereafter, dehydration was performed at the same temperature for 1 hour while cooling the glass trap in an ethanol dry ice bath. After dehydration, the temperature was lowered to 95 ° C. in a nitrogen atmosphere. Then, 376.8 g of ethylene oxide was introduced into the reactor while maintaining the temperature at 95 ° C. under a safe pressure (the dropping time was 192 minutes), and the temperature was maintained until the alkylene oxide addition reaction was completed to complete the reaction (ripening time). 60 minutes).
The obtained reaction product (A-9) had a weight average molecular weight of 16,300 and a number average molecular weight of 8,100.

Synthesis Example 10
A SUS autoclave reaction vessel equipped with a thermometer, a stirrer, a raw material introduction tube and a nitrogen introduction tube was charged with 194.2 g of a 20-mole ethylene oxide adduct of methallyl alcohol and 7.1 g of potassium hydroxide as an addition reaction catalyst and stirred. The reaction vessel was purged with nitrogen and heated to 105 ° C. Next, a pipe equipped with a glass trap was connected from the top of the reaction vessel while stirring, and the inside of the reaction vessel was depressurized to 10 Torr using a vacuum pump. Thereafter, dehydration was performed at the same temperature for 3 hours while cooling the glass trap in an ethanol dry ice bath. After dehydration, the temperature was lowered to 95 ° C. in a nitrogen atmosphere. And 105.8g of glycidol was introduce | transduced in the reactor over 4 hours, maintaining 95 degreeC under a normal pressure. Further, the reaction was completed by maintaining at 95 ° C. for 2 hours.
The obtained reaction product (A-10) had a weight average molecular weight of 1,900 and a number average molecular weight of 1,300.

Synthesis Example 11
A SUS autoclave reaction vessel equipped with a thermometer, a stirrer, a raw material introduction tube and a nitrogen introduction tube was charged with 371.8 g of 50 mol of ethylene oxide adduct of methallyl alcohol and 8.0 g of potassium hydroxide as an addition reaction catalyst. The reaction vessel was purged with nitrogen and heated to 105 ° C. Next, a pipe equipped with a glass trap was connected from the top of the reaction vessel while stirring, and the inside of the reaction vessel was depressurized to 10 Torr using a vacuum pump. Thereafter, dehydration was performed at the same temperature for 3 hours while cooling the glass trap in an ethanol dry ice bath. After dehydration, the temperature was lowered to 95 ° C. in a nitrogen atmosphere. And 36.4g of glycidol was introduce | transduced in the reactor over 2 hours, maintaining 95 degreeC under a normal pressure. Further, the reaction was completed by maintaining at 95 ° C. for 2 hours.
The weight average molecular weight of the obtained reaction product (A-11) was 3200, and the number average molecular weight was 2900.

Synthesis Example 12
In a SUS autoclave reaction vessel equipped with a thermometer, a stirrer, a raw material introduction tube and a nitrogen introduction tube, 209.0 g of the reaction product (A-11) obtained in Synthesis Example 11 (including 4.0 g of potassium hydroxide) The reaction vessel was purged with nitrogen while stirring, and then heated to 105 ° C. Next, a pipe equipped with a glass trap was connected from the top of the reaction vessel while stirring, and the inside of the reaction vessel was depressurized to 10 Torr using a vacuum pump. Thereafter, dehydration was performed at the same temperature for 1 hour while cooling the glass trap in an ethanol dry ice bath. After dehydration, the temperature was lowered to 95 ° C. in a nitrogen atmosphere. Then, 591.0 g of ethylene oxide was introduced into the reactor while maintaining the temperature at 95 ° C. under a safe pressure (the dropping time was 191 minutes), and the reaction was terminated by maintaining the temperature until the alkylene oxide addition reaction was completed (ripening time). 60 minutes).
The obtained reaction product (A-12) had a weight average molecular weight of 16,400 and a number average molecular weight of 9,800.

Synthesis Example 13
A SUS autoclave reaction vessel equipped with a thermometer, a stirrer, a raw material introduction tube and a nitrogen introduction tube was charged with 261.7 g of a 50-mole ethylene oxide adduct of methallyl alcohol and 5.0 g of potassium hydroxide as an addition reaction catalyst, and stirred. The reaction vessel was purged with nitrogen and heated to 105 ° C. Next, a pipe equipped with a glass trap was connected from the top of the reaction vessel while stirring, and the inside of the reaction vessel was depressurized to 10 Torr using a vacuum pump. Thereafter, dehydration was performed at the same temperature for 3 hours while cooling the glass trap in an ethanol dry ice bath. After dehydration, the temperature was lowered to 95 ° C. in a nitrogen atmosphere. And 59.7g of glycidol was introduce | transduced in the reactor over 4 hours, maintaining 95 degreeC under a normal pressure. Further, the reaction was completed by maintaining at 95 ° C. for 2 hours.
The obtained reaction product (A-13) had a weight average molecular weight of 3,500 and a number average molecular weight of 3,200.

Synthesis Example 14
140.2 g of reaction product (A-13) obtained in Synthesis Example 13 (including 2.2 g of potassium hydroxide) in a SUS autoclave reaction vessel equipped with a thermometer, a stirrer, a raw material introduction tube and a nitrogen introduction tube The reaction vessel was purged with nitrogen while stirring, and then heated to 105 ° C. Next, a pipe equipped with a glass trap was connected from the top of the reaction vessel while stirring, and the inside of the reaction vessel was depressurized to 10 Torr using a vacuum pump. Thereafter, dehydration was performed at the same temperature for 1 hour while cooling the glass trap in an ethanol dry ice bath. After dehydration, the temperature was lowered to 95 ° C. in a nitrogen atmosphere. Then, 709.8 g of ethylene oxide was introduced into the reactor while maintaining the temperature at 95 ° C. under a safe pressure (the dropping time was 344 minutes), and the temperature was maintained until the alkylene oxide addition reaction was completed to complete the reaction (ripening time). 60 minutes).
The obtained reaction product (A-14) had a weight average molecular weight of 31,700 and a number average molecular weight of 13,700.

Synthesis Example 15
A SUS autoclave reaction vessel equipped with a thermometer, a stirrer, a raw material introduction tube and a nitrogen introduction tube was charged with 201.4 g of an ethylene oxide 50 mol adduct of methallyl alcohol and 5.0 g of potassium hydroxide as an addition reaction catalyst, and stirred. The reaction vessel was purged with nitrogen and heated to 105 ° C. Next, a pipe equipped with a glass trap was connected from the top of the reaction vessel while stirring, and the inside of the reaction vessel was depressurized to 10 Torr using a vacuum pump. Thereafter, dehydration was performed at the same temperature for 3 hours while cooling the glass trap in an ethanol dry ice bath. After dehydration, the temperature was lowered to 95 ° C. in a nitrogen atmosphere. And 98.5g of glycidol was introduce | transduced in the reactor over 4 hours, maintaining 95 degreeC under a normal pressure. Further, the reaction was completed by maintaining at 95 ° C. for 2 hours.
The obtained reaction product (A-15) had a weight average molecular weight of 4,600 and a number average molecular weight of 3,600.

Synthesis Examples 1 to 15 are summarized in Table 1.

<Polycarboxylic acid copolymer>
Production Example 1
In a glass reactor equipped with a thermometer, a stirrer, a dropping device, a nitrogen introduction tube and a reflux cooling device, 285.3 g of ion-exchanged water and 280.7 g of the reaction product (A-3) obtained in Synthesis Example 3 Then, 3.9 g of acrylic acid and 0.72 g of acetic acid were charged, the inside of the reaction apparatus was purged with nitrogen under stirring, and heated to 80 ° C. in a nitrogen atmosphere. While maintaining the inside of the reaction vessel at 80 ° C., an aqueous solution in which 14.7 g of acrylic acid was dissolved in 116.0 g of ion-exchanged water was added for 3 hours, and 0.48 g of 3-mercaptopropionic acid was added to 149.5 g of ion-exchanged water. The dissolved aqueous solution was dropped in 3 hours, and an aqueous solution in which 3.5 g of ammonium persulfate was dissolved in 145.3 g of ion-exchanged water was dropped over 3.5 hours. Thereafter, the temperature was maintained at 80 ° C. for 1 hour, and then the polymerization reaction was terminated. Thereafter, the acidic reaction solution was adjusted to pH 6.0 using an aqueous sodium hydroxide solution and ion-exchanged water at a temperature lower than the polymerization reaction temperature, and a copolymer having a weight average molecular weight of 110,000 and Mw / Mn 3.65. An aqueous solution of (1) was obtained.

Production Example 2
In a glass reactor equipped with a thermometer, a stirrer, a dropping device, a nitrogen introduction tube and a reflux cooling device, 288.8 g of ion-exchanged water and 284.3 g of the reaction product (A-12) obtained in Synthesis Example 12 Then, 3.1 g of acrylic acid and 1.42 g of acetic acid were charged, and the inside of the reaction apparatus was purged with nitrogen under stirring, and heated to 80 ° C. in a nitrogen atmosphere. While maintaining the inside of the reaction vessel at 80 ° C., an aqueous solution in which 11.2 g of acrylic acid was dissolved in 119.5 g of ion-exchanged water was added in 3 hours, and 0.61 g of 3-mercaptopropionic acid was added to 149.4 g of ion-exchanged water. The dissolved aqueous solution was dropped in 3 hours, and an aqueous solution in which 2.8 g of ammonium persulfate was dissolved in 138.8 g of ion-exchanged water was dropped over 3.5 hours. Thereafter, the temperature was maintained at 80 ° C. for 1 hour, and then the polymerization reaction was terminated. Thereafter, the acidic reaction solution was adjusted to pH 6.0 using an aqueous sodium hydroxide solution and ion-exchanged water at a temperature not higher than the polymerization reaction temperature, and a copolymer having a weight average molecular weight of 125,000 and Mw / Mn 3.87. An aqueous solution of (2) was obtained.

Production Example 3
In a glass reactor equipped with a thermometer, a stirrer, a dripping device, a nitrogen inlet tube and a reflux cooling device, 167.7 g of ion-exchanged water and 387.9 g of the reaction product (A-14) obtained in Synthesis Example 14 Then, 2.4 g of acrylic acid and 1.10 g of acetic acid were charged, and the inside of the reaction apparatus was purged with nitrogen under stirring, and heated to 80 ° C. in a nitrogen atmosphere. While maintaining the inside of the reaction vessel at 80 ° C., an aqueous solution in which 8.6 g of acrylic acid was dissolved in 136.5 g of ion-exchanged water was added in 3 hours, and 0.20 g of 3-mercaptopropionic acid was added to 149.8 g of ion-exchanged water. The dissolved aqueous solution was dropped in 3 hours, and an aqueous solution in which 2.2 g of ammonium persulfate was dissolved in 143.6 g of ion-exchanged water was dropped over 3.5 hours. Thereafter, the temperature was maintained at 80 ° C. for 1 hour, and then the polymerization reaction was terminated. Thereafter, the acidic reaction solution was adjusted to pH 6.0 using an aqueous sodium hydroxide solution and ion-exchanged water at a temperature not higher than the polymerization reaction temperature, and a copolymer having a weight average molecular weight of 100,000 and Mw / Mn 3.17. An aqueous solution of (3) was obtained.

Comparative production example 1
In a glass reactor equipped with a thermometer, a stirrer, a dripping device, a nitrogen introduction tube and a reflux cooling device, 278.4 g of ion-exchanged water, an ethylene oxide 50 mol adduct of 3-methyl-3-buten-1-ol ( (Also referred to as IPN50) 272.8 g, 5.4 g of acrylic acid, and 0.21 g of acetic acid were charged, the inside of the reactor was purged with nitrogen under stirring, and the mixture was heated to 80 ° C. in a nitrogen atmosphere. While maintaining the inside of the reaction vessel at 80 ° C., an aqueous solution in which 21.6 g of acrylic acid was dissolved in 129.8 g of ion-exchanged water was added for 3 hours, and 1.27 g of 3-mercaptopropionic acid was added to 148.7 g of ion-exchanged water. An aqueous solution in which 5.7 g of ammonium persulfate was dissolved in 136.1 g of ion-exchanged water was dropped over 3 hours in 3 hours. Thereafter, the temperature was maintained at 80 ° C. for 1 hour, and then the polymerization reaction was terminated. Thereafter, the acidic reaction solution was adjusted to pH 6.0 with an aqueous sodium hydroxide solution and ion-exchanged water at a temperature not higher than the polymerization reaction temperature, and the weight average molecular weight was 103,000 and Mw / Mn was 4.69. An aqueous solution of the polymer (4) was obtained.

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

<Examples 1-3 and Comparative Example 1>
Copolymers (1) to (4) obtained in Production Examples 1 to 3 and Comparative Production Example 1 were mixed in the following composition, and mortar flow values and mortar compressive strengths were evaluated as cement dispersants. The results are shown in Table 3.
<Mortar evaluation method>
The mortar test was performed in an environment where the temperature was 20 ° C. ± 1 ° C. and the relative humidity was 60% ± 10%.
The mortar formulation was C / S / W = 600/1350/210 (g). However,
C: Ordinary Portland cement (manufactured by Taiheiyo Cement)
S: Standard sand for cement strength test (Cement Association)
W: As an ion exchange aqueous solution W of a polymer (copolymer) and an antifoaming agent, an addition amount of the polymer aqueous solution shown in Table 3 was weighed and an antifoaming agent MA-404 (manufactured by Pozoris) was used. In the form, 15% by mass was added to the solid content of the polymer, and ion-exchanged water was further added to obtain a predetermined amount, which was sufficiently uniformly dissolved. In Table 3, the addition amount of the polymer is represented by mass% of the polymer solid content with respect to the cement mass.
A stainless beater (stirring blade) was attached to a Hobart mortar mixer (model number N-50; manufactured by Hobart), C and W were added, and kneaded at a first speed for 30 seconds. Further, S was added over 30 seconds while kneading at a first speed. After the completion of S addition, after kneading for 30 seconds in duplicate, the mixer was stopped, the mortar was scraped off for 15 seconds, and then allowed to stand for 75 seconds. The mixture was allowed to stand for 75 seconds and then kneaded at a second speed for 60 seconds to prepare a mortar.

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

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

Claims (5)

An unsaturated polyalkylene glycol derivative represented by the following general formula (1):

(.Y ^wherein, R 1, ^{R 2} and ^{R 3} are the same or different, .A ¹ O represents a hydrogen atom or a methyl group, the same or different and each represents an oxyalkylene group having 2 to 18 carbon atoms Represents a residue of a compound having two or more active groups, Z represents the same or different and represents — (A ² O) _n —R ⁴ , A ² O represents the same or different and has 2 carbon atoms; Represents an oxyalkylene group having ˜18, R ⁴ represents a hydrogen atom or a hydrocarbon group having 1 to 30 carbon atoms, n represents the average number of moles of the oxyalkylene group represented by A ² O, and the same. Or, it is a number from 2 to 300. p is 0, 1 or 2. q is 0 or 1. t is the average number of moles added of the oxyalkylene group represented by A ¹ O. And is a number from 2 to 300. m is an integer of 2 or more, and represents an active group represented by Y. Is the number of the maximum number is determined depending on the activity groups of the compound having more than five.) 2. The unsaturated polyalkylene glycol derivative according to claim 1, wherein Y in the general formula (1) is represented by the following general formula (2).
_{- (C 3 H 6 O 2} ) r - (2)
(In the formula, r represents the average added mole number of a glyceryl group represented by C ₃ H ₆ O ₂ and is a number from 1 to 300. The glyceryl group represented by (C ₃ H ₆ O ₂ ) is The same or different, the following formula:

It consists of the structure represented by. ) A method for producing the unsaturated polyalkylene glycol derivative according to claim 1, comprising:
The production method includes the step 1 of reacting an epoxy alcohol and / or a polyhydric alcohol with an unsaturated polyalkylene glycol compound represented by the following general formula (3). Production method.

(.P ^wherein, R 1, ^{R 2} and ^{R 3} are the same or different, .A ¹ O represents a hydrogen atom or a methyl group, the same or different and each represents an oxyalkylene group having 2 to 18 carbon atoms Is 0, 1 or 2. q is 0 or 1. t represents the average number of moles added of the oxyalkylene group represented by A ¹ O, and is a number from 2 to 300.) 4. The method for producing an unsaturated polyalkylene glycol derivative according to claim 3, wherein the production method further comprises a step 2 in which an alkylene oxide is reacted with the polyhydric alcohol derivative obtained in the step 1. An intermediate of an unsaturated polyalkylene glycol derivative represented by the following general formula (4):

^(Wherein, R 1, ^{R 2} and ^{R 3} are the same or different, .R ⁴ represents a hydrogen atom or a methyl group are the same or different, represent a hydrogen atom or a hydrocarbon group having 1 to 30 carbon atoms A ¹ O is the same or different and represents an oxyalkylene group having 2 to 18 carbon atoms, Y ′ represents — (C ₃ H ₆ O ₂ ) _r —, and _r represents C ₃ H ₆ O _{2. .} in a mean addition number of moles of glyceryl group represented by the number of _{1~300 (C 3 H 6 O 2} ) glyceryl group represented by the same or different, the following formula:

It consists of the structure represented by. p is 0, 1 or 2. q is 0 or 1. t represents the average addition mole number of the oxyalkylene group represented by A ¹ O, and is a number of 2 to 300. m is an integer of 2 or more, and is a number whose maximum number is determined depending on the number of — (C ₃ H ₆ O ₂ ) _r — active groups represented by Y ′. )