JP3374369B2 - Method for producing cement dispersant and copolymer for cement dispersant - Google Patents

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a method for producing a cement dispersant and a copolymer for a cement dispersant.

[0002]

2. Description of the Related Art In the recent concrete industry, there is a strong demand for improvement in durability and strength of concrete structures, and reduction of the unit water amount is an important issue. Therefore, there are many proposals for cement dispersants. For example, Japanese Patent Publication Sho 58-3
In JP 8380, a polyethylene glycol monoallyl ether monomer (I), a maleic acid type monomer (II) and a monomer (III) copolymerizable with these monomers are used at a specific ratio. Cement dispersants containing the resulting copolymer as a main component have been proposed, but the water reducing performance is still insufficient.

[0003]

SUMMARY OF THE INVENTION It is, therefore, an object of the present invention to provide a method for producing a cement dispersant and a copolymer for a cement dispersant which are excellent in water reducing performance and slump retention performance.

[0004]

Means for Solving the Problems As a result of investigations, the present inventors have found that a specific copolymer (A) having a specific monomer composition ratio and a limited molecular weight exhibits high water reducing performance and slump loss. The inventors have found that it is an excellent cement dispersant that also prevents the above-mentioned problems and completed the present invention. That is, the present invention provides a method for producing a cement dispersant and a copolymer for a cement dispersant, which exhibits high water reducing performance and also prevents slump loss.

The above-mentioned objects are (1) general formula (1)

[0006]

[Chemical 5]

(In the formula, R ¹ , R ² and R ³ each independently represent hydrogen or a methyl group, and R ¹ , R ³ and R ² do not simultaneously represent a methyl group, and R ⁴ is -CH ₂ -,
Represents — (CH ₂ ) ₂ — or —C (CH ₃ ) ₂ —, R ¹ ,
The total number of carbon atoms in R ² , R ³ and R ⁴ is 3, and R ⁵ O represents one or a mixture of two or more oxyalkylene groups having 2 to 4 carbon atoms, and in the case of two or more, it is a block. also be added to Jo may also be added to the random form, R ⁶ is hydrogen
And p is the average number of moles of oxyalkylene groups added and represents an integer of 1 to 300. ) Unsaturated polyalkylene glycol ether monomer (I) 50-
99% by weight and the general formula (2)

[0008]

[Chemical 6]

(However, in the formula, M¹, M²Each independently water
Elementary, monovalent metal, divalent metal, ammonium or organic amine
And X is -OM²Or -Y- (R⁷O)_qR⁸Represents
Y represents -O- or -NH-, R⁷O is the carbon number
Mixture of 1 to 2 or 2 to 4 oxyalkylene groups
Represents an object, and if more than one type is added in blocks
R may be added at random or R⁸Is hydrogen, charcoal
Alkyl groups, phenyl groups, aminoalkyl groups having a prime number of 1 to 22
Group, alkylphenyl group or hydroxylalkyl group
(Aminoalkyl group, alkylphenyl group, hydroxy
The alkyl group in the alkyl group has 1 to 22 carbon atoms.
Represents the average addition mole of the oxyalkylene group.
It is a number and represents an integer of 0 to 300. However, M¹Concludes
The combined oxygen and the carbon to which X is bonded
What constitutes an acid anhydride group (-CO-O-CO-)
including. In this case M¹And X do not exist. )
Maleic acid-based monomer (II) 50 to 1% by weight, and copolymer
0 to 49% by weight of other compatible monomer (III) (however,
ThenLess than 30% by weight of unsaturated sulfonic acids. In addition,
The total of (I), (II), and (III) is 100 weight.
%) Is 10,000, and the weight average molecular weight is 10,000.
The copolymer (A) in the range of 100 to 100,000.
And a cement dispersant characterized by:

The present invention also provides (2) general formula (1)

[0011]

[Chemical 7]

(In the formula, R ¹ , R ² and R ³ each independently represent hydrogen or a methyl group, and R ¹ , R ³ and R ² do not simultaneously represent a methyl group, and R ⁴ represents -CH ₂ -,
Represents — (CH ₂ ) ₂ — or —C (CH ₃ ) ₂ —, R ¹ ,
The total number of carbon atoms in R ² , R ³ and R ⁴ is 3, and R ⁵ O represents one or a mixture of two or more oxyalkylene groups having 2 to 4 carbon atoms, and in the case of two or more, it is a block. also be added to Jo may also be added to the random form, R ⁶ is hydrogen
And p is the average number of moles of oxyalkylene groups added and represents an integer of 1 to 300. ) Unsaturated polyalkylene glycol ether monomer (I) 50-
99% by weight and the general formula (2)

[0013]

[Chemical 8]

(However, in the formula, M¹, M²Each independently water
Elementary, monovalent metal, divalent metal, ammonium or organic amine
And X is -OM²Or -Y- (R⁷O)_qR⁸Represents
Y represents -O- or -NH-, R⁷O is the carbon number
Mixture of 1 to 2 or 2 to 4 oxyalkylene groups
Represents an object, and if more than one type is added in blocks
R may be added at random or R⁸Is hydrogen, charcoal
Alkyl groups, phenyl groups, aminoalkyl groups having a prime number of 1 to 22
Group, alkylphenyl group or hydroxylalkyl group
(Aminoalkyl group, alkylphenyl group, hydroxy
The alkyl group in the alkyl group has 1 to 22 carbon atoms.
Represents the average addition mole of the oxyalkylene group.
It is a number and represents an integer of 0 to 300. However, M¹Concludes
The combined oxygen and the carbon to which X is bonded
What constitutes an acid anhydride group (-CO-O-CO-)
including. In this case M¹And X do not exist. )
Maleic acid-based monomer (II) 50 to 1% by weight, and copolymer
0 to 49% by weight of other compatible monomer (III) (however,
ThenLess than 30% by weight of unsaturated sulfonic acids. In addition,
The total of (I), (II), and (III) is 100 weight.
%) Is 10,000, and the weight average molecular weight is 10,000.
Method for producing copolymer (A) in the range of 100 to 100,000
Method, the half-life of the radical polymerization initiator is 0.5 to 5
Characterized by carrying out aqueous solution polymerization at a temperature of 00 hours
By the method for producing the copolymer (A) for cement dispersant according to
Is also achieved.

Further, (3) the cement dispersion as described in (2) above, wherein the amount of all the monomers used is in the range of 30 to 95% by weight based on the total amount of the raw materials used in the polymerization. It is also achieved by the method for producing the copolymer for agent (A). Furthermore, (4) a copolymer for a cement dispersant as described in (2) or (3) above, wherein a persulfate is used as a radical initiator and the polymerization temperature is in the range of 40 to 90 ° C. It is also achieved by the manufacturing method of (A).

[0016]

BEST MODE FOR CARRYING OUT THE INVENTION The monomer (I) is represented by the general formula (1) above.
It is shown by. Examples of the monomer that gives such a repeating unit include allyl alcohol, methallyl alcohol, 3-methyl-3-buten-1-ol, and 3
-Methyl-2-buten-1-ol, 2-methyl-3-
The compound which added 1 to 300 mol of alkylene oxides to unsaturated alcohols, such as butene-2-ol, can be mentioned, and these 1 type, or 2 or more types can be used.

In order to obtain high water reducing performance, the monomer (I)
It is important to disperse the cement particles with steric repulsion and hydrophilicity due to the polyalkylene glycol chain contained in. Therefore, it is preferable that many oxyethylene groups are introduced into the polyalkylene glycol chain. Also,
It is preferable to use a polyalkylene glycol chain having an average addition mole number of oxyalkylene groups of 1 to 300,
From the viewpoint of polymerizability and hydrophilicity, 1-100, or 5-
100 polyalkylene glycol chains are suitable.

The monomer (II) is represented by the above general formula (2). Examples of such a monomer (II) include maleic acid, maleic anhydride, half-esters of maleic acid and an alcohol having 1 to 22 carbon atoms; maleic acid and an amine having 1 to 22 carbon atoms. Half amides; Half amides or half esters of maleic acid and amino alcohols having 1 to 22 carbon atoms; Compound (C) obtained by adding 1 to 300 mol of oxyalkylene having 2 to 4 carbon atoms to these alcohols and malein Half-esters with acid; half-amides of a compound obtained by aminating a hydroxyl group at one end of the compound (C) with maleic acid; maleic acid and a glycol having 2 to 4 carbon atoms or the number of moles of addition of these glycols is 2 To 100-polyalkylene glycol half ester, maleamic acid and C2-C4 glycol or these glycols Number of moles added: 2 to 1
No. 00 half amide with polyalkylene glycol, and monovalent metal salts, divalent metal salts, ammonium salts and organic amine salts thereof, and the like.
One kind or two or more kinds can be used.

The monomer (III) is the monomer (I) and / or
Alternatively, it is a monomer copolymerizable with the monomer (II). Examples of such a monomer (III) include unsaturated dicarboxylic acids such as fumaric acid, itaconic acid and citraconic acid, and monovalent metal salts, divalent metal salts and ammonium salts thereof.
Monoesters and diesters of organic amine salts and their acids with alkyl alcohols having 1 to 20 carbon atoms and glycols having 2 to 4 carbon atoms or polyalkylene glycols having addition moles of these glycols of 2 to 100, and One-terminal aminated products of these acids with alkylamines having 1 to 20 carbon atoms and glycols having 2 to 4 carbon atoms, or the number of added moles of these glycols is 2 to 10
Monoamides and diamides of one-terminal aminated products of polyalkylene glycol of 0; maleic acid and 1 to 20 carbon atoms
Alkyl alcohols and C2-C4 glycols or diesters of these glycols with polyalkylene glycols having a mole number of 2-100, and these acids and C1-C20 alkyl amines and C2-C2. 4. A diamide of a glycol with a terminal at one end thereof, or a polyamide glycol having a number of added moles of these glycols of 2 to 100 with a terminal at the end of an amino compound;
Unsaturated carboxylic acids such as (meth) acrylic acid, their monovalent metal salts, divalent metal salts, ammonium salts, organic amine salts, and these acids, and alkyl alcohols having 1 to 20 carbon atoms and 2 to 4 carbon atoms. Glycols or esters of these glycols with a polyalkylene glycol having an addition mole number of 2 to 100, an aminated product of one end of a glycol having 2 to 4 carbon atoms, or a polyalkylene having an addition mole number of 2 to 100 of these glycols Amides of glycol with one-terminal aminated product; unsaturated sulfonic acids such as sulfoethyl (meth) acrylate, 2-methylpropanesulfonic acid (meth) acrylamide, and styrenesulfonic acid, and monovalent metal salts and divalent metal salts thereof. , Ammonium salts and organic amine salts; (meth) acrylamide, (meth) Unsaturated amides such as krylalkylamide; unsaturated amino compounds such as dimethylaminoethyl (meth) acrylate; vinyl esters such as vinyl acetate and vinyl propionate; aromatic vinyls such as styrene. , 1 type, or 2 or more types of these can be used. As a monomer (III), tired
Unsaturated sulfonic acids , if used
The amount of the class of monomers (I), (II) and (III)
It is less than 30% by weight of the total amount.

To obtain the copolymer (A) of the present invention, the above-mentioned monomer components may be copolymerized using a polymerization initiator.
The copolymerization can be performed by a known method such as solution polymerization or bulk polymerization. Solution polymerization can be carried out batchwise or continuously, and the solvent used in that case is water;
Alcohols such as methyl alcohol, ethyl alcohol and isopropyl alcohol; aromatic or aliphatic hydrocarbons such as benzene, toluene, xylene, cyclohexane and n-hexane; ester compounds such as ethyl acetate; ketone compounds such as acetone and methyl ethyl ketone. However, from the solubility of the raw material monomer and the resulting copolymer,
It is preferable to use at least one selected from the group consisting of water and lower alcohols having 1 to 4 carbon atoms, and among them, it is more preferable to use water as the solvent because the solvent removal step can be omitted. When maleic anhydride is used for the copolymerization, polymerization using an organic solvent is preferable.

When carrying out aqueous solution polymerization, persulfates such as ammonium persulfate, sodium persulfate and potassium persulfate are used as radical polymerization initiators; hydrogen peroxide; azoamidine compounds such as azobis-2methylpropionamidine hydrochloride and the like. The water-soluble polymerization initiator of is used, in which case an alkali metal sulfite such as sodium hydrogen sulfite,
F such as metabisulfite, sodium hypophosphite, Mohr salt
An accelerator such as e (II) salt, sodium hydroxymethanesulfinate dihydrate, hydroxylamine hydrochloride and thiourea can also be used in combination.

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

Bulk polymerization is carried out by radical polymerization initiators such as benzoyl peroxide, lauroyl peroxide and sodium peroxide; t-butyl hydroperoxide, cumene hydroperoxide and other hydroperoxides; azobisisobutyronitrile. It is carried out in the temperature range of 50 to 200 ° C. using an azo compound or the like.

As a particularly preferred method for producing the cement dispersant of the present invention, any one of the following methods (1) to (2) is exemplified. A method of performing aqueous solution polymerization at a temperature at which the half-life of the radical polymerization initiator is 0.5 to 500 hours. A method of carrying out aqueous solution polymerization at a temperature at which the half-life of the radical polymerization initiator is 0.5 to 500 hours and in the range of 30 to 95% by weight based on the total amount of raw materials used.

A method of performing aqueous solution polymerization at a polymerization temperature of 40 to 90 ° C. using a persulfate as a radical polymerization initiator. Using persulfate as a radical polymerization initiator, aqueous solution polymerization is carried out at a polymerization temperature of 40 to 90 ° C. and an amount of all monomers used of 30 to 95% by weight based on the total amount of raw materials used. Method.

In the processes (1) to (5), the half-life of the radical polymerization initiator is 0.5 to 500 hours, preferably 1 to 5 in order to obtain a specific average molecular weight and high monomer reactivity according to the present invention. 300 hours, more preferably 3 to 1
It is essential to carry out the polymerization reaction at a temperature of 50 hours. For example, when a persulfate is used as an initiator, the polymerization reaction is
It is necessary to carry out the treatment within the range of 0 to 90 ° C, preferably 42 to 85 ° C, and more preferably 45 to 80 ° C. At this time, the radical polymerization initiator may be charged into the reactor from the beginning, or may be added dropwise to the reactor, or these may be combined depending on the purpose. The polymerization time is preferably 2
The range is preferably 6 hours, more preferably 3 to 5 hours. If the polymerization time is longer or shorter than this range,
It is not preferable because it lowers the polymerization rate and productivity.
The amount of all monomers used is 30 to
The range of 95% by weight, preferably 40 to 93% by weight, and more preferably 50 to 90% by weight is good. If the amount used is higher or lower than this range, the polymerization rate and productivity are lowered. Not preferable. At this time, it is preferable to charge the monomer (I) into the reactor from the beginning,
The monomer (II) and the monomer (III) may be charged into the reactor from the beginning, or may be added dropwise to the reactor, or they may be combined depending on the purpose. Furthermore, the monomer (I
The neutralization rate of I) and the monomer (III) is in the range of 0 to 75%, and a neutralization rate of more than 75% is not preferable because the water reducing performance is deteriorated. The polymerization reaction is carried out under such conditions, and after the completion of the reaction, neutralization and concentration adjustment are carried out if necessary.

In the above various polymerizations, if necessary, mercaptoethanol, thioglycerol, thioglycolic acid, 2-mercaptopropionic acid, 3-mercaptopropionic acid, thiomalic acid, octylthioglycolate, and 3-mercaptopropion. Octyl acid, 2-
One or more chain transfer agents such as mercaptoethanesulfonic acid can be used.

Copolymer (A) thus obtained
Is used as it is as the main component of the cement dispersant, but if necessary, the copolymer (A) may be neutralized with an alkaline substance before use. Preferred examples of such an alkaline substance include inorganic salts such as hydroxides, chlorides and carbonates of monovalent and divalent metals; ammonia; organic amines and the like. When maleic anhydride is used for the copolymerization, the resulting copolymer may be used as it is as a cement dispersant or may be used after being hydrolyzed.

In the above-mentioned production methods (1) to (4), the weight ratio of monomer (I) / monomer (II) / monomer (III) in the copolymer (A) is (I) / (II). ) / (III)
= 50-99 / 50-1 / 0-49, preferably (I)
/ (II) / (III) = 60-95 / 40-5 / 0
30, more preferably (I) / (II) / (III) =
It is preferably in the range of 70 to 95/30 to 5/0 to 10. The weight average molecular weight of the copolymer (A) is determined by gel permeation chromatography (hereinafter referred to as "GP
Called "C") 1 in terms of polyethylene glycol
10,000-100,000, preferably 10,000
~ 80,000, more preferably 10,000-70,
It is 000. If the weight ratio and the weight average molecular weight are out of the ranges, a cement dispersant exhibiting high water reducing performance and slump loss preventing performance cannot be obtained.

In a cement composition containing at least cement, water and a cement dispersant, the cement dispersant of the present invention can be used as the cement dispersant.
Cement, which is a component of the cement composition, is a hydraulic cement such as ordinary Portland cement, alumina cement, and various mixed cements. There is no limit to the amount of water used per 1 m ^{3 of} concrete and the amount of cement used,
Cement composition using the cement dispersant of the present invention is particularly suitable for the production of high durability, high strength concrete,
From that meaning, the unit water volume is 120 to 200 kg / m.
³ , water / cement ratio = 15-70%, preferably unit water amount 120-185 kg / m ³ , water / cement ratio = 20-
60% is recommended.

The copolymer (A) can be used as the main component of the cement dispersant as it is in the form of an aqueous solution, either alone or as a mixture, or in combination with other known cement admixtures. Is also good. Such known cement admixtures include, for example, conventional cement dispersants, air entraining agents, cement wetting agents, expanding agents, waterproofing agents, retarders, quick-setting agents, water-soluble polymer substances, thickeners, and agglomerates. Agents, drying shrinkage reducing agents, strength enhancing agents, curing accelerators, defoaming agents and the like.

The copolymer (A) has a cement weight of 0.0
The amount may be 1 to 1.0%, preferably 0.02 to 0.5%. By this addition, various desirable effects such as reduction of the amount of unit water, increase of strength, improvement of durability, etc. are brought about. If the amount used is less than 0.01%, the performance is insufficient, and conversely, even if the amount used exceeds 1.0%, the effect is substantially leveled off and it is disadvantageous from the economical aspect.

[0033]

The present invention will be described in more detail with reference to the following examples, but the present invention is not limited thereto. In the examples,% means% by weight unless otherwise specified.
In addition, parts are parts by weight. <Example 1 for producing a cement dispersant (1)> 24.2 g of ion-exchanged water and 3-methyl-3 in a glass reaction container equipped with a thermometer, a stirrer, a dropping funnel, and a reflux condenser.
-Buten-1-ol was charged with 50 g of an unsaturated alcohol obtained by adding 35 mol of ethylene oxide (hereinafter referred to as IPN-35) and 6.4 g of maleic acid, and 60
After the temperature was raised to ℃, an aqueous solution prepared by dissolving 0.86 g of ammonium persulfate in 13.4 g of ion-exchanged water was added thereto.
Dropped in minutes. Then, the temperature is maintained at 60 ° C. for 60 minutes to complete the polymerization reaction, and the weight average molecular weight of 34,
A cement dispersant (1) of the present invention consisting of 000 polymer aqueous solutions was obtained. <Example 2 for producing a cement dispersant (2)> 131.6 g of ion-exchanged water and IPN-35 in a glass reaction container equipped with a thermometer, a stirrer, a dropping funnel, and a reflux condenser.
Of 50 g and maleic acid of 6.4 g were charged and the temperature was raised to 60 ° C., and then an aqueous solution in which 0.86 g of ammonium persulfate was dissolved in 94 g of ion-exchanged water was added dropwise over 180 minutes. Then, the temperature was maintained at 60 ° C. for 60 minutes to complete the polymerization reaction, and a cement dispersant (2) composed of an aqueous polymer solution having a weight average molecular weight of 17,600 was obtained. <Example 3 for producing cement dispersant (3)> In a glass reaction container equipped with a thermometer, a stirrer, a dropping funnel, and a reflux condenser, 1.61 g of ion-exchanged water, 50 g of IPN-35, and maleic acid. 6.4 g of was added and the temperature was raised to 60 ° C., and then an aqueous solution prepared by dissolving 1.2 g of ammonium persulfate in 1.68 g of ion-exchanged water was added dropwise over 180 minutes. Thereafter, the polymerization reaction was completed by continuously maintaining the temperature at 60 ° C. for 60 minutes to obtain a cement dispersant (3) composed of an aqueous polymer solution having a weight average molecular weight of 25,400. <Comparative Example 1 for producing a comparative cement dispersant (1)>
A comparative cement dispersant (1) was synthesized according to the example of JP-B-4-68323. That is, 16.7 g of ion-exchanged water and IPN-in a glass reaction vessel equipped with a thermometer, a stirrer, a dropping funnel, a nitrogen introduction tube and a reflux condenser.
After charging 50 g of 35 and raising the temperature to 95 ° C., an aqueous solution prepared by dissolving 6.4 g of maleic acid and 0.57 g of ammonium persulfate in 9.9 g of ion-exchanged water was added dropwise thereto over 120 minutes. Then, while maintaining the temperature at 95 ° C., an aqueous solution prepared by dissolving 0.29 g of ammonium persulfate in 3.8 g of ion-exchanged water was added dropwise over 60 minutes to complete the polymerization reaction, and a polymer having a weight average molecular weight of 7,800 was obtained. A comparative cement dispersant (1) consisting of an aqueous solution was obtained. <Comparative Example 2 for producing a comparative cement dispersant (2)
A comparative cement dispersant (2) composed of a polymer aqueous solution having a weight average molecular weight of 4,300 was obtained in exactly the same manner as in Example 2 of JP-B-4-68323.

The above results are shown in Table 1. From Table 1, the cement dispersant of the present invention has a higher polymerization rate of the monomer (I) than the comparative cement dispersant, and the weight average molecular weight can be freely increased to a molecular weight suitable for the cement dispersant. I understand.

[0035]

[Table 1]

<Examples 4 to 6 and Comparative Examples 3 to 4> [Mortar test example] Cement dispersant (1) of the present invention
The polymer aqueous solution of (3) and a comparative cement dispersant (1),
Mortar flow values were compared using the polymer aqueous solution of (2). The materials used in the test and the composition of the mortar are
Chichibu Onoda Ordinary Portland cement 400g, Toyoura standard sand 800g, ion exchange water 260g containing various polymers
Is.

Mortar was prepared by mechanical kneading with a mortar mixer for 3 minutes at room temperature, and the diameter was 55 mm and the height was 55 mm.
Fill the hollow cylinder with mortar. Next, after the cylinder was lifted vertically, the diameter of the mortar spread on the table was measured in two directions, and the average was used as the flow value. The results are shown in Table 2.

[0038]

[Table 2]

From Table 2, it can be seen that the cement dispersant of the present invention has a higher weight average molecular weight of the polymer as compared with the comparative cement dispersant, so that a small addition amount gives an equivalent mortar flow value. Further, the cement dispersant (1) of the present invention
Has a high polymerization rate because it uses a polymerization method with a polymerization concentration of 60%, so the cement dispersant of the present invention with a polymerization concentration of 20% (2) or the cement dispersant of the present invention with a polymerization concentration of 96% (3) The retention of mortar flow value is superior to that of

[0040]

EFFECT OF THE INVENTION The cement dispersant of the present invention is a polycarboxylic acid type polymer, and by specifying the monomer composition ratio and the weight average molecular weight thereof, it is excellent in high water reducing performance and slump loss preventing ability. Construction obstacles are improved.

─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Shogo Iwai 14-1 Chidori-cho, Kawasaki-ku, Kawasaki-shi, Kanagawa Incorporated in Nippon Shokubai Co., Ltd. Incorporated by Nippon Shokubai (56) Reference JP-A-8-48852 (JP, A) JP-A-5-345647 (JP, A) JP-A-5-310458 (JP, A) JP-A-57-118058 ( JP, A) JP-A-4-149056 (JP, A) JP-A-9-142905 (JP, A) JP-A-7-172891 (JP, A) (58) Fields investigated (Int. Cl. ⁷ , DB name) C04B 24/26 C04B 103: 32

Claims (7)

(57) [Claims] 1. A general formula (1): (However, in the formula, R ¹ , R ² and R ³ each independently represent hydrogen or a methyl group, and R ¹ , R ³ and R ² do not simultaneously become a methyl group, and R ⁴ is —CH ₂ -, - (CH _{2) 2}
- or -C (CH _{3) 2} - ^{represents, R 1, R 2, R} 3 and the total number of carbons in R ⁴ is 3, R ⁵ O is one oxyalkylene group having 2 to 4 carbon atoms Or a mixture of two or more kinds, and in the case of two or more kinds, they may be added blockwise or randomly, and R ⁶ represents hydrogen, p
Is the average number of moles of oxyalkylene groups added and is 1 to 30.
Represents an integer of 0. 50 to 99% by weight of the unsaturated polyalkylene glycol ether-based monomer (I) represented by
And the general formula (2): (However, in the formula, M ¹ and M ² each independently represent hydrogen, a monovalent metal, a divalent metal, ammonium or an organic amine,
X represents -OM ² or _{^{-Y- (R 7 O) q R}} 8, Y is -
O- or represents -NH-, R ⁷ O represents one kind or a mixture of two or more kinds of oxyalkylene groups having 2 to 4 carbon atoms, in the case of two or more randomly also be added in a block form shape R ⁸ may be hydrogen or C 1 to C 1
22 represents an alkyl group, a phenyl group, an aminoalkyl group, an alkylphenyl group or a hydroxylalkyl group (the alkyl group in the aminoalkyl group, the alkylphenyl group and the hydroxylalkyl group has 1 to 22 carbon atoms), and q is The average number of moles of oxyalkylene groups added,
It represents an integer of 0 to 300. However, including those that make up the oxygen M ¹ is bond, X is bonded to that carbon and is bonded to the acid anhydride group (-CO-O-CO-). In this case, M ¹ and X do not exist. ) 50 to 1% by weight of the maleic acid-based monomer (II) and 0 to 49% by weight of the other copolymerizable monomer (III) (however, unsaturated sulfonic acids are less than 30% by weight. Note that (I), (I
The total of (I) and (III) is 100% by weight), and the weight average molecular weight obtained by polymerization is 10,000 to 100,0.
A cement dispersant characterized by containing a copolymer (A) in the range of 00. 2. The unsaturated polyalkylene glycol A
Average addition mode of oxyalkylene group of ter type monomer (I)
The cement dispersion according to claim 1, wherein the number of leule is 1 to 100.
Agent. 3. The unsaturated polyalkylene glycol A
The ter-based monomer (I) is 3-methyl-3-butene-1-
Unsaturated alcohol with ethylene oxide added to all
The cement dispersant according to claim 1, wherein the cement dispersant is 4. The copolymer (A) is prepared by aqueous solution polymerization.
The sem according to claim 1, which is obtained.
Agent dispersant. 5. A compound represented by the general formula (1): (However, in the formula, R ¹ , R ² and R ³ each independently represent hydrogen or a methyl group, and R ¹ , R ³ and R ² do not simultaneously become a methyl group, and R ⁴ is —CH ₂ -, - (CH _{2) 2}
- or -C (CH _{3) 2} - ^{represents, R 1, R 2, R} 3 and the total number of carbons in R ⁴ is 3, R ⁵ O is one oxyalkylene group having 2 to 4 carbon atoms Or a mixture of two or more kinds, and in the case of two or more kinds, they may be added blockwise or randomly, and R ⁶ represents hydrogen, p
Is the average number of moles of oxyalkylene groups added and is 1 to 30.
Represents an integer of 0. 50 to 99% by weight of the unsaturated polyalkylene glycol ether-based monomer (I) represented by
And the general formula (2): (However, in the formula, M ¹ and M ² each independently represent hydrogen, a monovalent metal, a divalent metal, ammonium or an organic amine,
X represents -OM ² or _{^{-Y- (R 7 O) q R}} 8, Y is -
O- or represents -NH-, R ⁷ O represents one kind or a mixture of two or more kinds of oxyalkylene groups having 2 to 4 carbon atoms, in the case of two or more randomly also be added in a block form shape R ⁸ may be hydrogen or C 1 to C 1
22 represents an alkyl group, a phenyl group, an aminoalkyl group, an alkylphenyl group or a hydroxylalkyl group (the alkyl group in the aminoalkyl group, the alkylphenyl group and the hydroxylalkyl group has 1 to 22 carbon atoms), and q is The average number of moles of oxyalkylene groups added,
It represents an integer of 0 to 300. However, including those that make up the oxygen M ¹ is bond, X is bonded to that carbon and is bonded to the acid anhydride group (-CO-O-CO-). In this case, M ¹ and X do not exist. ) 50 to 1% by weight of the maleic acid-based monomer (II) and 0 to 49% by weight of the other copolymerizable monomer (III) (however, unsaturated sulfonic acids are less than 30% by weight. Note that (I), (I
The total of (I) and (III) is 100% by weight), and the weight average molecular weight obtained by polymerization is 10,000 to 100,0.
In the method for producing the copolymer (A) having a range of 00,
A method for producing a copolymer (A) for cement dispersant, which comprises performing aqueous solution polymerization at a temperature at which the half-life of the radical polymerization initiator is 0.5 to 500 hours. 6. The method according to claim 5 , wherein the amount of all the monomers used is in the range of 30 to 95% by weight based on the total amount of the raw materials used in the polymerization. 7. Using persulfate as a radical initiator, the manufacturing method according to claim 5 or 6, wherein the polymerization temperature is in the range of 40 to 90 ° C..