JPH107749A - Thickener and hydraulic composition containing the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a hydraulic compsn, which is excellent in resistance to separation of ingredients and does not exhibit delay in coagulation by using, as the thickener, a polymer obtd. by polymerizing a monomer component essentially contg. a specific (alkoxy)polylkylene glycol mono(meth)acrylate monomer. SOLUTION: This thickener is a polymer obtd. from a monomer component essentially contg, an (alkoxy)poltalkylene glycol mono(meth)acrylate monomer represented by the formula [wherein R<1> is H or methyl; R<2> O is a 2-4C oxylakylene group provided (R<2> O)m may be a mixture of two or more kinds of 2-4C oxyalkylene groups and, in the case of two or more kinds, those groups may be added in block or randomly; R<3> is H or a 1-5C alkyl; and m is an integer of 1-10]. The viscosity of a 0.5% aq. soln. of the polymer is 2-1000cP. the thickener may be a copolymer obtd. from the above-mentioned monomer and a monomer copolymerizable therewith.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a thickener and a hydraulic composition containing the same, which has excellent resistance to material separation.

[0002]

2. Description of the Related Art In general, when the fluidity of concrete is increased, material separation occurs, and as a result, the filling property and the concrete composition become non-uniform, resulting in a decrease in concrete strength. In addition, since thickeners used for high-fluidity concrete and water-inseparable concrete generally have a setting retarding effect on cement, the setting of this concrete is delayed more than that of ordinary concrete. In addition, when a water reducing agent is used in combination, the setting delay is further increased (see the guideline for construction of underwater non-separable concrete published by the Japan Society of Civil Engineers (draft)).
As described above, while a commercially available thickener can provide resistance to material separation, it is a serious problem that setting retardation occurs.

[0003]

SUMMARY OF THE INVENTION An object of the present invention is to provide a novel thickener and a hydraulic composition using the same which has excellent material separation resistance and has no setting retardation.

[0004]

The above objects are achieved by the following general formula (1):

[0005]

Embedded image

A polymer derived from a monomer component essentially comprising an (alkoxy) polyalkylene glycol mono (meth) acrylate monomer (a) represented by the formula: % Aqueous solution viscosity is 2-1000C
This is achieved by a thickener characterized by being P.

Further, the present invention provides the above-mentioned thickener, water reducing agent,
It is a hydraulic composition containing water and hydraulic powder.

[0008]

DESCRIPTION OF THE PREFERRED EMBODIMENTS Examples of the (alkoxy) polyalkylene glycol mono (meth) acrylate monomer (a) used in the present invention include hydroxyethyl (meth) acrylate and hydroxypropyl (meth).
Acrylate, polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate, (poly) butylene glycol mono (meth)
Acrylate, (poly) ethylene glycol (poly) propylene glycol mono (meth) acrylate, (poly) ethylene glycol (poly) butylene glycol mono (meth) acrylate, (poly) propylene glycol (poly) butylene glycol mono (meth) acrylate, (Poly) ethylene glycol (poly) propylene glycol (poly) butylene glycol mono (meth) acrylate, methoxy (poly) ethylene glycol mono (meth) acrylate, methoxy (poly) propylene glycol mono (meth) acrylate, methoxy (poly)
Butylene glycol mono (meth) acrylate, methoxy (poly) ethylene glycol (poly) propylene glycol mono (meth) acrylate, methoxy (poly) ethylene glycol (poly) butylene glycol mono (meth) acrylate, methoxy (poly) propylene glycol (poly ) Butylene glycol mono (meth) acrylate, methoxy (poly) ethylene glycol (poly) propylene glycol (poly) butylene glycol mono (meth) acrylate, ethoxy (poly) ethylene glycol mono (meth) acrylate, ethoxy (poly) propylene glycol mono (Meth) acrylate, ethoxy (poly) butylene glycol mono (meth) acrylate, ethoxy (poly) ethylene glycol (poly) propylene glycol (Meth) acrylate, ethoxy (poly) ethylene glycol (poly) butylene glycol mono (meth) acrylate, ethoxy (poly) propylene glycol (poly) butylene glycol mono (meth) acrylate, ethoxy (poly) ethylene glycol (poly) butylene glycol (Poly) alkylene glycol mono (meth) acrylates such as (poly) propylene glycol mono (meth) acrylate can be mentioned, and one or more of these can be used.

In order to obtain good hydrophilicity and salt resistance of the obtained polymer, (alkoxy) polyethylene glycol mono (meth) acrylate is preferred.

Further, the monomer (a) may be replaced with the monomer (a)
May be copolymerized with the monomer (b) copolymerizable with the monomer (b). Examples of the monomer (b) include (meth) acrylic acid, maleic acid, fumaric acid, itaconic acid, citraconic acid, mesaconic acid, and monovalent metal, divalent metal salt, ammonium salt, and organic amine salt thereof. Monoester or diester of (meth) acrylic acid, maleic acid, fumaric acid, itaconic acid, citraconic acid, mesaconic acid and an aliphatic alcohol having 1 to 20 carbon atoms; (meth) acrylamide, (meth) acrylalkylamide Unsaturated amides such as vinyl acetate; vinyl esters such as vinyl acetate and vinyl propionate;
Aromatic vinyls such as styrene; vinyl sulfonic acid,
Unsaturated sulfonic acids such as (meth) allylsulfonic acid, sulfoethyl (meth) acrylate, 2-methylpropanesulfonic acid (meth) acrylamide, styrenesulfonic acid, etc. and their monovalent metal salts, divalent metal salts, ammonium salts, organic Examples thereof include amine salts, and one or more of these can be used.

The polyalkylene glycol-based thickener is derived from a monomer component consisting of the monomer (a) and, if necessary, the monomer (b).

In order to obtain a polymer, the above monomer component may be polymerized using a polymerization initiator. The polymerization can be performed by a method such as polymerization in a solvent or bulk polymerization.

The polymerization in a solvent can be carried out either batchwise or continuously, with the solvent used being water; alcohols such as methyl alcohol, ethyl alcohol and isopropyl alcohol; benzene, toluene, xylene and cyclohexane. Or an aromatic or aliphatic hydrocarbon such as n-hexane; an ester compound such as ethyl acetate; a ketone compound such as acetone and methyl ethyl ketone; From the solubility of the raw material monomer and the obtained polymer and the convenience at the time of using the polymer, water and C1-4
At least one selected from the group consisting of lower alcohols
Preferably, a seed is used. In that case, methyl alcohol, ethyl alcohol, and isopropyl alcohol are particularly effective among the lower alcohols having 1 to 4 carbon atoms.

When the polymerization is carried out in an aqueous medium, a water-soluble polymerization initiator such as ammonium or alkali metal persulfate, hydrogen peroxide, and a water-soluble azo polymerization initiator is used as the polymerization initiator. At this time, an accelerator such as sodium bisulfite and Mohr's salt can be used in combination. For polymerization using lower alcohols, aromatic hydrocarbons, aliphatic hydrocarbons, ester compounds or ketone compounds as solvents, peroxides such as benzoyl peroxide and lauroyl peroxide; hydroperoxides such as cumene hydroperoxide; Aromatic azo compounds such as bisisobutyronitrile; and the like are used as the polymerization initiator. In this case, an accelerator such as an amine compound may be used in combination. More water
When a lower alcohol mixed solvent is used, it can be appropriately selected from the above combinations of various polymerization initiators and accelerators. The polymerization temperature is appropriately determined depending on the solvent and the polymerization initiator used, but is usually in the range of 0 to 120 ° C.

In order to control the molecular weight of the obtained polymer, a thiol chain transfer agent can be used in combination. The thiol-based chain transfer agent used at this time has the general formula HS
-RL (wherein, R represents an alkyl group having 1 to 2 carbon atoms, and L represents -OH, -COOM, -COOR, -SO3
Represents an M group, M represents hydrogen, a monovalent metal, a divalent metal, an ammonium group or an organic amine group, and R has 1 to 10 carbon atoms.
Represents an alkyl group. ), For example, mercaptoethanol, thioglycerol, thioglycolic acid, 2
-Mercaptopropionic acid, 3-mercaptopropionic acid, thiomalic acid, octyl thioglycolate, octyl 3-mercaptopropionate and the like. ) Can be used alone or in combination.

The viscosity of a 0.5% aqueous solution of the polymer used as a thickener of the present invention is 2 to 1000 CP.
Must be within the range. When the 0.5% aqueous solution viscosity is 2 CP or less, the effect of preventing material separation of the hydraulic composition is poor, which is not preferable. If the viscosity is 1000 CP or more, the viscosity of the hydraulic composition increases, and the amount of the admixture used to obtain the desired fluidity increases, which is disadvantageous in cost.

The polymer can be used alone or as a mixture as it is as a thickener. When the polymer is used in combination with a known cement admixture, such a known cement admixture includes, for example, a conventional cement dispersant, an air entrainer, an antifoaming agent, a cement wetting agent, a swelling agent, Waterproofing agents, retarding agents, quick-setting agents, water-soluble polymer substances, coagulants, drying shrinkage reducing agents, strength enhancers, curing accelerators and the like can be mentioned.

The thickener of the present invention can be used for hydraulic cements such as portland cement, belite-rich cement, alumina cement, various types of mixed cements, and hydraulic materials other than cements such as gypsum.

When the thickener of the present invention is used in mortar or concrete using hydraulic cement, the amount of the cement is preferably 0.01 to 10%, more preferably 0.1 to 5% of the weight of the cement. May be added at the time of kneading. This addition has a favorable effect of improving the material separation preventing effect of the hydraulic composition. If the added amount is less than 0.01%, the performance is insufficient. Conversely, even if a large amount exceeding 10% is used, the effect is substantially flattened and disadvantageous in terms of economy.

The thickener of the present invention can be used not only for concrete, such as in-water non-separable concrete, high-fluidity concrete and compaction-free concrete, but also for general thickeners. . Examples include food thickeners, papermaking formation aids, retention aids, pharmaceutical thickeners (thickeners), dispersion stabilizers, cosmetic emulsifiers, emulsifiers, thickeners / gelling agents, Mud viscosity modifier for drilling, thickener for grout, cementing agent for oil mining,
It can also be used as an agent for polymer flooding for forced oil recovery and myseller polymer flooding.

[0021]

EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples, but the present invention is not limited to these examples. In the examples, unless otherwise specified,% means% by weight and part means part by weight.

Example 1 for producing thickener (1) 2325 parts of water was charged into a glass reactor equipped with a thermometer, a stirrer, a dropping funnel, a nitrogen inlet tube and a reflux condenser.
The atmosphere in the reaction vessel was replaced with nitrogen under stirring, and 80
Heated to ° C. Next, 300 parts of methoxypolyethylene glycol monomethacrylate (average number of moles of ethylene oxide added: 25), a monomer mixture aqueous solution composed of 75 parts of water, and 200 parts of a 0.03% V-50 aqueous solution were each dropped for 2 hours. After the addition, 0.03% V-50
100 parts of the aqueous solution was added dropwise over 1 hour. Thereafter, the temperature was maintained at 80 ° C. continuously for 1 hour to complete the polymerization reaction,
A thickener (1) of the present invention comprising a polymer having a 0.5% aqueous solution viscosity of 9.7 CP was obtained.

"Measurement Test for Viscosity Thickening" Aska Clean manufactured by Shin-Etsu Chemical Co., Ltd. as the thickener (1) and the comparative thickener (1) of the present invention, and Daicel Chemical Industries Co., Ltd. as the comparative thickener (2) The material separability and mortar flow of mortar when using celcrete were measured.

"Measurement method of viscosity increase" 630 g of ordinary Portland cement, 1016 g of Toyoura standard sand, 340 g of water, 1.89 g of polycarboxylic acid type high-performance water reducing agent (0.3% by weight of cement; Aqualoc FC-600 manufactured by Nippon Shokubai) ) And a predetermined amount of a thickener were kneaded with a mortar mixer for 3 minutes, then transferred to a 500 ml measuring cylinder and allowed to stand for 1 hour,
The amount of separated water appearing at the top of the measuring cylinder was measured. Further, a part of the mortar was put into water, and the turbidity of the water was visually determined.

"Mortar test" The mortar prepared by the above method is packed in a hollow cylinder having a diameter of 55 mm and a height of 55 mm. Next, after lifting the cylinder, the diameter of the mortar spread on the table was measured in two directions, and the average was taken as the flow value.

[0026]

[Table 1]

From Table 1, it can be seen that the thickener (1) of the present invention has the same thickening effect as Comparative Examples (1) and (2) which are conventional thickeners.

"Curing time measurement test" Aska Clean (manufactured by Shin-Etsu Chemical Co., Ltd.) as the thickener (1) and the comparative thickener (1) of the present invention, and Daicel Chemical Industries, Ltd. as the comparative thickener (2) The setting time of the cement paste when using celcrete was measured.

"Method of measuring hardening time" After 800 g of ordinary Portland cement was kneaded with 432 g of water and a predetermined amount of an agent for 5 minutes using a mortar mixer, the resulting cement paste was transferred to an insulated container, and the change with time of heat generation was measured.

[0030]

[Table 2]

From Table 2, it can be seen that when the thickener (1) of the present invention was used, the time during which the curing exothermic peak was exhibited was faster than that using the thickeners of Comparative Examples (3) and (4). Further, it can be seen from the fact that the thickening agent of the present invention has no curing delay from the same heat generation peak time as in Comparative Example (5) in which no agent was used.

"Salt resistance test" The viscosity of an aqueous solution of the thickener (1) of the present invention in an aqueous sodium chloride solution was measured.

"Measuring method of salt resistance" 1% of the thickener (1) of the present invention was added to 1, 5 and 10% aqueous sodium chloride solution based on the total amount, and the aqueous solution viscosity was measured.

[0034]

[Table 3]

Table 3 shows that the viscosity hardly decreases even in an aqueous solution of sodium chloride, and that the thickener of the present invention is excellent in salt resistance.

[0036]

The thickener of the present invention solves the setting retardation property of the conventional thickener for concrete. Therefore, according to the thickener of the present invention, it is possible to prepare a hydraulic composition having an extremely small setting retardation property and an excellent material separation resistance, and an obstacle in construction is improved.

The thickener of the present invention has excellent salt resistance and can be applied to various uses.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁶ Identification code Agency reference number FI Technical display location C04B 103: 44

Claims (4)

[Claims] (1) The following general formula (1): A polymer derived from a monomer component having an (alkoxy) polyalkylene glycol mono (meth) acrylate-based monomer (a) as an essential component, and a 0.5% aqueous solution viscosity of the polymer Is 2 to 1000 CP. 2. A hydraulic composition comprising the thickener, water reducing agent, water and hydraulic powder according to claim 1. 3. The method according to claim 2, wherein the water reducing agent is a formaldehyde condensate of one or more compounds selected from the group consisting of methylolates and sulfonates of any of naphthalene, melamine, phenol, urea and aniline. Hydraulic composition. 4. The water reducing agent is a (co) polymer derived from one or more monomers selected from the group consisting of unsaturated monocarboxylic acids and derivatives thereof, unsaturated dicarboxylic acids and derivatives thereof. Item 3. The hydraulic composition according to Item 2.