CN105884978B - It is a kind of to promote to coagulate Early-strength polycarboxylate superplasticizer and preparation method thereof - Google Patents
It is a kind of to promote to coagulate Early-strength polycarboxylate superplasticizer and preparation method thereof Download PDFInfo
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Abstract
Promote to coagulate Early-strength polycarboxylate superplasticizer and preparation method thereof the invention discloses a kind of, which is made of the raw material components of following parts by weight：1~3 parts by weight of quaternaries cation monomer, 16~18 parts by weight of 190~210 parts by weight of polyether monomer, unsaturated monocarboxylic acid and its derivative, 1.5~2.0 parts by weight of oxidant, 0.1~0.3 parts by weight of the first reducing agent, 0.1~0.3 parts by weight of the second reducing agent, 210~230 parts by weight of 0.8~0.9 parts by weight of chain-transferring agent, 14~18 parts by weight of alkaline conditioner and water with terminal double bond.The rush of the present invention, which coagulates Early-strength polycarboxylate superplasticizer, has the function of promotion hydrated reaction of cement outstanding, applied to steam-curing concrete, low temperature environment concrete and have in the concrete of form removal requirement ahead of time, plastering and the presetting period of forming panel can be significantly shorter, with significant early strong effect, also there is good thixotropic property simultaneously, the construction speed that can accelerate concrete improves the turnover rate of template.
Description
Technical field
The invention belongs to technical field of concrete additives, and in particular to it is a kind of promote coagulate Early-strength polycarboxylate superplasticizer and its
Preparation method.
Background technology
With the quickening of concrete works project construction, the dosage of precast concrete product also present it is ever-increasing become
Gesture.Compared to normal concrete, precast concrete requires concrete that there is preferable early strength to develop rate, to improve template
Turnover rate, or meet the strength development under cryogenic conditions, the production period of precast concrete is extended into even winter in late autumn, and
Also there is higher requirement to concrete durability.Realize that polycarboxylate water-reducer promotees there are two types of solidifying early powerful technological approaches：One
Kind, which is synthetic polymer itself, has the solidifying morning epistasis energy of rush well, another is the conventional polycarboxylate water-reducer of synthesis, logical
It crosses compounding and reaches the solidifying early strong effect of rush.
CN101024565A discloses a kind of by compounding the accelerating components such as anhydrous calcium chloride, triethanolamine, sodium benzoate
Whether obtained morning strong composite water-reducing agent, can be improved compression strength to a certain extent, but do not refer to having and promote to coagulate effect, and contain
Villaumite has corrosion to armored concrete；Japan Patent JP6005050 discloses a kind of using the compound of sodium carbonate and aluminum sulfate
Early strength agent, can be improved the early strength of concrete, but be easy to cause later stage degradation, and improves the alkali in concrete and contain
Amount, can accelerate alkali.In conclusion using traditional inorganic salt or organic accelerating component, it can so that water-reducing agent is in weak base
Property or strong basicity, are not only easily layered, cause water-reducing agent poor storage stability, while can make under the later strength of concrete
Drop.
CN101376576B discloses a kind of early strength type polycarboxylic acid series high-performance dehydragent and its preparation process, the technical side
Case uses the polyethylene glycol monoether esters of acrylic acid polymeric monomer, (methyl) acrylic acid, Sodium Allyl Sulfonate of two kinds of different chain numbers
Or methylpropene sodium sulfonate, the polyoxyalkylene acrylate esters monomer with defoaming function take primary throwing under the conditions of nitrogen protection
The mode of material carries out copolyreaction.CN101357834B discloses a kind of early-strength polycarboxylic acids plasticiser, and the invention is using different
Methoxy poly (ethylene glycol) carboxylic acid esters polymeric monomer, (methyl) acrylic acid, 2- acrylamide-2-methyl propane sulfonics and the nothing of molecular weight
Rule/block ether is copolymerized preparation in 60 DEG C~90 DEG C of aqueous solution.There are early strong effect unobvious in above technical solution, and
It generates early strong while sacrificing part water-reducing property, cost is led to problems such as to increase.
Invention content
It is an object of the invention to overcome prior art defect, a kind of solidifying Early-strength polycarboxylate superplasticizer of rush is provided.
Another object of the present invention is to provide the preparation methods that above-mentioned rush coagulates Early-strength polycarboxylate superplasticizer.
The specific technical solution of the present invention is as follows：
It is a kind of to promote to coagulate Early-strength polycarboxylate superplasticizer, it is made of the raw material components of following parts by weight：With terminal double bond
1~3 parts by weight of quaternaries cation monomer, 190~210 parts by weight of polyether monomer, unsaturated monocarboxylic acid and its derivative
16~18 parts by weight, 1.5~2.0 parts by weight of oxidant, 0.1~0.3 parts by weight of the first reducing agent, the second reducing agent 0.1~0.3
Parts by weight, 210~230 parts by weight of 0.8~0.9 parts by weight of chain-transferring agent, 14~18 parts by weight of alkaline conditioner and water, first also
The weight ratio of former agent and the second reducing agent is 1:1~3, wherein
Polyether monomer is the isobutene alcohol polyoxyethylene ether and/or prenol polyoxy of number-average molecular weight 3000~6000
Vinyl ethers；
Quaternaries cation monomer with terminal double bond is MethacryloyloxyethylTrimethyl Trimethyl Ammonium Chloride, acryloyl
Oxy-ethyl-trimethyl salmiac or diallyldimethylammonium chloride；
First reducing agent is 2- hydroxyl -2- sulfinatoacetic acids, 2- hydroxyl -2- sulfinatoacetic acids disodium salt, 2- hydroxyls -
2- sulfonatoacetic acids or 2- hydroxyl -2- sulfonatoacetic acid disodium salts；
Second reducing agent is two isobutyl imidazoline hydrochloride of azo, azo diisobutyl amidine hydrochloride, two N- hydroxyls of azo
Isobutyl amidine hydrate, azo two N, N ' cyclobutyl isobutyl amidine hydrate or azo dimethyl N-2- hydroxyl butylacrylamides.
In a preferred embodiment of the invention, the unsaturated monocarboxylic acid and its derivative are acrylic acid, first
Base acrylic acid, hydroxy-ethyl acrylate, hydroxyethyl methacrylate, hydroxypropyl acrylate, hydroxy propyl methacrylate, acrylic acid first
At least one of ester, methyl methacrylate, acrylamide and Methacrylamide.
In a preferred embodiment of the invention, the oxidant be ammonium persulfate, potassium peroxydisulfate, sodium peroxydisulfate or
Hydrogen peroxide.
In a preferred embodiment of the invention, the chain-transferring agent is thioacetic acid, thioglycerin, 3- mercaptopropionic acids
Different monooctyl ester, lauryl mercaptan, 3- mercaptopropionic acids or thiomalic acid.
In a preferred embodiment of the invention, the alkaline conditioner is that sodium hydroxide solution, potassium hydroxide are molten
Liquid, ethanol amine, diethanol amine, triethanolamine, isopropanolamine, diisopropanolamine (DIPA), triisopropanolamine, dihydroxy ethyl ethylenediamine, two
At least one of hydroxypropylethylendiamine diamine, tetrahydroxyethyl-ethylene diamine and tetrahydroxypropyl ethylenediamine.
It is further preferred that its pH value is 6~7.
A kind of above-mentioned rush coagulates the preparation method of Early-strength polycarboxylate superplasticizer, includes the following steps：
(1) by quaternaries cation monomer, polyether monomer, oxidant and 148~160 parts by weight with terminal double bond
Water mixes, then adjusts pH to 4~6 with part unsaturated monocarboxylic acid, in 15~30 DEG C of stirrings to dissolving；
(2) the first reducing agent, the second reducing agent, chain-transferring agent and remaining unsaturated monocarboxylic acid are divided with remaining water
It is not configured to reducing agent solution, chain-transferring agent solution and unsaturated monocarboxylic acid solution；
(3) above-mentioned reducing agent solution, chain-transferring agent solution and unsaturated monocarboxylic acid solution are added dropwise in 3~4h simultaneously
Into the material of step (1), after being added dropwise at 35~40 DEG C 1~1.5h of insulation reaction；
(4) it after the material reaction of step (3) is complete, is added in alkaline conditioner and pH to 6~7 promotees to coagulate early to get described
Strong type polycarboxylate water-reducer.
The beneficial effects of the invention are as follows：
1, rush of the invention, which coagulates Early-strength polycarboxylate superplasticizer, has the function of promotion hydrated reaction of cement outstanding, applies
In steam-curing concrete, low temperature environment concrete and have in the concrete of form removal requirement ahead of time, forming panel can be significantly shorter
Plastering and presetting period have significant early strong effect, while also having good thixotropic property, can accelerate the construction of concrete
Progress improves the turnover rate of template.
2, the preparation method of the solidifying Early-strength polycarboxylate superplasticizer of rush of the invention is by molecule tailoring technology, to master, side chain
Group etc. point minor structure is designed, and part unsaturated monocarboxylic acid is added in reacting bottom material, and the pH value adjusted in bottom material is in
Faintly acid, and Raolical polymerizable is caused using the higher combined oxidation reduction initiating system of activity, it overcomes previous early strong
Type water-reducing agent water-reducing rate is high, slump-retaining bad disadvantage, has dispersion performance outstanding.
3, the preparation method of the solidifying Early-strength polycarboxylate superplasticizer of rush of the invention carries out under normal pressure and temperature completely, operation letter
It is single, it is with short production cycle, it is of low cost.
Specific implementation mode
Technical scheme of the present invention is further detailed and is described below by way of specific implementation mode.
Embodiment 1
Equipped with thermometer, blender, peristaltic pump four-hole boiling flask in 1.5 parts by weight methylacryoyloxyethyls three are added
Ammonio methacrylate, 200 parts by weight of isobutylene alcohol polyoxyethylene ether polymeric monomers (molecular weight Mw is 3000), 1.5 parts by weight persulfuric acid
Ammonium and 156 parts by weight water add 7 parts by weight of acrylic acid, and it is 4~5 to adjust bottom material pH value, is stirred at 20 DEG C.After to be dissolved,
By 0.15 parts by weight 2- hydroxyl -2- sulfinatoacetic acids, 0.15 parts by weight azo, two isobutyl imidazoline hydrochloride and 25 parts by weight
Water be made into reducing agent solution, 0.8 parts by weight thioacetic acid and 25 parts by weight water the chain-transferring agent solution and 10 weights that are made into
The unsaturated monocarboxylic acid solution that the water of the acrylic acid and 15 parts by weight of measuring part is made into, while above-mentioned reducing agent solution, chain is added dropwise
Shift agent solution and unsaturated monocarboxylic acid solution, time for adding is 3 hours, after completion of dropwise addition at 35~40 DEG C insulation reaction
1 hour.After the completion of reaction, it is neutralized to pH value 6~7 with 16 parts by weight, 32% sodium hydroxide, promotees to coagulate early-strength to obtain
Polycarboxylate water-reducer PCE-1.
Embodiment 2
Equipped with thermometer, blender, peristaltic pump four-hole boiling flask in 2 parts by weight propylene acyloxyethyl trimethyl chlorine are added
Change ammonium, 200 parts by weight of isobutylene alcohol polyoxyethylene ether polymeric monomers (molecular weight Mw is 4000), 1.6 parts by weight sodium peroxydisulfates and 158
Parts by weight water adds 6 weight parts of methacrylic acid, and it is 4~5 to adjust bottom material pH value, is stirred at 25 DEG C.It, will after to be dissolved
0.25 parts by weight 2- hydroxyl -2- sulfinatoacetic acids disodium salt, 0.30 parts by weight azo diisobutyl amidine hydrochloride and 25 weight
The chain-transferring agent solution and 10 that the water of reducing agent solution, 0.9 parts by weight 3- mercaptopropionic acids, 25 parts by weight that the water of part is made into is made into
The unsaturated monocarboxylic acid solution that the methacrylic acid of parts by weight and the water of 15 parts by weight are made into, while it is molten that above-mentioned reducing agent is added dropwise
Liquid, chain-transferring agent solution and unsaturated monocarboxylic acid solution, time for adding are 3 hours, are protected at 35~40 DEG C after completion of dropwise addition
Temperature reaction 1 hour.After the completion of reaction, it is neutralized to pH value 6~7 with 15 parts by weight triethanolamines, it is poly- to obtain the solidifying early-strength of rush
Carboxylic acid water reducer PCE-2.
Embodiment 3
Equipped with thermometer, blender, peristaltic pump four-hole boiling flask in 3 parts by weight diallyidimethylammonium chlorides are added
Ammonium, 200 parts by weight of isobutylene alcohol polyoxyethylene ether polymeric monomers (molecular weight Mw is 5000), 1.9 parts by weight potassium peroxydisulfates and 158 weights
Part water is measured, 5 parts by weight of acrylic acid hydroxyl ethyl esters are added, it is 5~6 to adjust bottom material pH value, is stirred at 30 DEG C.It, will after to be dissolved
0.18 parts by weight 2- hydroxyl -2- sulfonatoacetic acids, 0.2 parts by weight azo, two N- hydroxyisobutyl amidine hydrates and 25 parts by weight
The chain-transferring agent solution and 12 parts by weight that the water of reducing agent solution, 0.8 parts by weight thioglycerin and 25 parts by weight that water is made into is made into
Hydroxy-ethyl acrylate and 15 parts by weight the unsaturated monocarboxylic acid solution that is made into of water, while be added dropwise above-mentioned reducing agent solution,
Chain-transferring agent solution and unsaturated monocarboxylic acid solution, time for adding are 3 hours, are kept the temperature instead at 35~40 DEG C after completion of dropwise addition
It answers 1 hour.After the completion of reaction, after being cooled to 30 DEG C, it is neutralized to pH value 6~7 with 18 parts by weight ethylenediamines, promotees to coagulate early to obtain
Strong type polycarboxylate water-reducer PCE-3.
Embodiment 4
Equipped with thermometer, blender, peristaltic pump four-hole boiling flask in 1 parts by weight methylacryoyloxyethyl front three is added
Ammonium chloride, 200 parts by weight of isobutylene alcohol polyoxyethylene ether polymeric monomers (molecular weight Mw be 6000), 1.5 parts by weight hydrogen peroxide and
149 parts by weight water add 7 parts by weight of acrylic acid methyl esters, and it is 4~5 to adjust bottom material pH value, is stirred at 15 DEG C.After to be dissolved,
By 0.13 parts by weight 2- hydroxyl -2- sulfonatoacetic acids disodium salt, azo two N, N ' the cyclobutyl isobutyl amidine water of 0.25 parts by weight
Reducing agent solution, 0.8 parts by weight 3- isooctyl mercaptopropionates and the water of 25 parts by weight that conjunction object and the water of 25 parts by weight are made into are matched
At the unsaturated monocarboxylic acid solution that is made into of chain-transferring agent solution and the methyl acrylate of 10 parts by weight and the water of 15 parts by weight,
Above-mentioned reducing agent solution, chain-transferring agent solution and unsaturated monocarboxylic acid solution are added dropwise simultaneously, time for adding is 3 hours, is added dropwise
After keep the temperature 1 hour at 35~40 DEG C.After the completion of reaction, it is neutralized to pH value 6~7 with 14 parts by weight of isopropyl alcohol amine, to
It obtains and promotees to coagulate Early-strength polycarboxylate superplasticizer PCE-4.
Embodiment 5
The above-mentioned rush that the embodiment of the present invention 1 to 4 provides coagulates Early-strength polycarboxylate superplasticizer according to GB/T8077-2012
《Methods for testing uniformity of concrete admixture》Defined relevant criterion carries out paste flowing degree test, and cement is Fujian good fortune cement
42.5R, comparative sample are certain external Products, code name PCE-0, and testing result is as shown in the table：
Concrete mix is cement：Flyash:Miberal powder:Sand:Stone=330:70:40:698:1126.Wherein：Cement is
Fujian good fortune P.O42.5R, flyash are II grade of ash, and sand is the middle sand of fineness modulus 2.7, and stone is that 5~20 continuous grading of grain size is broken
Stone matches as parts by weight；Go out the machine slump in 70 ± 20mm, design strength C50；With reference to GB8076-2008《Concrete is additional
Agent》Relevant regulations test mobility and the setting time of concrete.Test result see the table below shown：
Skilled person will appreciate that when component and technical parameter of the invention changes in following ranges, it still is able to
To same as the previously described embodiments or similar technique effect：
A kind of to promote to coagulate Early-strength polycarboxylate superplasticizer, pH value is 6~7, is made of the raw material components of following parts by weight：Have
1~3 parts by weight of quaternaries cation monomer of terminal double bond, 190~210 parts by weight of polyether monomer, unsaturated monocarboxylic acid
And its 16~18 parts by weight of derivative, 1.5~2.0 parts by weight of oxidant, 0.1~0.3 parts by weight of the first reducing agent, the second reduction
0.1~0.3 parts by weight of agent, 210~230 weight of 0.8~0.9 parts by weight of chain-transferring agent, 14~18 parts by weight of alkaline conditioner and water
The weight ratio of amount part, the first reducing agent and the second reducing agent is 1:1~3, wherein
Polyether monomer is the isobutene alcohol polyoxyethylene ether and/or prenol polyoxy of number-average molecular weight 3000~6000
Vinyl ethers；
Quaternaries cation monomer with terminal double bond is MethacryloyloxyethylTrimethyl Trimethyl Ammonium Chloride, acryloyl
Oxy-ethyl-trimethyl salmiac or diallyldimethylammonium chloride；
First reducing agent is 2- hydroxyl -2- sulfinatoacetic acids, 2- hydroxyl -2- sulfinatoacetic acids disodium salt, 2- hydroxyls -
2- sulfonatoacetic acids or 2- hydroxyl -2- sulfonatoacetic acid disodium salts；
Second reducing agent is two isobutyl imidazoline hydrochloride of azo, azo diisobutyl amidine hydrochloride, two N- hydroxyls of azo
Isobutyl amidine hydrate, azo two N, N ' cyclobutyl isobutyl amidine hydrate or azo dimethyl N-2- hydroxyl butylacrylamides；
Unsaturated monocarboxylic acid and its derivative are acrylic acid, methacrylic acid, hydroxy-ethyl acrylate, hydroxyethyl methacrylate, third
Olefin(e) acid hydroxypropyl acrylate, hydroxy propyl methacrylate, methyl acrylate, methyl methacrylate, acrylamide and Methacrylamide
At least one of.
Oxidant is ammonium persulfate, potassium peroxydisulfate, sodium peroxydisulfate or hydrogen peroxide.
Chain-transferring agent be thioacetic acid, thioglycerin, 3- isooctyl mercaptopropionates, lauryl mercaptan, 3- mercaptopropionic acids or
Thiomalic acid.
Alkaline conditioner is sodium hydroxide solution, potassium hydroxide solution, ethanol amine, diethanol amine, triethanolamine, isopropanol
Amine, diisopropanolamine (DIPA), triisopropanolamine, dihydroxy ethyl ethylenediamine, dihydroxypropyl ethylenediamine, tetrahydroxyethyl-ethylene diamine and four hydroxypropyls
At least one of base ethylenediamine.
A kind of above-mentioned rush coagulates the preparation method of Early-strength polycarboxylate superplasticizer, includes the following steps：
(1) by quaternaries cation monomer, polyether monomer, oxidant and 148~160 parts by weight with terminal double bond
Water mixes, then adjusts pH to 4~6 with part unsaturated monocarboxylic acid, in 15~30 DEG C of stirrings to dissolving；
(2) the first reducing agent, the second reducing agent, chain-transferring agent and remaining unsaturated monocarboxylic acid are divided with remaining water
It is not configured to reducing agent solution, chain-transferring agent solution and unsaturated monocarboxylic acid solution；
(3) above-mentioned reducing agent solution, chain-transferring agent solution and unsaturated monocarboxylic acid solution are added dropwise in 3~4h simultaneously
Into the material of step (1), after being added dropwise at 35~40 DEG C 1~1.5h of insulation reaction；
(4) it after the material reaction of step (3) is complete, is added in alkaline conditioner and pH to 6~7 promotees to coagulate early to get described
Strong type polycarboxylate water-reducer.
The foregoing is only a preferred embodiment of the present invention, therefore cannot limit the scope of implementation of the present invention according to this, i.e.,
According to equivalent changes and modifications made by the scope of the claims of the present invention and description, all should still belong in the range of the present invention covers.
Claims (6)
1. a kind of promote to coagulate Early-strength polycarboxylate superplasticizer, it is characterised in that：It is made of the raw material components of following parts by weight：With end
1~3 parts by weight of quaternaries cation monomer of terminal double bond, 190~210 parts by weight of polyether monomer, unsaturated monocarboxylic acid and
Its 16~18 parts by weight of derivative, 1.5~2.0 parts by weight of oxidant, 0.1~0.3 parts by weight of the first reducing agent, the second reducing agent
0.1~0.3 parts by weight, 210~230 weight of 0.8~0.9 parts by weight of chain-transferring agent, 14~18 parts by weight of alkaline conditioner and water
Part, the weight ratio of the first reducing agent and the second reducing agent is 1: 1~3, wherein
Polyether monomer is the isobutene alcohol polyoxyethylene ether and/or prenol polyoxyethylene of number-average molecular weight 3000~6000
Base ether；
Quaternaries cation monomer with terminal double bond is MethacryloyloxyethylTrimethyl Trimethyl Ammonium Chloride, acryloyl-oxy second
Base trimethyl ammonium chloride or diallyldimethylammonium chloride；
First reducing agent is 2- hydroxyl -2- sulfinatoacetic acids, 2- hydroxyl -2- sulfinatoacetic acids disodium salt, 2- hydroxyl -2- sulphurs
Acidic group acetic acid or 2- hydroxyl -2- sulfonatoacetic acid disodium salts；
Second reducing agent is two isobutyl imidazoline hydrochloride of azo, azo diisobutyl amidine hydrochloride, two N- hydroxy-isobutyrics of azo
Base amidine hydrate, azo two N, N ' cyclobutyl isobutyl amidine hydrate or azo dimethyl N-2- hydroxyl butylacrylamides；
Preparation method includes the following steps：
(1) quaternaries cation monomer, polyether monomer, oxidant and 148~160 parts by weight water with terminal double bond are mixed
It closes, then pH to 4~6 is adjusted with part unsaturated monocarboxylic acid, in 15~30 DEG C of stirrings to dissolving；
(2) the first reducing agent, the second reducing agent, chain-transferring agent and remaining unsaturated monocarboxylic acid are matched respectively with remaining water
Reducing agent solution, chain-transferring agent solution and unsaturated monocarboxylic acid solution is made；
(3) above-mentioned reducing agent solution, chain-transferring agent solution and unsaturated monocarboxylic acid solution are added dropwise to step in 3~4h simultaneously
Suddenly in the material of (1), after being added dropwise at 35~40 DEG C 1~1.5h of insulation reaction；
(4) it after the material reaction of step (3) is complete, is added in alkaline conditioner and pH to 6~7 promotees to coagulate early-strength to get described
Polycarboxylate water-reducer.
2. a kind of rush as described in claim 1 coagulates Early-strength polycarboxylate superplasticizer, it is characterised in that：The unsaturation unitary carboxylic
Acid and its derivative are acrylic acid, methacrylic acid, hydroxy-ethyl acrylate, hydroxyethyl methacrylate, hydroxypropyl acrylate, first
At least one of base hydroxypropyl acrylate, methyl acrylate, methyl methacrylate, acrylamide and Methacrylamide.
3. a kind of rush as described in claim 1 coagulates Early-strength polycarboxylate superplasticizer, it is characterised in that：The oxidant is over cure
Sour ammonium, potassium peroxydisulfate, sodium peroxydisulfate or hydrogen peroxide.
4. a kind of rush as described in claim 1 coagulates Early-strength polycarboxylate superplasticizer, it is characterised in that：The chain-transferring agent is mercapto
Guanidine-acetic acid, thioglycerin, 3- isooctyl mercaptopropionates, lauryl mercaptan, 3- mercaptopropionic acids or thiomalic acid.
5. a kind of rush as described in claim 1 coagulates Early-strength polycarboxylate superplasticizer, it is characterised in that：The alkaline conditioner is
Sodium hydroxide solution, potassium hydroxide solution, ethanol amine, diethanol amine, triethanolamine, isopropanolamine, diisopropanolamine (DIPA), three isopropyls
At least one in hydramine, dihydroxy ethyl ethylenediamine, dihydroxypropyl ethylenediamine, tetrahydroxyethyl-ethylene diamine and tetrahydroxypropyl ethylenediamine
Kind.
6. the rush as described in any claim in claim 1 to 5 coagulates Early-strength polycarboxylate superplasticizer, it is characterised in that：Its
PH value is 6~7.
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| US6869998B2 (en) * | 2003-06-23 | 2005-03-22 | Geo Specialty Chemicals, Inc. | Concrete or cement dispersant and method of use |
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| CN1777565A (en) * | 2004-06-25 | 2006-05-24 | 日本西卡株式会社 | Cement dispersing agent and concrete composition comprising same |
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