CN112313186A - Additive for hydraulic composition - Google Patents
Additive for hydraulic composition Download PDFInfo
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- CN112313186A CN112313186A CN201880094821.2A CN201880094821A CN112313186A CN 112313186 A CN112313186 A CN 112313186A CN 201880094821 A CN201880094821 A CN 201880094821A CN 112313186 A CN112313186 A CN 112313186A
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- additive
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B24/00—Use of organic materials as active ingredients for mortars, concrete or artificial stone, e.g. plasticisers
- C04B24/12—Nitrogen containing compounds organic derivatives of hydrazine
Abstract
The additive for hydraulic compositions is composed of an organic amine salt of a fatty alcohol phosphate obtained by neutralization with a first component containing at least one or more fatty alcohol phosphates and a second component containing an organic amine.
Description
Technical Field
The present invention relates to an additive for hydraulic compositions. More specifically, the present invention relates to an additive for hydraulic compositions which has high stability of an aqueous solution thereof, is excellent in compatibility with conventional additives for hydraulic compositions, and can improve freeze-thaw resistance of hardened concrete products and the like obtained from hydraulic compositions.
Background
In recent years, hardened products (for example, hardened concrete products) obtained from hydraulic compositions are often required to have high durability. As one of the indexes indicating the high durability, "freeze-thaw resistance" is known. Accordingly, in order to improve the freeze-thaw resistance of the hardened concrete body, AE concrete obtained by mixing fine air bubbles into the hardened concrete body was produced. However, depending on various conditions such as various materials used for a concrete hardened body and a blending ratio of the various materials, even AE concrete may not have sufficient anti-freezing effectiveness. Therefore, various adjustment operations such as an increase in the amount of air and a modification of the recipe are performed according to the manufacturing conditions.
For example, in the process of manufacturing AE concrete, additives are used to adjust the amount of air. In this case, the freeze-thaw resistance of the obtained hardened concrete body differs depending on the kind of the additive used. Here, as an additive excellent in freeze-thaw resistance, the use of a phosphate-based additive as an AE regulator has been proposed (see patent documents 1 to 3).
Documents of the prior art
Patent document
Patent document 1: japanese laid-open patent publication No. 61-048480
Patent document 2: japanese patent laid-open publication No. 2010-100478
Patent document 2: japanese laid-open patent publication No. 2010-285291
Disclosure of Invention
Problems to be solved by the invention
However, in the case of the phosphate additives disclosed in the above patent documents 1 to 3, the compatibility with water or conventional additives for hydraulic compositions is not good, and as a result, there is a problem that the freeze-thaw resistance of hardened concrete or the like is not sufficient in some cases.
In view of the above-mentioned circumstances, an object of the additive for hydraulic compositions of the present invention is to provide an additive for hydraulic compositions which has high stability as an aqueous solution, is excellent in compatibility with conventional additives for hydraulic compositions, and can give a cured concrete product or the like having a good freeze-thaw resistance.
Means for solving the problems
The present inventors have conducted extensive studies to solve the above problems, and as a result, have found that an additive for hydraulic compositions containing a specific aliphatic alcohol phosphate and a specific organic amine is particularly suitable.
That is, the present invention relates to an additive for hydraulic compositions, which comprises an organic amine salt of an aliphatic alcohol phosphate obtained by neutralizing a first component comprising at least one of aliphatic alcohol phosphates represented by the following chemical formulae 1, 2 and 3 and a second component comprising an organic amine represented by the following chemical formula 4,
[ chemical formula 1]
[ chemical formula 2]
[ chemical formula 3]
Wherein, in the above chemical formulas 1 to 3, R1To R5A residue obtained by removing a hydroxyl group from an aliphatic alcohol having 6 to 24 carbon atoms or a residue obtained by adding ethylene oxide and/or propylene oxide to each mole of an aliphatic alcohol having 6 to 24 carbon atoms in a total amount of 1 to 10 moles; n represents an integer of 2 or 3; m1To M4Represents hydrogen, an alkali metal and an alkaline earth metal, and M1To M4At least one of which comprises an alkali metal or an alkaline earth metal.
[ chemical formula 4]
Wherein, in the above chemical formula 4,
R6represents an alkyl group having 1 to 30 carbon atoms and/or carbonAlkenyl of atomic number 2 to 30; AO and BO each represent an oxyalkylene group; a. b is an integer of 0 or more, and satisfies a condition of a + b ≦ 100.
Here, as described above, in the above chemical formula 1, R1The residue is the residue of an aliphatic alcohol having 6 to 24 carbon atoms after removal of a hydroxyl group, or the residue of a substance obtained by adding ethylene oxide and/or propylene oxide to each mole of an aliphatic alcohol having 6 to 24 carbon atoms in a total amount of 1 to 10 moles.
As the R1Examples thereof include: 1) a hydroxyl-removed residue of aliphatic alcohols having 6 to 24 carbon atoms such as hexanol, heptanol, octanol, 2-ethyl-hexanol, nonanol, decanol, 2-propyl-heptanol, undecanol, dodecanol, 2-butyl-octanol, tridecanol, tetradecanol, hexadecanol, octadecanol, isooctadecanol, oleyl alcohol, eicosanol, behenyl alcohol, and tetracosanol; 2) a residue obtained by removing a hydroxyl group from a substance obtained by adding ethylene oxide and/or propylene oxide to each mole of aliphatic alcohols having 6 to 24 carbon atoms such as hexanol, heptanol, octanol, 2-ethyl-hexanol, nonanol, decanol, 2-propyl-heptanol, undecanol, dodecanol, 2-butyl-octanol, tridecanol, tetradecanol, hexadecanol, octadecanol, isooctadecanol, oleyl alcohol, eicosanol, behenyl alcohol, and lignoceryl alcohol in a total amount of 1 to 10 moles. Wherein, as R1The hydroxyl group-removed residue is preferably an aliphatic alcohol having 8 to 22 carbon atoms such as octanol, 2-ethyl-hexanol, nonanol, dodecanol, 2-butyl-octanol, tridecanol, tetradecanol, hexadecanol, octadecanol, isooctadecanol, oleyl alcohol, or the like.
As the aliphatic alcohol phosphate represented by chemical formula 1, there may be mentioned: monohexyl phosphate, monooctyl phosphate, mono 2-ethyl-hexyl phosphate, monononyl phosphate, monodecanyl phosphate, mono 2-butyl-octyl phosphate, monodecanyl phosphate, monotetradecyl phosphate, monocetyl phosphate, monostearyl phosphate, monoisostearyl phosphate, monooleyl phosphate, and the like.
In chemical formula 2, R2、R3And R in chemical formula 11The description is the same. Therefore, the details are omittedAnd (4) description.
Examples of the aliphatic alcohol phosphate represented by chemical formula 2 include dioctyl phosphate, di-2-ethylhexyl phosphate, dinonyl phosphate, didecyl phosphate, didodecyl phosphate, di-2-butyloctyl phosphate, ditridecyl phosphate, ditetradecyl phosphate, dihexadecyl phosphate, dioctadecyl phosphate, diisooctadecyl phosphate, dioleyl phosphate, didecyl oleyl phosphate, and the like.
In chemical formula 3, R4、R5And R in chemical formula 11The description is the same. Therefore, detailed description is omitted. Further, n is an integer of 2 or 3.
Examples of the aliphatic alcohol phosphate represented by chemical formula 3 include monooctyl pyrophosphate, dioctyl pyrophosphate, mono-2-ethylhexyl pyrophosphate, di-2-ethylhexyl pyrophosphate, monononyl pyrophosphate, dinonyl pyrophosphate, monododecyl pyrophosphate, didodecyl pyrophosphate, monooleyl pyrophosphate, dioleyl pyrophosphate, dodecaoleyl pyrophosphate, dioleyl polyphosphate, and the like.
In chemical formula 4, R6Is an alkyl group having 1 to 30 carbon atoms and/or an alkenyl group having 2 to 30 carbon atoms. As the R6Examples thereof include: methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, eicosyl, heneicosyl, docosyl, tricosyl, tetracosyl, octadecenyl and the like. R6The amino group of the amine may be removed from the amine such as tallow amine, hydrogenated tallow amine, coconut oil amine, palm oil amine, and soybean oil amine.
R6May be composed of either a straight chain or a branched chain. R6The number of carbon atoms of (a) is 1 to 30, but most preferably 6 to 22. When R is6When the number of carbon atoms of (2) exceeds 30, the hydrophobicity of such an organic amine increases.
In chemical formula 4, AO, BO are oxyalkylene groups having 2 to 4 carbon atoms, and are preferably oxyethylene groups or oxypropylene groups, more preferably oxyethylene groups. a. b represents the number of moles of addition of the oxyalkylene group.
In chemical formula 4, a and b are integers not less than 0, and an integer satisfying a + b ≦ 100. Preferably, the integer satisfying 1 ≦ a + b ≦ 50, more preferably, the integer satisfying 2 ≦ a + b ≦ 50, particularly preferably, the integer satisfying 2 ≦ a + b ≦ 35, and most preferably, the integer satisfying 3 ≦ a + b ≦ 35.
Further, in the aliphatic alcohol phosphate of the first component, R in the above chemical formulae 1 to 31To R5An alkyl group and/or an alkenyl group having 8 to 22 carbon atoms may be used.
In addition, in the second component organic amine, R in the above chemical formula 46An alkyl group and/or an alkenyl group having 6 to 22 carbon atoms may be used.
The acid value of the aliphatic alcohol phosphate as the first component is not particularly limited, and may be, for example, in the range of 0.1mg/g to 500 mg/g. Preferably in the range of 40mg/g to 400mg/g, more preferably in the range of 100mg/g to 250 mg/g.
Here, as the acid value, for example, a mixed solution of isopropyl alcohol and xylene/isopropyl alcohol (capacity ratio 1/1), a sample dissolved in a solvent such as water, and a mixed solution of ethylene glycol/isopropyl alcohol (capacity ratio 1/1) of 0.1N potassium hydroxide are used, potentiometric titration is performed using an automatic potentiometric titrator, a titration amount (ml) at the end point of titration is measured, and the mg number of potassium hydroxide required for neutralizing the acid group of the phosphate ester contained in 1g of the sample is calculated by the following mathematical formula 1, and the obtained value is the acid value.
[ mathematical formula 1]
Acid value (KOHmg/g) ═ a1 xf 1 × 5.61)/W1
In the above-mentioned mathematical formula 1,
a1: titration amount (ml);
f 1: titer of 0.1N potassium hydroxide solution;
w1: amount of sample (g).
The amine value of the organic amine of the second component is not particularly limited, and may be, for example, in the range of 20mg/g to 200 mg/g. Preferably, it is set in the range of 30mg/g to 150mg/g, more preferably, it is set in the range of 50mg/g to 100 mg/g.
The amine value is obtained by performing potentiometric titration using an automatic potentiometric titrator using, for example, a mixed solution of isopropanol, xylene/isopropanol (capacity ratio 1/1), a sample dissolved in a solvent such as water, and a mixed solution of 0.1N hydrochloric acid and ethylene glycol/isopropanol (capacity ratio 1/1), measuring the titration amount (ml) at the end point of the titration, and calculating the mg number of potassium hydroxide equivalent to hydrochloric acid required for neutralizing the amino group of the organic amine contained in 1g of the sample by the following mathematical formula 2.
[ mathematical formula 2]
Amine number (KOHmg/g) ═ a2 xf 2 × 5.61)/W2
In the above-mentioned numerical expression 2,
a2: titration amount (ml);
f 2: titer of 0.1N potassium hydroxide solution;
w2: amount of sample (g).
Further, a value obtained by dividing the amine value of the second component by the acid value of the first component and multiplying by 100 (hereinafter referred to as "amine value/acid value × 100") may be set to be in a range of 10 to 300. Preferably, it may be set in a range of 30 to 250, and more preferably, may be set in a range of 50 to 150.
An organic amine salt of an aliphatic alcohol phosphate constituting the additive for hydraulic compositions according to the present invention is obtained by reacting, for example, phosphorus pentoxide with an aliphatic alcohol having 6 to 24 carbon atoms or with a substance obtained by adding ethylene oxide and/or propylene oxide to each mole of an aliphatic alcohol having 6 to 24 carbon atoms in a total amount of 1 to 10 moles to obtain an aliphatic alcohol phosphate, and then neutralizing the aliphatic alcohol phosphate with an alkaline component such as potassium hydroxide and an organic amine represented by chemical formula 4. The above-mentioned aliphatic alcohol phosphate is generally a compound of the aliphatic alcohol phosphate represented by chemical formula 1 and the aliphatic alcohol phosphate represented by chemical formula 2, but may be a mixture further containing the aliphatic alcohol phosphate represented by chemical formula 3 according to circumstances.
The additive for hydraulic compositions according to the present invention is used in hydraulic compositions containing a hydraulic binder in civil engineering, construction, secondary products, etc. Examples of the hydraulic composition include a slurry, a mortar, and concrete.
The additive for hydraulic compositions according to the present invention can be used together with existing additives for hydraulic compositions. Examples of such additives for hydraulic compositions include: an AE water reducing agent, a high-performance AE water reducing agent, an AE agent as an air quantity adjusting agent, an antifoaming agent, a shrinkage inhibitor, a thickener, a hardening accelerator, and the like.
Examples of the hydraulic binder used for preparing the hydraulic composition to be used as the additive for hydraulic compositions according to the present invention include various portland cements such as ordinary portland cement, early strength portland cement, and moderate heat cement; and various mixed cements such as blast furnace cement, fly ash cement, and silica cement. Further, various mixed materials such as fine blast furnace slag powder, fly ash, and silica fume may be used together with the various cements described above.
When aggregate is used for the production of the hydraulic composition, fine aggregate and coarse aggregate are exemplified as the aggregate in this case, river sand, mountain sand, sea sand, crushed sand, fine aggregate of furnace slag and the like are exemplified as the fine aggregate, and river sand stone, crushed stone, light aggregate and the like are exemplified as the coarse aggregate.
The water/binder ratio of the hydraulic composition is usually 70% or less, preferably 20 to 60%, more preferably 30 to 55%, and particularly preferably 35 to 55%. In general, if the water/binder ratio is increased, the freeze-thaw resistance of the hydraulic composition is reduced, and if it exceeds 70%, the freeze-thaw resistance is not obtained in many cases.
ADVANTAGEOUS EFFECTS OF INVENTION
According to the present invention, the following effects can be obtained: the aqueous solution itself has high stability and high solubility with conventional additives for hydraulic compositions, and as a result, the hardened product obtained has excellent freeze-thaw resistance.
Examples
Hereinafter, examples and the like are given to further illustrate the configuration and effects of the present invention, but the present invention is not limited to these examples. In the following examples and comparative examples, "part" and "%" represent "part by mass" and "% by mass", respectively, unless otherwise specified.
1. Synthesis of polycarboxylic acid water reducing agent
244.3 parts of ion-exchanged water and 368.3 parts of poly (average addition mole number of 53 moles) ethylene glycol mono (3-methyl-3-butenyl) ether were charged into a reaction vessel, and the atmosphere was replaced with nitrogen gas, and the mixture was slowly heated while stirring. While the temperature of the reaction system was kept at 70 ℃ by using a hot water bath, 23.5 parts of a 3.5% aqueous solution of hydrogen peroxide was dropped over 3 hours, and at the same time, an aqueous solution obtained by dissolving 23.5 parts of acrylic acid in 117.5 parts of ion-exchanged water was dropped over 3 hours, and at the same time, an aqueous solution obtained by dissolving 1.9g of L-ascorbic acid and 1.9g of 3-mercaptopropionic acid in 15.0 parts of ion-exchanged water was dropped over 4 hours, thereby allowing them to react. To the obtained copolymer, 45.5 parts of a 30% aqueous solution of sodium hydroxide and ion-exchanged water were added to obtain a 40% aqueous solution of a water-soluble vinyl copolymer (water reducing agent B solution). The water-soluble vinyl copolymer was analyzed, and the mass average molecular weight thereof was found to be 45000. The weight average molecular weight of the copolymer was measured by gel permeation chromatography.
2. Measurement conditions
The device comprises the following steps: shodex GPC-101 (manufactured by Showa Denko K.K.).
Column: ohapak SB-G + SB-806M HQ + SB-806M HQ (manufactured by Showa Denko K.K.).
A detector: differential Refractometer (RI).
Eluent: 50mM aqueous sodium nitrate solution.
Flow rate: 0.7 mL/min.
Column temperature: at 40 ℃.
Sample concentration: eluent solution with sample concentration of 0.5 wt%.
Standard substance: PEG/PEO (manufactured by アジレント)
3. Example 1(AE-1) (preparation of organic amine salt of aliphatic alcohol phosphate ester, etc.)
41.6 parts of 1-octanol was charged into the reaction vessel, and after dehydration treatment was carried out at 120 ℃ and 0.05MPa for 2 hours, the pressure was returned to atmospheric pressure, and 18.1 parts of phosphorus pentoxide was charged at 60. + -. 5 ℃ for 0.5 hours while stirring. After aging at 80 ℃ for 3 hours, 1.2 parts of ion-exchanged water was added thereto and the mixture was aged for 0.5 hour. 18.8 parts of a 48% aqueous potassium hydroxide solution was added dropwise thereto at 50 ℃ to carry out neutralization. The acid value was determined by potentiometric titration and was 222 mg/g. 182.4 parts by mass of a 20-mole adduct of dodecylamine-polyethylene oxide (amine value 55mg/g) was added dropwise thereto at 50 ℃ to perform neutralization, and ion-exchanged water was added to prepare a 25% aqueous solution of an additive for hydraulic compositions (example (AE-1)).
4. Examples 2 to 17(AE-2 to AE-17) and comparative example 1(RAE-1), comparative example 2(RAE-2)
As in the case of example 1, 25% aqueous solutions of examples 2 to 17((AE-2) to (AE-17)) and comparative examples 1(RAE-1) and 2(RAE-2) of the additive for hydraulic compositions were prepared.
5. Comparative example 3(RAE-3)
135.8 parts by mass of 1-octanol was charged into the reaction vessel, and after dehydration treatment was carried out at 120 ℃ and 0.05MPa for 2 hours, 59.1 parts of phosphorus pentoxide was charged at 60. + -. 5 ℃ for 0.5 hours while stirring while returning to atmospheric pressure. After aging at 80 ℃ for 3 hours, 4.1 parts of ion-exchanged water was added thereto and the mixture was aged for 0.5 hour. 153.4 parts of a 48% potassium hydroxide aqueous solution was added dropwise thereto at 50 ℃ to perform neutralization, and then ion-exchanged water was added thereto, thereby preparing a 25% aqueous solution of an additive for hydraulic compositions (comparative example 3 (RAE-3)).
6. Comparative example 4(RAE-4), comparative example 5(RAE-5)
In the same manner as in comparative example 3(RAE-3), 25% aqueous solutions of comparative example 4(RAE-4) and comparative example 5(RAE-5) were prepared, respectively.
7. Comparative example 6(RAE-6)
701.7 parts of ion-exchanged water and 76.3 parts of a 48% aqueous potassium hydroxide solution were added to the reaction vessel, followed by heating to 90 ℃. 222.0 parts of rosin (Wako pure chemical industries, Ltd.) was added thereto while stirring. After the addition, aging was performed for 1 hour to prepare a 25% aqueous solution of potassium Rosin salt (Rosin K).
The contents of the organic amine salts of aliphatic alcohol phosphoric acid esters and the like of the respective examples prepared in the above items 1.to 6 are summarized and shown in the following table 1. The P-nuclear integration ratio is determined by adding an excessive amount of KOH to an organic amine salt of an aliphatic alcohol phosphoric acid ester or the like so that the pH is 12 or more31The measured value obtained by P-NMR (trade name MERCURY plus NMR Spectrometor System, manufactured by VALIAN Co., Ltd.; 300MHz) was calculated from the following numerical expressions 3 to 5. As the solvent, a mixed solvent of heavy water/tetrahydrofuran (8/2 by volume) was used.
[ Table 1]
[ mathematical formula 3]
[ mathematical formula 4]
[ math figure 5]
Here, in the above mathematical formulae 3 to 5, "P-type 1" represents a P-nuclear NMR integrated value assigned to the organic amine salt of the aliphatic alcohol phosphate ester shown in chemical formula 1, or the like, "P-type 2" represents a P-nuclear NMR integrated value assigned to the organic amine salt of the aliphatic alcohol phosphate ester shown in chemical formula 2, or the like, and "P-type 3" represents a P-nuclear NMR integrated value assigned to the organic amine salt of the aliphatic alcohol phosphate ester shown in chemical formula 3, or the like.
In addition, in table 1 above, "formula 1" represents the P-kernel integration ratio calculated by equation 3, "formula 2" represents the P-kernel integration ratio calculated by equation 4, and "formula 3" represents the P-kernel integration ratio calculated by equation 5.
In addition, in the first component (aliphatic alcohol phosphate) of table 1, "C8" represents octanol, "C9" represents nonanol, "C12" represents dodecanol, and "C18" represents oleyl alcohol (and, in AE-13, AE-15 alone, "C18: oleyl alcohol-polyoxyethylene 4 mol adduct"); in the second component (organic amine) R6In the above formula, "C12" represents a dodecyl group, "C18" represents an octadecyl group, and "C8" represents an octyl group; further, "K" represents a potassium salt, "Na" represents a sodium salt, and "EO" represents ethylene oxide.
10. Stability of aqueous solution of additive for hydraulic composition and compatibility with Water reducing agent (conventional additive for hydraulic composition)
10-1 stability of aqueous solution of additive for Hydraulic composition
The additives for hydraulic compositions prepared in Table 1 were mixed with a 25% aqueous solution thereof thoroughly with shaking, poured into a transparent container, allowed to stand at 5 ℃ 20 ℃ and 40 ℃ for 1 week, and evaluated by visual observation for solubility according to the evaluation criteria described later. The results are summarized and shown in table 2 below.
10-2 compatibility of aqueous solution of additive for Hydraulic composition with Water reducing agent
To a polycarboxylic acid-based high-performance AE water reducing agent "CHUPOL HP-11 (liquid water reducing agent a made of bamboo oil and fat)", a water reducing agent B liquid, and an AE water reducing agent "CHUPOL EX60 (liquid water reducing agent C made of bamboo oil and fat)" which is a composite of a modified lignin sulfonic acid and a polycarboxylic acid-based compound, a 25% aqueous solution of an additive for a hydraulic composition was added, and the mixture was allowed to stand at 20 ℃ for 1 week, and the solubility was visually observed, and evaluated by the evaluation criteria described later. The results are summarized and shown in table 2 below.
10-3 evaluation criteria for stability and compatibility
A: dissolving for 1 week
B: dissolving for 1 day
C: separating within 1 day
[ Table 2]
Preparation and evaluation of AE concrete compositions
Preparation of AE concrete compositions
Under the mixing conditions shown in Table 3, a predetermined amount of ordinary portland cement (an equivalent mixture of ordinary portland cements manufactured by Taiyang cement, Mitsubishi cement of Uyu, and Sumitomo Osaka cement) was mixed at a density of 3.16g/cm3) And land sand (produced by Dajing river water with density of 2.58 g/cm)3) Crushed stone (crushed stone produced by Okazaki, density 2.66 g/cm)3) An AE concrete composition having a predetermined slump of 18 ± 1cm and a predetermined air amount of 4.5 ± 0.5% was prepared by charging 25% aqueous solution of an additive for a hydraulic composition, a 25% aqueous solution of a water reducing agent a or B, and an antifoaming agent "AFK-2 (made of bamboo fat and oil)" of 0.0005% by mass of cement into a 50L disk-forced mixer together with kneading water (tap water) and kneading for 90 seconds, and the slump, the air amount, and a freeze-thaw resistance index (300 cycles) as an index of freeze-thaw resistance were determined (described later in detail), and the results are summarized and shown in table 4. In addition, the same test was carried out according to the mixing conditions shown in table 5 for the case of using the water-reducing agent C liquid. The results are summarized and shown in table 6.
11-2. determination of air quantity, slump, and Freeze-thaw resistance index
Air amount (% by volume): the AE concrete composition immediately after kneading was measured according to JIS a 1128.
Slump (cm): the air amount was measured in accordance with JIS a 1101.
Freeze-thaw resistance index: the hardened body of the AE concrete composition prepared using a 25% aqueous solution of each example of the additive for hydraulic compositions was calculated using a value measured in accordance with JIS A1148 and using the durability index of ASTM-C666-75. The maximum value of this value is 100, and the closer to 100, the more excellent the freeze-thaw resistance.
[ Table 3]
[ Table 4]
[ Table 5]
[ Table 6]
In tables 4 and 6, the amount of the water reducing agent and the amount of the 25% aqueous solution of the additive for hydraulic compositions are shown as percentages with respect to the cement (C).
11-3 evaluation basis of freeze-thaw resistance index
The evaluation of the freeze-thaw resistance was performed based on the following evaluation criteria. That is, the case where the freeze/thaw resistance index is 80% or more is referred to as "a", and the case where the freeze/thaw resistance index is less than 80% is referred to as "B".
From the results shown in tables 2, 4 and 6, it was confirmed that the additive for hydraulic compositions of the present invention has excellent stability and good solubility (compatibility) with conventional additives for hydraulic compositions, and the obtained hardened concrete or the like has excellent freeze-thaw resistance.
Claims (6)
1. An additive for hydraulic compositions, comprising an organic amine salt of an aliphatic alcohol phosphate obtained by neutralization with a first component containing at least one or more of the aliphatic alcohol phosphates represented by the following chemical formulae 1, 2 and 3, respectively, and a second component containing an organic amine represented by the following chemical formula 4,
[ chemical formula 1]
[ chemical formula 2]
[ chemical formula 3]
Wherein R is1To R5A residue obtained by removing a hydroxyl group from an aliphatic alcohol having 6 to 24 carbon atoms or a residue obtained by adding ethylene oxide and/or propylene oxide to each mole of an aliphatic alcohol having 6 to 24 carbon atoms in a total amount of 1 to 10 moles; n represents an integer of 2 or 3; m1To M4Represents hydrogen, an alkali metal and an alkaline earth metal, and M1To M4At least one of which comprises an alkali metal or an alkaline earth metal,
[ chemical formula 4]
Wherein R is6Represents an alkyl group having 1 to 30 carbon atoms and/or an alkenyl group having 2 to 30 carbon atoms; AO and BO each represent an oxyalkylene group; a. b is an integer of 0 or more, and satisfies a condition of a + b ≦ 100.
2. The additive for hydraulic compositions according to claim 1, wherein,
in the aliphatic alcohol phosphoric acid ester of the first component,
r in the chemical formulas 1 to 31To R5Is an alkyl group and/or an alkenyl group having 8 to 22 carbon atoms.
3. The additive for hydraulic compositions according to claim 1 or 2, wherein,
in the organic amine of the second component,
r in the chemical formula 46Is an alkyl group and/or an alkenyl group having 6 to 22 carbon atoms.
4. The additive for hydraulic compositions according to any one of claims 1 to 3, wherein,
the acid value of the first component is in the range of 0.1mg/g to 500mg/g,
the amine value of the second component is in the range of 20mg/g to 200mg/g, and
the value obtained by dividing the amine value by the acid value and multiplying by 100 is in the range of 10 to 300.
5. The additive for hydraulic compositions according to claim 4, wherein the amine value is in the range of 30mg/g to 150 mg/g.
6. The additive for hydraulic compositions according to claim 4 or 5, wherein,
the value obtained by dividing the amine value by the acid value and multiplying by 100 is in the range of 50 to 150.
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Also Published As
| Publication number | Publication date |
|---|---|
| TWI748111B (en) | 2021-12-01 |
| WO2019244300A1 (en) | 2019-12-26 |
| TW202000626A (en) | 2020-01-01 |
| JP6653848B1 (en) | 2020-02-26 |
| JPWO2019244300A1 (en) | 2020-06-25 |
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