TW202037635A - Defoaming agent for hydraulic composition, and hydraulic composition - Google Patents

Abstract

Through the present invention, it is possible to provide a defoaming agent for a hydraulic composition, having high compatibility with an admixture as well as excellent defoaming ability and foam stability, and a hydraulic composition. The present invention provides a defoaming agent for a hydraulic composition, the defoaming agent containing a specific nitrogen-containing polyoxyalkylene compound.

Description

Defoamer for hydraulic composition and hydraulic composition

The present invention relates to a defoamer for hydraulic composition and a hydraulic composition containing the defoamer. In detail, the present invention relates to a defoamer for a hydraulic composition with high compatibility with blends, excellent defoaming properties and foam stability, and a hydraulic composition containing the defoamer.

The hydraulic composition represented by concrete is manufactured by mixing cement, water, fine aggregates, coarse aggregates, and admixtures. The blends used include lignosulfonic acid (salt), hydroxycarboxylic acid (salt), naphthalenesulfonic acid-formaldehyde condensate (salt), melamine sulfonic acid formaldehyde condensate (salt), polycarboxylic acid compounds, etc. In addition to the water-reducing ingredients, in order to reduce the rough air in the hydraulic composition caused by the entrainment of mixing and stirring, or to adjust the amount of air to an appropriate range, defoamers are often used. As the above-mentioned defoaming agent, alkylene oxides, silicons, alcohols, mineral oils, fatty acids or fatty acid esters are known.

In order to achieve the goal of maintaining a uniform aqueous solution even with a defoamer, there have been proposed additives made of a mixture of polycarboxylic acid compounds and specific nitrogen-containing polyoxyalkylene compounds (Patent Document 1), or specific Polyoxyalkylene compounds (Patent Documents 2 to 6) are used to form cured products with excellent strength and durability.

[Prior Technical Literature]

Patent literature

Patent Document 1: Japanese Patent Publication No. 7-232945

Patent Document 2: Japanese Patent Publication No. 10-226550

Patent Document 3: Japanese Invention Publication No. 2003-226565

Patent Document 4: Japanese Invention Publication No. 2003-226566

Patent Document 5: Japanese Invention Publication No. 2003-226567

Patent Document 6: Japanese Invention Publication No. 2003-300766

However, defoamers with high defoaming properties are usually highly hydrophobic. When combined with a blend, due to the difference in density, the defoamer will separate to the upper part of the blend over time, and the derivation is difficult to control The problem of the stability of the air volume of the hydraulic composition. Although the defoamers shown in Patent Documents 1 to 6 seem to improve the compatibility with the blend, there is a problem that they cannot have both excellent defoaming properties and foam stability at the same time.

In view of the above situation, the problem to be solved by the present invention is to provide a defoaming agent for hydraulic compositions that has high compatibility with blends, excellent defoaming properties, and excellent foam stability, and contains The hydraulic composition of the defoamer.

As a result of intensive research in order to solve the above-mentioned problems, the inventors have found that a defoamer for hydraulic compositions in which polyoxyalkylene is added to a specific alkylamine in a specific ratio is particularly suitable. According to the present invention, the following antifoaming agent for hydraulic composition and hydraulic composition containing the antifoaming agent are provided.

[1] A defoamer for a hydraulic composition containing a nitrogen-containing polyoxyalkylene compound represented by the following general formula (1).

However, R ¹ in the formula represents an alkyl or alkenyl group with 10 to 24 carbons, R ² and R ³ are the same or different, and represent a hydrogen atom and/or a hydrocarbon group with 1 to 10 carbons, A ¹ O and A ² O is the same or different and represents an oxyalkylene group with 2 to 4 carbon atoms, m and n are the same or different, an integer from 0 to 100, and satisfies the condition of 20≦m+n≦100, A ¹ O And in A ² O, the oxyalkylene group with carbon number 3 and/or 4 accounts for more than 65 mol%.

[2] The defoamer for hydraulic compositions according to the above [1], wherein among the A ¹ O and the A ² O, oxyalkylene groups having 3 and/or 4 carbon atoms occupy 86 moles Ear% or more.

[3] The defoamer for hydraulic compositions as described in [1] above, wherein among the A ¹ O and the A ² O, oxyalkylene groups having 3 and/or 4 carbon atoms occupy 90 moles Ear% or more.

[4] The defoamer for a hydraulic composition according to any one of the above [1] to [3], wherein the m and the n are the same or different, and are an integer of 0 to 80, and Satisfy the condition of 30≦m+n≦80.

[5] The defoamer for hydraulic compositions according to any one of [1] to [3], wherein the m and the n are the same or different, and are an integer of 0 to 80, And meet the condition of 35≦m+n≦80.

[6] The defoamer for a hydraulic composition as described in any one of [1] to [5], wherein the R ² and R ³ represent a hydrogen atom.

[7] The defoamer for a hydraulic composition according to any one of [1] to [6], wherein the R ¹ represents an alkyl or alkenyl group having 14 to 18 carbon atoms.

[8] The defoamer for hydraulic compositions according to any one of [1] to [7], wherein the A ¹ O and the A ² O are the same or different, and have a carbon number of 2 and /Or 3 oxyalkylene groups (However, at least one of A ¹ O and A ² O contains an oxyalkylene group having 3 carbon atoms).

[9] A hydraulic composition comprising the defoamer for a hydraulic composition as described in any one of [1] to [8].

[10] The hydraulic composition as described in [9], which has a pH of 8 or less.

The defoaming agent for hydraulic composition of the present invention can achieve the effects of high compatibility with blends, superior defoaming properties and superior foam stability.

Hereinafter, the embodiments of the present invention will be described. However, the present invention does not Limited to the following implementation aspects. Therefore, it should be understood that within the scope not departing from the spirit of the present invention, those skilled in the art can appropriately change or improve the following embodiments based on general knowledge. In the following examples, unless otherwise specified,% represents mass %, and parts represent parts by mass.

The defoamer for hydraulic compositions of the present invention is a nitrogen-containing polyoxyalkylene compound represented by the following general formula (1).

R ¹ in the general formula (1) is an alkyl group having 10 to 24 carbons or an alkenyl group having 10 to 20 carbons, and may have a linear or branched structure. Although not particularly limited, it can be derived from, for example, petroleum raw materials, vegetable oils such as palm oil or sunflower oil, or animal oils such as butter.

As an alkyl group with 10 to 24 carbon atoms, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, and heptadecyl can be cited Alkyl, octadecyl, nonadecyl, eicosyl, behenyl, behenyl, tricosyl or tetracosyl, etc. Among them, as the aforementioned alkyl group, an alkyl group having 14 to 18 carbon atoms such as a tetradecyl group, a pentadecyl group, a hexadecyl group, an isohexadecyl group, a heptadecyl group, or an octadecyl group is preferable. However, compounds where R ¹ is an alkyl group with less than 10 carbons have low defoaming properties or foam stability, while compounds where R ¹ is an alkyl group with more than 24 carbons have high hydrophobicity and are compatible with the blend. Low sex.

Examples of alkenyl groups with 10 to 24 carbon atoms include decenyl, undecenyl, dodecenyl, tridecenyl, tetradecenyl, pentadecenyl, hexadecenyl, and heptadecenyl. , Octadecenyl, undecenyl, eicosenyl, eicosyl, icosadienyl, icostrienyl or icostetraenyl, etc. Among them, as the aforementioned alkenyl group, an alkenyl group having 14 to 18 carbon atoms such as tetradecenyl, pentadecenyl, hexadecenyl, heptadecenyl, or octadecenyl is preferred. However, the compound in which R ¹ is an alkenyl group with less than 10 carbons has low defoaming properties or foam stability, while the compound in which R ¹ is an alkenyl group with more than 24 carbons has high hydrophobicity and is compatible with the blend. Low capacity.

R ² and R ³ in the general formula (1) are the same or different, and are a hydrogen atom and/or a hydrocarbon group having 1 to 10 carbon atoms.

As a C1-C10 hydrocarbon group, it may have a straight-chain or branched structure, and may also be a saturated hydrocarbon group or an unsaturated hydrocarbon group. Examples of the hydrocarbon group having 1 to 10 carbons include an alkyl group having 1 to 10 carbons or an alkenyl group having 2 to 10 carbons. Examples of alkyl groups having 1 to 10 carbon atoms include methyl, ethyl, propyl, isopropyl, butyl, pentyl, hexyl, heptyl, octyl, isooctyl, nonyl or decyl. Wait. Among them, as the alkyl group of the term, an alkyl group having 1 to 3 carbon atoms such as a methyl group, an ethyl group, or a propyl group is preferable. However, compounds in which R ² and R ³ are alkyl groups with a carbon number exceeding 10 have high hydrophobicity and low compatibility with the blend. In addition, examples of alkenyl groups having 2 to 10 carbon atoms include vinyl, propenyl, butenyl, pentenyl, hexenyl, heptenyl, octenyl, nonenyl, or decenyl. Wait. Among them, as the above-mentioned alkenyl group, alkenyl groups having 2 and 3 carbon atoms such as vinyl and propenyl are preferred. However, compounds in which R ² and R ³ are alkenyl groups with a carbon number exceeding 10 have high hydrophobicity and low compatibility with the blend.

R ² and R ³ in the general formula (1) are preferably hydrogen atoms.

In the general formula (1), A ¹ O and A ² O are the same or different, and are oxyalkylene groups having 2 to 4 carbon atoms, and examples thereof include oxyethylene, oxypropylene, or oxybutenyl. Examples of the oxypropylene group include 1,2-oxypropylene group and 1,3-oxypropylene group. As an oxbutenyl group, examples include 1,2-oxobutenyl, 1,3-oxobutenyl, 1,4-oxobutenyl, 2,3-oxobutenyl, oxyisobutenyl, etc. . A ¹ O and A ² O are the same or different, and are oxyalkylene groups having 2 and/or 3 carbon atoms. However, at this time, at least one of A ¹ O and A ² O contains an oxyalkylene group having 3 carbon atoms. As the oxyalkylene group described above, an oxyethylene group and an oxypropylene group are preferable. When A ¹ O and A ² O are two or more types, they can also be random adducts, block adducts or alternative adducts.

In the general formula (1), m represents the number of added moles of A ¹ O, and n represents the number of added moles of A ² O. m and n are the same or different, and are an integer of 0-100, and preferably an integer of 0-80. At the same time, m and n are integers satisfying the condition of 20≦m+n≦100, and are preferably integers satisfying the condition of 30≦m+n≦80, and more preferably satisfying the condition of 35≦m+n≦80 The integer. When the total of m and n is less than 20, the defoaming property is insufficient and the foam stability is also low. When the total exceeds 100, it is difficult to manufacture due to high viscosity, and the compatibility with the blend is also insufficient.

In addition, in order to obtain excellent defoaming properties, in the general formula (1), among A ¹ O and A ² O, oxyalkylene groups having 3 and/or 4 carbon atoms account for 65 mol% or more, preferably 86 mol%. Ear% or more, more preferably 90 mole% or more. Among A ¹ O and A ² O, when the oxyalkylene group with carbon number 3 and/or 4 is less than 65 mol%, the water solubility is too improved, sufficient defoaming properties cannot be obtained, and foam stability is also reduced.

The actual specific examples of the nitrogen-containing polyoxyalkylene compound represented by the general formula (1) described above include decylamine-(poly)oxyethylene/polyoxypropylene adduct, undecylamine-(poly)oxy Ethylene/polyoxypropylene adduct, dodecylamine-(poly)oxyethylene/polyoxypropylene adduct, tridecylamine-(poly)oxyethylene/polyoxypropylene adduct, tetradecane Base amine-(poly)oxyethylene/polyoxypropylene adduct, pentadecylamine-(poly)oxyethylene/polyoxypropylene adduct, cetylamine-(poly)oxyethylene/polyoxypropylene adduct Compound, 2-hexyldecylamine-(poly)oxyethylene/polyoxypropylene adduct, heptadecylamine-(poly)oxyethylene polyoxypropylene adduct, stearylamine-(poly)oxy Ethylene polyoxypropylene adduct, nonadecylamine-(poly)oxyethylene/polyoxypropylene adduct, eicosanamine-(poly)oxyethylene-polyoxypropylene adduct, behenylamine Amine-(poly)oxyethylene-polyoxypropylene adduct, behenylamine-(poly)oxyethylene/polyoxypropylene adduct, trichloroamine-(poly)oxyethylene/polyoxypropylene adduct Compounds, tetracyclic amine-(poly)oxyethylene/polyoxypropylene adduct, decenamine-(poly)oxyethylene/polyoxypropylene adduct, undecenylamine-(poly)oxyethylene/polyoxy Propylene adduct, dodecenylamine-(poly)oxyethylene/polyoxypropylene adduct, tridecenylamine-(poly)oxyethylene/polyoxypropylene adduct, tetradecenylamine-( Poly)oxyethylene/polyoxypropylene adduct, pentadecenylamine-(poly)oxyethylene/polyoxypropylene adduct, hexadecenylamine-(poly)oxyethylene polyoxypropylene adduct, Heptadecenylamine-(poly)oxyethylene polyoxypropylene adduct, octadecenylamine-(poly)oxyethylene polyoxypropylene adduct, nonadecanylamine-(poly)oxyethylene/polyoxy Propylene adduct, eicosenylamine-(poly)oxyethylene/polyoxypropylene adduct, eicosenylamine-(poly)oxyethylene/polyoxypropylene adduct, docodienylamine -(Poly)oxyethylene/polyoxypropylene adduct, tricyclic amine-(poly)oxyethylene/polyoxypropylene adduct, tetramethylamine-(poly)oxyethylene/polyoxypropylene adduct, Tallow amine-(poly)oxyethylene polyoxypropylene adduct, pickled tallow amine-(poly)oxyethylene polyoxypropylene adduct, tetradecylamine-polyoxypropylene adduct, pentadecylamine -Polyoxypropylene adduct, hexadecylamine-polyoxypropylene adduct, 2-hexyldecylamine-polyoxypropylene adduct, heptadecylamine-polyoxypropylene adduct, octadecane Amine-polyoxypropylene adduct, tetradecenylamine-polyoxypropylene adduct, pentadecenylamine-polyoxypropylene adduct, hexadecenylamine-polyoxypropylene adduct, ten Heptaenylamine-polyoxypropylene adduct, octadecenylamine-polyoxypropylene adduct, tallow amine-polyoxypropylene adduct, cured tallow amine-polyoxypropylene adduct, fourteen Alkylamine-(poly)oxyethylene (poly)oxypropylene (poly)oxybutylene adduct, pentadecylamine-(poly)oxyethylene (poly)oxypropylene (poly)oxybutylene adduct, Cetylamine-(poly)oxyethylene (poly)oxypropylene (poly)oxybutylene adduct, 2-hexyldecylamine-(poly)oxyethylene (poly)oxypropylene (poly)oxybutylene adduct Compounds, heptadecylamine-(poly)oxyethylene (poly)oxypropylene (poly)oxybutene adduct, stearylamine-(poly)oxyethylene (poly)oxypropylene (poly)oxybutene Adduct, tetradecenylamine-(poly)oxyethylene (poly)oxypropylene (poly)oxybutene adduct, pentadecenylamine-(poly)oxyethylene (poly)oxypropylene (poly)oxy Butene adduct, hexadecenylamine-(poly)oxyethylene (poly)oxypropylene (poly)oxybutene adduct, heptatenylamine-(poly)oxyethylene (poly)oxypropylene (poly) ) Oxybutene adduct, octadecenylamine-(poly)oxyethylene (poly)oxypropylene (poly)oxybutene adduct, tallow amine (poly)oxyethylene (poly)oxypropylene (poly)oxy Butene adducts, cured tallow amine-(poly)oxyethylene (poly)oxypropylene (poly)oxybutylene adducts, etc. Among them, tetradecylamine-(poly)oxyethylene/polyoxypropylene adduct, pentadecylamine-(poly)oxyethylene/polyoxypropylene adduct, hexadecylamine-(poly) Oxyethylene polyoxypropylene adduct, 2-hexyldecylamine-(poly)oxyethylene/polyoxypropylene adduct, heptadecylamine-(poly)oxyethylene polyoxypropylene adduct, octadecyl Amine-(poly)oxyethylene polyoxypropylene adduct, tetradecenylamine-(poly)oxyethylene/polyoxypropylene adduct, pentadecenylamine-(poly)oxyethylene/polyoxypropylene adduct Compounds, hexadecenylamine-(poly)oxyethylene polyoxypropylene adduct, heptadecenylamine-(poly)oxyethylene polyoxypropylene adduct, stearylamine-(poly)oxyethylene poly Oxypropylene adduct, tallow amine-(poly)oxyethylene polyoxypropylene adduct, cured tallow amine-(poly)oxyethylene polyoxypropylene adduct, etc.

The method for producing the nitrogen-containing polyoxyalkylene compound represented by the general formula (1) is not There are special restrictions. For example, the addition of a specific alkylene oxide to a specific alkylamine or alkenylamine can be used to produce a nitrogen-containing polyoxyalkylene compound represented by the general formula (1).

Here, when alkylene oxide is added, a catalyst can be used, and can be used as a catalyst. Examples include alkali metals and alkaline earth metals and their hydroxides, such as alkali metal hydrides, alcoholates and other basic catalysts or Among Lewis acid catalysts, composite metal catalysts, etc., basic catalysts are preferably used.

Usable basic catalysts include, for example, sodium, potassium, sodium potassium amalgam, sodium hydroxide, potassium hydroxide, sodium hydride, sodium methoxide, potassium methoxide, sodium ethoxide, potassium ethoxide, potassium butoxide, etc. Among them, preferred are Sodium hydroxide, potassium hydroxide, sodium methoxide, potassium methoxide and potassium butoxide.

Usable Lewis acid catalysts include tin tetrachloride, boron trifluoride, boron trifluoride diethyl ether complex, boron trifluoride di-n-butyl ether complex, boron trifluoride tetrahydrofuran complex Compounds, boron trifluoride compounds such as boron trifluoride phenol complex and boron trifluoride acetate complex.

These catalysts can be neutralized and removed after the addition reaction, but it does not matter if they remain contained. To neutralize the catalyst, it can be carried out by a known method.

The defoamer for hydraulic compositions of the present invention may contain not only the nitrogen-containing polyoxyalkylene compound represented by the general formula (1), but also other optional components without impairing the effects of the present invention. The above optional ingredients include antioxidants, other defoamers such as polyoxyalkylene alkyl ethers, and diluents such as water and alcohols.

The defoamer for hydraulic compositions of the present invention is used in hydraulic compositions containing hydraulic binders such as civil engineering, construction, or secondary products.

The defoamer for hydraulic compositions of the present invention can be used in combination with known blends. Related blends can include AE water reducer, high-efficiency AE water reducer, AE agent, defoamer, shrinkage reducing agent, thickener, hardening accelerator, etc.

From the viewpoint of obtaining excellent compatibility with the defoamer for hydraulic compositions, the blend to be used in combination with the defoamer for hydraulic compositions of the present invention preferably has a pH value of 8 or less, more preferably It is 7 or less, and more preferably 6 or less.

It becomes the object of use of the defoamer for the hydraulic composition of the present invention, that is, the hydraulic composition. The hydraulic binder required for its preparation, except for ordinary Portland cement, early strength Portland cement, and medium heat In addition to various Portland cements such as Portland cement and low-temperature Portland cement, various mixed cements such as blast furnace cement, fly ash cement or silica fume cement can also be cited. In addition, various blends such as fine blast furnace slag powder, fly ash, or silica fume can be used alone or in combination with the various cements just listed.

Moreover, when the preparation of hydraulic composition requires the use of aggregates, fine aggregates or coarse aggregates can be cited as aggregates, and fine aggregates include river sand, mountain sand, sea sand, crushed sand, and slag fine aggregates. Examples of coarse aggregates include gravel, crushed stone, lightweight aggregates, granular slag, and recycled aggregates. These aggregates can be used alone or in combination.

Furthermore, the water-binder ratio of the hydraulic composition is not particularly limited. The usually used water-to-glue ratio can show excellent results.

The hydraulic composition of the present invention preferably contains 0.0001 to 0.1 parts by mass per 100 parts by mass of the hydraulic binder 100, the ratio of the defoamer for the hydraulic composition of the present invention. When the defoaming agent for hydraulic composition of the present invention is contained in such a ratio, high defoaming or foam stability can be achieved, and it has the effect of high compatibility with the blend used in combination.

[Example]

Hereinafter, several examples are listed to more specifically illustrate the structure and effects of the present invention, but the present invention is not limited to these examples. In the following examples and comparative examples, the number of added moles of the oxyalkylene group represents the average number of added moles, and unless otherwise specified, "parts" represent parts by mass, and "%" represents mass%.

Test category 1 (synthesis of defoamer for hydraulic composition)

Synthesis of defoamer (A-1) for hydraulic composition

1347.6 parts of octadecylamine was added to the high-pressure reactor, and the high-pressure reactor was completely replaced with nitrogen. While stirring, it was maintained at 150°C, 660.8 parts of ethylene oxide was injected while reacting at 0.4 MPa, and then aged at the same temperature for 0.5 hours. After cooling to 80°C, 12 parts of potassium hydroxide powder as a catalyst was put in, and the high-pressure reactor was completely replaced with nitrogen. While stirring, 17430 parts of propylene oxide was pressure-injected while reacting at 0.4 MPa, and then aged at the same temperature to complete the reaction. The catalyst was removed to obtain the octadecylamine-polyoxyethylene (3 mol) polyoxypropylene (60 mol) adduct (A-1).

Antifoaming agents for hydraulic compositions (A-2), (A-4), (A-5), (A-11)~(A-15), (AR-1), (AR-2) and Synthesis of (AR-4)

Synthesize (A-2), (A-4), (A-5), (A-11)~(A-15), (AR-) in the same manner as the defoamer (A-1) for hydraulic composition 1), (AR-2) and (AR-4).

Synthesis of defoamer (A-3) for hydraulic composition

Add 1207.3 parts of hexadecyl groups and 13.4 parts of potassium hydroxide powder as a catalyst in the high-pressure reactor to completely replace the high-pressure reactor with nitrogen. While stirring, maintain at 100°C, inject 440.5 parts of ethylene oxide while reacting at 0.4MPa, then increase the temperature to 150°C, and press 881 parts of ethylene oxide while reacting at 0.4MPa . After that, while stirring, maintaining the same temperature, 19754 parts of propylene oxide was injected while reacting at 0.4 MPa, then aged at the same temperature for 1 hour, and the reaction was terminated. The catalyst is removed to obtain a cetylamine-polyoxyethylene (6 mol) polyoxypropylene (68 mol) adduct (A-3).

Synthesis of defoamer (A-6) for hydraulic composition

1296.8 parts of tallow amine (amine value 216.3 mg/g) was added to the high-pressure reactor, and the inside of the high-pressure reactor was completely replaced with nitrogen. While stirring, the temperature was maintained at 150°C, 1162 parts of propylene oxide was injected while reacting at 0.4 MPa, and then aged at the same temperature for 1 hour. After cooling to 80°C, 8.2 parts of potassium hydroxide powder was added as a catalyst, and the high-pressure reactor was completely replaced with nitrogen. While stirring, the temperature was maintained at 150°C, 9296 parts of propylene oxide was injected while reacting at 0.4 MPa, and then Aging at the same temperature for 1 hour, and ending the reaction. The catalyst was removed to obtain a tallow amine-polyoxypropylene (36 mol) adduct (A-6).

Synthesis of defoamer (A-7) for hydraulic composition

In a glass reaction vessel, add 3140 parts of methoxy polyethylene (2 mol) polyoxypropylene (25 mol) adduct and 2024 parts of triethylamine, and cool to 0°C, and The inside of the reaction vessel was completely replaced with nitrogen. After 252 parts of methanesulfonyl chloride was dropped while stirring, the mixture was heated to 20°C and stirred for 2 hours. Then the reaction system was cooled to 0°C, and a solution of 630 parts of ethanol dissolved in 270 parts of octadecylamine was slowly dropped. After the dropping was completed, it was heated to 40°C and aged and purified for 2 hours to obtain Stearylamine-methoxy polyoxyethylene (4 mol) polyoxypropylene (50 mol) adduct (A-7).

Synthesis of defoamer (A-8) for hydraulic composition

Add 1207.3 parts of heptadecylamine into the high-pressure reactor, and completely replace the inside of the high-pressure reactor with nitrogen. The temperature was maintained at 150°C while stirring, 440.5 parts of ethylene oxide was reacted at 0.4 MPa while being pressed in, and then aged at the same temperature for 0.5 hours. After cooling to 80°C, 8.3 parts of potassium hydroxide powder was added as a catalyst, and then the high-pressure reactor was completely replaced with nitrogen. While stirring, the temperature is maintained at 100°C. After injecting 881 parts of ethylene oxide while reacting at 0.4MPa, the temperature is raised to 150°C, and 11329.5 parts of propylene oxide is reacted at 0.4MPa while reacting. injection. It was aged for 1 hour at the same temperature and the reaction was terminated. The catalyst is removed to obtain heptadecylamine-polyoxyethylene (6 mol) polyoxypropylene (39 mol) adduct (A-8).

Synthesis of defoamers (A-9), (A-10), (A-16), (A-17), (AR-3) and (AR-5) for hydraulic compositions

(A-9), (A-10), (A-16), (A-17), (AR-3) and (AR-3) were synthesized in the same manner as the defoamer (A-7) for hydraulic compositions (AR-5).

Synthesis of defoamer (AR-6) for hydraulic composition

Add 1352.5 parts of stearyl alcohol and 8.3 parts of potassium hydroxide powder as a catalyst to the high pressure reactor, and completely replace the high pressure reactor with nitrogen. While stirring, maintain the temperature at 100°C, and inject 881 parts of ethylene oxide while reacting at 0.4MPa After the feeding, the temperature was raised to 150°C, 11,620 parts of propylene oxide was pressed in while reacting at 0.4 MPa, then aged at the same temperature for 1 hour, and the reaction was terminated. The catalyst is removed to obtain stearyl alcohol-polyoxyethylene (4 mol) polyoxypropylene (40 mol) adduct (AR-6). AR-6 is a defoamer for hydraulic compositions used as a comparative example.

Synthesis of defoamer (AR-7) for hydraulic composition

In the same place as the defoamer for synthetic hydraulic composition (AR-6), it is the defoamer for synthetic hydraulic composition (AR-7). AR-7 is a defoamer for hydraulic composition used as a comparative example.

Synthesis of defoamer (AR-8) for hydraulic composition

Add 750.9 parts of triethylene glycol and 4.7 parts of potassium hydroxide powder as a catalyst to the high-pressure reactor, and completely replace the high-pressure reactor with nitrogen. While stirring, the temperature was maintained at 150°C, 8715 parts of propylene oxide was injected while reacting at 0.4 MPa, then aged at the same temperature for 1 hour, and the reaction was terminated. Remove the catalyst, polyoxyethylene (3 mol) polyoxypropylene (30 mol) condensate (AR-8). AR-8 is used as a defoamer for hydraulic compositions of comparative examples.

The defoamers for hydraulic compositions (A-1) to (A-17) synthesized above and the defoamers for hydraulic compositions (AR-1) to (AR-8) used as comparative examples A summary of the contents is shown in Table 1.

In Table 1: AR-6: stearyl alcohol-polyoxyethylene (4 mol) polyoxypropylene (40 mol) adduct; AR-7: dodecyl alcohol-polyoxyethylene (3 mol) )/Polyoxypropylene (60 mol) adduct; AR-8: polyoxyethylene (3 mol) polyoxypropylene (30 mol) condensate.

The R ¹ system is as follows: C8: octyl

C12: Dodecyl

C14 *: tetradecenyl

C15: Pentadecyl

C16: Cetyl

C16 branch: 2-hexyldecyl

C17: Heptadecyl

C18: Octadecyl

C18 *: octadecenyl

C20: Eicosyl

C25 *: Pentadecenyl

Test category 2 (Synthesis of polycarboxylate water-reducing agent as a blend)

Synthesis of polycarboxylic acid water reducer (B-1)

Add ion-exchanged water and α-(3-methyl-3-butenyl)-ω-hydroxy-poly(45 mol) oxyethylene into the reaction vessel, replace the ambient gas with nitrogen, and add slowly while stirring temperature. The temperature of the reaction system was maintained at 70°C in a warm water bath to stabilize the temperature. After that, acrylic acid was dropped over 3 hours. At the same time, an aqueous solution of thioglycolic acid, L-ascorbic acid and 5% hydrogen peroxide dissolved in water was dropped in 3 hours to start the radical polymerization reaction. One hour after the completion of the dropping, water and a 30% sodium hydroxide aqueous solution were added to the obtained copolymer to obtain a polycarboxylic acid water reducing agent (B-1) having a solid content of 25%. As a result of analyzing the polycarboxylic acid water reducing agent, the mass average molecular weight was 42,000 and the pH was 3.6. The mass average molecular weight of the copolymer is measured by gel permeation chromatography.

Adjustment of polycarboxylic acid water reducing agent (B-2) and (B-3)

A 30% sodium hydroxide aqueous solution and water are added to the polycarboxylic acid water reducing agent (B-1) to obtain 25% aqueous solutions (B-2) and (B-3). As a result of measuring the pH value, (B-2) was 6.8, and (B-3) was 8.9.

GPC method for measuring conditions of mass average molecular weight

Device: Shodex GPC-101 (manufactured by Showa Denko)

Column: OHpak SB-G+SB-806M HQ+SB-806M HQ (manufactured by Showa Denko) Made)

Detector: Differential Refractometer (RI)

Eluent: 50mM sodium nitrate aqueous solution

Flow rate: 0.7mL/min

Column temperature: 40℃

Sample concentration: Eluent solution with sample concentration of 0.5% by mass

Standard material: PEG/PEO (manufactured by Agilent)

pH measurement conditions

100 g of ion-exchanged water was added to 1 g of polycarboxylic acid water reducing agent, and the measurement was performed at 20° C. with a pH measuring device (manufactured by HORIBA).

The contents of the blends used are shown in Table 2.

In Table 2: B-4: Polycarboxylic acid compound (High performance AE water reducer for concrete manufactured by Takemoto Oil Co., Ltd., trade name Tupole HP-11); B-5: Modified lignosulfonic acid compound and polycarboxylic acid compound (The AE water reducing agent for concrete manufactured by Takemoto Oil Co., Ltd., trade name Tupole EX60).

Test category 3 (preparation of blend composition for evaluation)

Combine the defoamers (A-1)~(A-17) and (AR-1)~(AR-8) for hydraulic compositions shown in Table 1 with the blends (B-1) shown in Table 2. )~(B-5) Mix and stir to prepare the blend composition for evaluation (125 samples in total). However, in the mixing ratio-based blends (B-1) to (B-4), the blend is 99.5% by mass, and the defoamer for hydraulic composition is 0.5% by mass, and the blend (B-5) Among them, the blend content is 99.7% by mass, and the defoamer for hydraulic composition is 0.3% by mass.

Test category 4 (preparation of concrete composition)

Examples 1 to 17 and comparative examples 1 to 9

Using a forced twin-screw mixer with a capacity of 60 liters, mixing was carried out for 90 seconds with the contents described in Table 3, and the concrete compositions in each example were prepared. The temperature of the prepared concrete composition is 20±3°C. However, for the concrete composition shown in Comparative Example 1 that did not contain the defoamer for hydraulic composition, AE-300 (trade name made by Takemoto Oil Co., Ltd.) was used as the air volume adjuster, and the air volume was adjusted to 7.0 ±1.0%, and the slump measured in accordance with JIS A 1150 is adjusted to 15±2.5cm. The concrete composition in each example, the admixture and the admixture composition prepared in test category 3 are used stable.

In Table 3: Binder: Ordinary Portland Cement (Density=3.16g/cm3); Fine Aggregate: Land Sand (Saturated Surface Dry Density) =2.57g/cm3); Coarse aggregate: Crushed stone produced by Okazaki (surface saturated dry density = 2.66g/cm3).

Test category 5 (test of concrete composition and evaluation of defoamer for hydraulic composition)

For the prepared concrete compositions in each example, the air volume was measured, and the compatibility, defoaming properties and foam stability of the hydraulic composition defoamer with the admixture were evaluated as follows, and The results are summarized in Table 4.

Air volume (volume%): For the concrete composition that has just been mixed and mixed, it is measured in accordance with the specifications of JIS A 1128.

Compatibility of blends: For the concrete composition just prepared, compare the air volume I (vol%) measured by the blend composition when the defoamer for the hydraulic composition is just mixed , And use the air volume II (volume %) set by removing the upper 50% by mass and the lower 50% by mass in the blend composition that has been allowed to stand at 40°C for a week, and evaluate its effect on blending according to the following criteria Compatibility of objects.

S: Very good (the value of air volume II minus air volume I is less than ±0.5)

A: Good (The value of air volume II minus air volume I is 0.5 or more but less than 1.0)

B: Yes (the value of air volume II minus air volume I is above 1.0 but less than 2.0)

C: Poor (the value of air volume II minus air volume I is 2.0 or more)

Defoaming properties: For the concrete composition just prepared, compare the air volume III (volume %, comparative example 1) measured with a blend that does not contain a defoamer for hydraulic composition and the concrete composition just mixed The measured air volume I (volume %) of the blend composition was evaluated based on the following criteria.

S: Very good (the value of air volume III minus air volume I is 4.0 or more)

A: Good (The value of air volume III minus air volume I is 3.0 or more, but less than 4.0)

B: Yes (the value of air volume III minus air volume I is above 2.0 but less than 3.0)

C: Poor (the value of air volume III minus air volume I is less than 2.0)

Foam stability: For the concrete composition prepared by using the admixture composition just mixed with the defoamer for hydraulic composition, visually observe the state of bubbles and follow The foam stability was evaluated according to the following criteria.

S: Very good (the breakage of surface bubbles can hardly be confirmed)

A: Good (the breaking of surface bubbles is very slightly confirmed)

B: Yes (the breakage of surface bubbles is slightly confirmed)

C: Poor (a large number of surface bubbles are confirmed to be broken)

In Table 4: AR-6: stearyl alcohol-polyoxyethylene (4 mol) polyoxypropylene (40 mol) adduct; AR-7: dodecyl alcohol-polyoxyethylene (3 mol) ) Polyoxypropylene (60 mol) adduct; AR-8: Polyoxyethylene (3 mol) polyoxypropylene (30 mol) condensate.

result

From the results shown in Table 4, it can be clearly confirmed that according to the present invention, it is possible to provide a defoamer for hydraulic compositions that has high compatibility with the blend and excellent defoaming properties and foam stability.

[Industrial availability]

The blend for a hydraulic composition of the present invention can be used as a defoamer when preparing a hydraulic composition.

Claims (10)

An antifoaming agent for hydraulic compositions, comprising a nitrogen-containing polyoxyalkylene compound represented by the following general formula (1),

In the above formula, R ¹ represents an alkyl or alkenyl group with 10 to 24 carbons, R ² and R ³ are the same or different, and represent a hydrogen atom and/or a hydrocarbon group with 1 to 10 carbons, A ¹ O and A ² O They are the same or different and represent oxyalkylene groups with 2 to 4 carbon atoms, m and n are the same or different, are integers from 0 to 100 and satisfy the condition of 20≦m+n≦100, and A ¹ O and A ² O Among them, the oxyalkylene group having 3 and/or 4 carbon atoms is 65 mol% or more. The defoamer for a hydraulic composition according to claim ¹ , wherein among the A ¹ O and the A ² O, the oxyalkylene group with carbon number 3 and/or 4 is 86 mol% or more The defoamer for hydraulic compositions described in 1. The defoamer for a hydraulic composition according to claim ¹ , wherein among the A ¹ O and the A ² O, the oxyalkylene group having 3 and/or 4 carbon atoms is 90 mol% or more. The defoamer for a hydraulic composition according to claim 1, wherein the m and the n are the same or different, are an integer of 0 to 80, and satisfy the condition of 30≦m+n≦80. The defoamer for a hydraulic composition according to claim 1, wherein the m and the n are the same or different, are an integer of 0 to 80, and satisfy the condition of 35≦m+n≦80. The defoamer for hydraulic compositions according to claim ¹ , wherein the R ² and R ³ represent a hydrogen atom. The defoamer for hydraulic compositions according to claim ¹ , wherein the R ¹ is an alkyl or alkenyl group having 14 to 18 carbon atoms in the formula. The defoamer for a hydraulic composition according to claim ¹ , wherein the A ¹ O and the A ² O are the same or different, and are an oxyalkylene group having 2 and/or 3 carbon atoms, and A ¹ O At least one of A ² O and A ² O includes an oxyalkylene group having 3 carbon atoms. A hydraulic composition comprising the defoamer for a hydraulic composition as described in claim 1. The hydraulic composition as described in claim 9 and contains a blend having a pH of 8 or less.