TW202003419A - Antifoaming agent for hydraulic composition, additive for hydraulic composition, and hydraulic composition - Google Patents

Abstract

An antifoaming agent for hydraulic compositions which is a polyoxyalkylene-based compound represented by general formula (1), the compound satisfying a first requirement, which is 0.16 ≤ n/(p+n+m) ≤ 0.40, and a second requirement, which is 20 ≤ (p+n+m) ≤ 48. General formula (1): RO-(AO)p-(EO)n-(AO)m-H (wherein R represents a C8-30 alkyl or alkenyl group and has a linear or branched structure; the AO moieties are the same or different, C3-18 oxyalkylene groups; EO represents an oxyethylene group; and p, n, and m, each indicating the average number of moles added, are 0 or larger, 1 or larger, and 1 or larger, respectively.).

Description

Antifoaming agent for hydraulic composition, additive for hydraulic composition and hydraulic composition

The present invention relates to a defoamer for hydraulic composition, an additive for hydraulic composition and a hydraulic composition, and more specifically to an excellent compatibility with a dispersant and even in a small amount An antifoaming agent for a hydraulic composition capable of exerting a high antifoaming effect, an additive for a hydraulic composition containing the antifoaming agent for the hydraulic composition, and a hydraulic composition containing the antifoaming agent for the hydraulic composition.

Conventionally, a hydraulic composition is a hardened body obtained by kneading various materials such as a hydraulic binder and water, filling a mold, and hardening the mold. In particular, the concrete composition, which is one of the hydraulic compositions, is mixed and kneaded with various materials such as cement, water, aggregates, and dispersants, and poured into a mold prepared in advance to harden at a predetermined time. To be manufactured. Such a concrete composition has characteristics of excellent strength and durability, and is widely used in various buildings or building structures to fully exert the characteristics.

Here, in order to increase gas transmission characteristics or fluidity when kneading various materials, concrete compositions generally add additives (additives for hydraulic compositions). With the use of additives like this, it is possible to maintain good dispersion characteristics even when the concrete composition has been reduced in water. In addition, the operating characteristics (construction characteristics) during kneading or construction can be made good. Therefore, the durability and strength of the concrete composition can be improved, and it can be built into a concrete composition with excellent stability and operability over time.

Especially in recent years, among additives for hydraulic compositions added to hydraulic compositions, it is known to use a polycarboxylic acid type dispersant as a dispersant, which can improve the dispersion characteristics of various materials of hydraulic compositions. Mix and knead evenly. By using a polycarboxylic acid type dispersant, the water reducing properties of the hydraulic composition can be improved. On the other hand, although the use of a polycarboxylic acid type dispersant provides excellent gas transmission characteristics, the bubbles generated during kneading have a large bubble diameter, which may affect construction work. In order to solve the above problems and generate fine and fine-textured air bubbles to improve the freezing solubility, the so-called AE agent (air entraining agent) is currently used in combination.

In this case, when a polycarboxylic acid type dispersant and an AE agent are used in combination, in general, an antifoaming agent (antifoaming agent for hydraulic composition) is used to eliminate most of the bubbles generated by the AE agent and the like. For example, a concrete composition containing polyoxyalkylene compound, cement, water, fine aggregate, and coarse aggregate as essential components is known (refer to Patent Document 1). In this concrete composition, the polyoxyalkylene compound is when the total number of added moles of oxyethylene groups in the oxyalkylene group is u and the total number of added moles of oxyalkylene groups with a carbon number of 3 or more is v , Satisfying the relationship of "0.15<u/(u+v)<0.9", and having at least one carbon atom with 5 or more continuous aliphatic hydrocarbon groups in the molecule. This can reduce the increase in air volume as the kneading time increases, and has the advantage of stably maintaining the air volume. As a result, a high-quality concrete composition with excellent durability and strength can be provided.

That is, in the conventional technology, it is considered to use a highly hydrophobic material as a defoaming agent for the concrete composition, but the oxyethylene group of the polyoxyalkylene compound improves the hydrophilicity, which can effectively suppress bubbles caused by the AE agent and the like This can suppress the increase in the amount of air as the kneading time increases. As a result, the air volume can be stabilized without increasing the air volume.

【Prior Technical Literature】 Patent Literature

Patent Document 1: Japanese Patent Publication No. 2003-226565

On the other hand, in the case of the general polyoxyalkylene compound disclosed in Patent Document 1, the following problems may occur. Compared with the polycarboxylic acid type dispersant used at the same time, the antifoaming agent for hydraulic composition can show the defoaming effect greatly with a small amount of addition. Therefore, in order to prevent the measurement error of the measuring device, try to mix it up to A method in which a carboxylic acid type dispersant forms a single liquid. However, there is a problem of "compatibility" between the polyoxyalkylene compound and the polycarboxylic acid type dispersant. That is, the change over time after the mixing of the polycarboxylic acid type dispersant and the defoaming agent causes the problem that both of them return to the separated state. At this time, the defoamer is biased in the storage tank, so it is difficult to control the air volume, and it is impossible to obtain a hydraulic composition with stable air volume each time it is kneaded. The strength is uneven, and it is difficult to obtain a hydraulic composition that is stable and has excellent durability and strength.

The polyoxyalkylene compound disclosed in the above Patent Document 1 has good compatibility with the polycarboxylic acid type dispersant. However, in order to exert a high defoaming effect with this polyoxyalkylene compound, it is necessary to mix in a relatively high ratio in the hydraulic composition. In other words, the addition amount (use amount) of the polyoxyalkylene compound must be increased. As a result, the addition amount of the defoamer to be used is increased compared with usual, and the cost of the hydraulic composition is increased accordingly.

In order to solve the above-mentioned problems, the inventors of the present invention have repeatedly studied and found that by optimizing the polyoxyalkylene compound used as the defoaming agent of the hydraulic composition, the oxyethylene group constituting the polyoxyalkylene compound The molar ratio and the total added mole number of the oxyethylene group constituting the polyoxyalkylene compound and the oxyethylene group having 3 to 18 carbon atoms have excellent compatibility with the polycarboxylic acid type dispersant, and A small amount of the foaming agent itself can also exhibit a high defoaming effect, a defoaming agent for a hydraulic composition, an additive for a hydraulic composition comprising the defoaming agent for the hydraulic composition, and the hydraulic composition It is a hydraulic composition prepared with antifoaming agent.

In view of the above facts, the subject of the present invention is to provide a hydraulic property which has good compatibility with polycarboxylic acid type dispersants and can exert high defoaming performance even if the defoamer itself is added in a small amount Defoamer for composition, additive for hydraulic composition, and hydraulic composition.

According to the present invention, the antifoaming agent for hydraulic composition, the additive for hydraulic composition and the hydraulic composition disclosed below are provided.

[1] An antifoaming agent for a hydraulic composition, which is a polyoxyalkylene compound represented by the following general formula (1) and satisfies the following relationship: first condition: 0.16≦n/(p+n+m) ≦0.40; and the second condition: 20≦p+n+m≦48; RO-(AO)p-(EO)n-(AO)mH...(1). However, R represents an alkyl or alkenyl group having 8 to 30 carbon atoms and has a linear or branched structure. AO is an alkylene oxide group having the same or different carbon number of 3 to 18, and EO is an oxyethylene group. p, n, and m represent the average additive mole numbers, respectively, and p is 0 or more, n is 1 or more, and m is 1 or more.

[2] The defoamer for hydraulic compositions described in [1], wherein R in the general formula (1) is an alkyl or alkenyl group having 14 to 22 carbon atoms, and is self-unsaturated and/or branched. The residue obtained by removing the hydroxyl group of the alcohol contains 50% by mass or more relative to the total amount of R.

[3] The defoamer for hydraulic compositions described in [1] or [2], wherein AO in the general formula (1) is an oxypropylene group.

[4] The defoamer for a hydraulic composition according to any one of [1] to [3], wherein the first condition further satisfies the condition of 0.16≦n/(p+n+m)≦0.38.

[5] The defoamer for a hydraulic composition according to any one of [1] to [4], wherein the second condition further satisfies the condition of 24≦p+n+m≦40.

[6] The defoamer for a hydraulic composition according to any one of [1] to [5], wherein the carbon number of R in the general formula (1) is 14-22.

[7] An additive for a hydraulic composition comprising the antifoaming agent for a hydraulic composition described in any one of [1] to [6], a polycarboxylic acid type dispersant, and water as essential components.

[8] A hydraulic composition comprising the antifoaming agent for a hydraulic composition described in any one of [1] to [6], a polycarboxylic acid type dispersant, and cement as essential components.

[9] A hydraulic composition comprising the antifoaming agent for a hydraulic composition described in any one of [1] to [6], a polycarboxylic acid type dispersant, cement, and a fine aggregate and/or Coarse aggregates are essential components.

According to the defoamer for hydraulic compositions of the present invention, it has excellent compatibility with dispersants such as polycarboxylic acid type dispersants, and can exhibit high defoaming efficiency with a small amount of addition. Furthermore, by using the antifoaming agent for a hydraulic composition or the additive for a hydraulic composition containing the antifoaming agent for a hydraulic composition, a hydraulic composition excellent in durability and strength can be produced.

Hereinafter, an embodiment of the defoamer for hydraulic compositions, the additive for hydraulic compositions, and the hydraulic composition will be described. Here, the antifoaming agent for hydraulic composition of the present invention (hereinafter simply referred to as "antifoaming agent"), the additive for hydraulic composition and the hydraulic composition are not limited to the following embodiments, without departing from the present invention. Changes, modifications, or improvements can be made within the scope of the invention.

1. Antifoaming agent (antifoaming agent for hydraulic composition)

An antifoaming agent according to one embodiment of the present invention is a polyoxyalkylene compound represented by the following general formula (1), and satisfies the first condition: 0.16≦n/(p+n+m)≦0.40; And the second condition: the relationship of 20≦p+n+m≦48; RO-(AO)p-(EO)n-(AO)mH... (1).

In the above general formula (1), "R" represents an alkyl or alkenyl group having 8 to 30 carbon atoms, and has a linear or branched structure. In addition, "AO" means the same or different C 3-18 oxyalkylene groups, and "EO" means the oxyethylene group. On the other hand, p, n, and m each represent an average addition mole number, and p is 0 or more, n is 1 or more, and m is 1 or more.

That is, the antifoaming agent of the present embodiment is the polyoxyalkylene compound represented by the above general formula (1), and is composed of: the oxyethylene (EO) group and the EO group constituting the polyoxyalkylene compound The average addition mole number of the alkylene oxide (AO) group having 3 to 18 carbon atoms at the end satisfies the first and second conditions shown above.

Here, R in the general formula (1) is an alkyl group or alkenyl group having 8 to 30 carbon atoms, particularly preferably 14 to 22 carbon atoms, and has a linear or branched structure. In particular, R can use residues obtained by removing hydroxyl groups from alcohols. The alcohols that can be used are not particularly limited, and may be, for example, octanol, nonanol, decanol, undecanol, dodecanol, tridecanol, tetradecyl alcohol, pentadecyl alcohol, cetyl alcohol, heptadecyl alcohol, Octadecanol, nonadecanol, eicosanol, twenty-one alcohol, behenyl alcohol, twenty-three alcohol, twenty-four alcohol, twenty-five alcohol, twenty-six alcohol, twenty-seven alcohol, twenty-eight alcohol Straight-chain alcohols such as alcohol, 29 alcohol and triocanol; 2-ethylhexanol, 2-propylheptanol, 2-butyloctanol, 1-methylheptadecanol, 2-hexyloctanol Alcohol, 2-hexyldecanol, isodecyl alcohol, isotridecyl alcohol, 3,5,5-trimethylhexanol and other branched chain alcohols; octenol, nonenol, decenol, undecenol , Dodecenol, tridecanol, tetradecenol, pentadecenol, hexadecenol, pentadecenol, hexadecenol, heptadecenol, octadecenol, nonapenol , Eicosenol, docosenol, twenty-four-enol, twenty-five-carbon dilute alcohol, hexadecenol, twenty-seven-carbon enol, octacosanol, thirty Straight-chain enols such as carbenols, thirty-three-carbon dilute alcohols, etc.; or branched-chain dilute alcohols such as 2-ethylhexenol, 1-methylheptadecanol, isoynyl alcohol, isostearyl alcohol, etc. . Furthermore, the alcohol used only as R may be used by selecting only one type from the above list, or two or more alcohols may be used in combination.

Here, when the above alcohols are used, it is preferably 14 to 22 carbon atoms, and it is preferable that the residue from which the hydroxyl group is removed from the unsaturated and/or branched primary alcohol contains 50% by mass or more relative to the total amount of R. Thereby, the defoaming efficiency of the hydraulic composition can be improved. The alcohol used at this time is preferably liquid in nature, and more preferably liquid at 20°C. This allows good mixing with other materials of hydraulic compositions such as polycarboxylic acid type dispersants described below at around room temperature.

Furthermore, specific examples of alcohols that can be used include high-grade alcohols derived from natural oils and fats, KALCOL series (Kao Corporation), CONOL series (New Japan Physical and Chemical Corporation), FINEOXOCOL series (Nissan Chemical Industry Corporation), NEODOL series (SHELL CHEMICALS Ltd.), SAFOL series (SASOL), EXXAL series (EXXON MOBIL CORPORATION), etc. As mentioned above, these alcohols are preferably liquid at 20°C.

On the other hand, AO (oxyalkylene group) in the general formula (1) is an oxyalkylene group having 3 to 18 carbon atoms. Examples of the oxyalkylene groups having 3 to 18 carbon atoms include oxypropylene groups, oxybutylene groups, oxyhexylene groups, oxyoctylene groups, and oxystyryl groups. In particular, AO is preferably an oxypropylene group. Thereby, the defoaming performance can be improved, and the compatibility with the polycarboxylic acid type dispersant and the like can be stabilized.

In addition, in the defoamer of the present embodiment, the first condition in the general formula (1) may satisfy the condition of 0.16≦n/(p+n+m)≦0.38. That is, the range of the aforementioned first condition can also be narrowed. On the other hand, the second condition in the general formula (1) may satisfy the condition of 24≦p+n+m≦40. That is, similarly to the above-mentioned first condition, the range of the above-mentioned second condition can be further narrowed. With this, the range of the first condition and/or the second condition can be more limited, and a higher defoaming effect can be exerted, and an antifoaming agent with excellent compatibility can be obtained.

2. Additives for hydraulic compositions and hydraulic compositions

By using the defoaming agent as described above, the additive for hydraulic composition and the hydraulic composition can be obtained. Here, the additive for a hydraulic composition contains a polycarboxylic acid type dispersant and water as essential components in addition to the defoamer mentioned above. Thereby, the compatibility with the antifoaming agent and the polycarboxylic acid type dispersant is good, and the additive for hydraulic composition with high antifoaming efficiency can be obtained. On the other hand, in addition to the additives for the hydraulic composition, the hydraulic composition further contains cement as an essential component or cement and aggregate as an essential component. However, the additive for the hydraulic composition or the water contained in the hydraulic composition is a well-known substance, and therefore its detailed description is omitted here. Furthermore, as the aggregate contained in the hydraulic composition, fine aggregate such as sand and/or coarse aggregate such as gravel, crushed stone, groundwater slag, and recycled aggregate can be suitably used. In addition, the detailed description of the polycarboxylic acid type dispersant will be described later, and the description is omitted here.

3. Manufacturing method of antifoaming agent (polyoxyalkylene compound)

The method for producing the defoamer (polyoxyalkylene compound) of the present embodiment is not particularly limited, and a well-known production method can be used. For example, polyoxyalkylene compounds can be obtained by adding alkylene oxides to alcohols. Here, when adding alkylene oxide, a catalyst may be used, and as the catalyst, alkali catalysts such as hydroxides and alkoxides of alkali metals, alkaline earth metals or the like, or Lewis acid catalysts and composite metal catalysts may be used, especially alkaline catalysts. good.

Examples of usable basic catalysts include sodium, potassium, sodium-potassium amalgam, sodium hydroxide, potassium hydroxide, sodium hydride, sodium methoxide, potassium methoxide, sodium ethoxide, potassium ethoxide, and potassium butoxide. Sodium oxide, potassium hydroxide, sodium methoxide, potassium methoxide and potassium butoxide are particularly preferred.

On the other hand, examples of usable Lewis acid catalysts include tin tetrachloride, boron trifluoride, boron trifluoride ether complex, boron trifluoride di-n-butyl ether complex, and boron trifluoride Boron trifluoride compounds such as tetrahydrofuran complex, boron trifluoride phenol complex, boron trifluoride acetic acid complex, etc.

These catalysts can be neutralized and removed after the addition reaction, on the other hand, they can also be kept contained. The neutralization of the catalyst can be carried out by well-known techniques. For example, when the catalyst is an alkaline catalyst, acids such as hydrochloric acid, sulfuric acid, methanesulfonic acid, phosphoric acid, acetic acid, lactic acid, citric acid, succinic acid, or silicates such as aluminum silicate and magnesium silicate, activated clay, acid Adsorbents such as clay, silicone rubber, acidic ion exchange resin, etc. are used as neutralizing agents.

Furthermore, neutralization will be described more specifically. As commercially available adsorbents, for example, KYOWAAD600, 700 (respectively trade names of Kyowa Chemical Industry), MIZUKALIFEP-1, P-1S, P-1G, F-1G ( Silicates of Mizusawa Chemical Industry, TOMITA-AD600, 700 (trade names of Tomita Pharmaceuticals), etc.; or DIAION (trade name of Mitsubishi Chemical Corporation), AMBERLYST, AMBERLITE, DOWEX (respectively for DOW CHEMICAL COMPANY's trade name), ion exchange resins, etc. Only one kind of neutralizing agent may be used, or two or more kinds of neutralizing agents may be used in combination.

The neutralization salts (neutralization products) generated by the neutralization of the catalyst can be further solid-liquid separated. For the solid-liquid separation method of neutralizing salts, for example, well-known filtration or centrifugal separation methods can be used. Here, the solid-liquid separation type caused by filtration uses, for example, filter paper, filter cloth, cartridge filter, two-layer filter of cellulose and polyester, metal mesh filter, metal sintered filter, etc. In the case of pressurization, the temperature is 20 to 140°C. On the other hand, the solid-liquid separation by centrifugal separation can be implemented with a centrifugal separator such as a decanter or a centrifugal clarifier. However, about 1 to 30 parts by mass of water can also be added to 100 parts by mass of the solution before solid-liquid separation according to needs. When the above solid-liquid separation requires special filtration, it is advisable to use filter aids to increase the filtration speed.

The filter aid used for filtration is not particularly limited, and examples thereof include diatomaceous earth, HYFLO SUPER CEL., CELL PURE series (trade name of ADVANCED MINERALS CORPORATION), silicon dioxide #645, silicon dioxide # Diatomite such as 600H, silica #600S, silica #300S, silica #100F (central SILICA trade name), white diatomite (GREFCO trade name); and ROKAHELPR (Mitsui Metal Mining (Trade name), TOPCO (trade name of Showa Chemical), and other perlite; KC-FLOCK (trade name of Japanese paper company), FIBERACELL (manufactured by ADVANCED MINERALS CORPORATION) and other cellulose-based filter aids; SAIROPYUTO (Fuji Silicone of Silysia Chemical Co., Ltd. etc.). In addition, only one kind of the above filter aid may be used, or two or more kinds may be used in combination.

Furthermore, a well-known thing can be used for a carboxylic acid type polycarboxylic acid type dispersant. For example, a copolymer containing a monomer represented by the following general formula (2) and an unsaturated carboxylic acid monomer can be exemplified.

R ¹ -OAR ² ... (2)

(Only, in the general formula (2), R ¹ is an alkenyl group having 2 to 5 carbon atoms or an unsaturated acetyl group having 3 or 4 carbon atoms, and A is a carbon atom having 2 to 4 carbon atoms or more. (Poly)oxyalkylene units with an average addition mole number of 1 to 500 composed of alkylene oxide groups, R ² represents a hydrogen atom or an alkyl group having 1 to 22 carbon atoms or an aliphatic group having 1 to 22 carbon atoms Acrylic.)

As the unsaturated carboxylic acid monomers, there are (meth)acrylic acid, crotonic acid and the like and their salts as the monocarboxylic acid type monomers, while the dicarboxylic acid monomers are maleic acid, itaconic acid, fumaric acid and the like And its equivalent. Among them, (meth)acrylic acid, maleic acid and their salts are particularly preferred. The salt is not particularly limited, but examples thereof include alkali metal salts such as sodium and potassium, alkaline earth metal salts such as magnesium and calcium, aluminum and iron metal salts, ammonium salts, and amine salts.

The copolymer may be obtained by reacting any suitable monomer (third monomer) in addition to the above-mentioned monomers and unsaturated carboxylic acid monomers. In this case, as the third monomer, for example, (meth)allylsulfonic acid and its salts, (meth)acrylamide, acrylonitrile, (meth)acrylate, and the like can be used.

Furthermore, the carboxylic acid type polycarboxylic acid type dispersant can be produced by a known method. In addition, the copolymer can be produced by a known method. For example, the copolymer is synthesized by radical polymerization, and is obtained by mixing (heating) the above monomer, unsaturated carboxylic acid monomer, and third monomer with a radical initiator. Examples of the free radical accelerator used include potassium persulfate, ammonium persulfate, hydrogen peroxide, 2,2-azobis(2-amidinopropane) dihydrochloride, and azobisisobutyronitrile. These can be combined with reducing substances such as sulfite and L-ascorbic acid, or further combined with amines, etc., to be used as redox initiators. In order to make the mass average molecular weight of the obtained copolymer within the desired range, chain transfer agents such as 2-mercaptoethanol, 2-mercaptopropionic acid, 3-mercaptopropionic acid, thioglycolic acid, mercaptoethanol, and thioglycerol can be used . In addition, water or an organic solvent may be used as a solvent for the polymerization, or a solvent may not be used.

Examples

Hereinafter, the defoaming agent of the present invention and the hydraulic composition containing the defoaming agent will be described based on the following examples and the like. However, the defoamer and hydraulic composition of the present invention are not limited to the following examples. The conditions of the specific method (addition reaction, etc.) for producing an antifoaming agent have already been described, and therefore detailed descriptions thereof are omitted here.

1. Synthesis of defoamer (polyoxyalkylene compound)

Initially, alcohols were used as R in the general formula (1) to synthesize an antifoaming agent (polyoxyalkylene compound). First, 130.7 g of alcohol A1 ("UNJECOL85AN (new Japanese physical and chemical trade name)") and 1.1 g of potassium hydroxide were added to a pressure vessel equipped with a stirrer, pressure gauge and thermometer. Alcohol A1 ("UNJECOL85AN") has a melting point of about 11°C, and is in a liquid state at room temperature around 20°C.

In this state, after dehydration treatment, while maintaining the reaction system in the pressure vessel at 110±5°C, 217.8 g of ethylene oxide was pressed in at a gauge pressure of 0.4 MPa for one hour, and then for two hours ripe. Furthermore, while maintaining the above-mentioned reflection system at 135±5°C, 777.4 grams of propylene oxide was pressed in at a gauge pressure of 0.4 MPa for five hours and then matured in two hours to complete the reaction.

After that, "KYOWAAD600 (trade name of Kyowa Chemical Industry Co., Ltd.)" was used as an adsorbent for neutralization treatment, and filtration purification was performed to obtain a purified product. According to the analysis results of NMR and gel permeation chromatography (converted to the mass average molecular weight of polystyrene) of this purified product, 10.1 mol of ethylene oxide and 27.2 mol of epoxy were sequentially added to 1.0 mol of lauryl alcohol Propane defoamer af-1 (polyoxyalkylene compound). The measurement conditions of NMR and gel permeation chromatography are as follows.

Measurement conditions

(1) NMR

Device: Varian Mercury 300 (300MHz)

Nuclear species: 1H, 13C

Solvent: CDCl3

(2) Gel permeation chromatography

Device: HLC-8120GPC (TOSOH Corporation)

Column: TSK gel Super H4000+TSK gel Super H3000+TSK gel Super H2000 (TOSOH Co., Ltd.)

Detector: Differential Refractometer (RI)

Dissolution solution: Tetrahydrofuran

Flow rate: 0.5mL/min

Column temperature: 40℃

Sample concentration: 0.5% by mass of eluent solution

Standard material: Polystyrene (TOSOH Corporation)

The types of alcohols A1 to A5 used, alkylene oxide (oxypropylene group), addition order and amount of addition reaction, etc. were changed according to the conditions shown in Table 1 below. The synthesis of -1 is similar to the treatment to synthesize various defoamers af-2~af-9 and af-e1~af-e3. The detailed information and characteristics (linear/branched, saturated/unsaturated, carbon number, etc.) of the alcohols A1 to A5 used in the synthesis of the defoamer are summarized in Table 2 below.

In the above Table 1, the defoamers af-1 to af-9 are synthesized to satisfy the first and second conditions of the defoamer of the present invention. On the other hand, the defoamers af-e1 and af-e3 are deviated from the first condition, while the defoamers af-e2 are deviated from the second condition and synthesized to be compared with af-1 and the like.

2. Synthesis of copolymer used in carboxylic acid type polycarboxylic acid type dispersant

(1) Production Example 1 (Production of copolymer PC-1)

Combine 140.1 grams of ion-exchanged water, 163.0 grams of α-methacryloyl-ω-methoxy-poly(n=9) ethylene oxide, 28.8 grams of methacrylic acid, 3.8 grams of 3-mercaptopropionic acid, and 9.9 grams of 30 % Aqueous sodium hydroxide solution is prepared in a reaction vessel with a thermometer, stirrer, dropping funnel, and nitrogen introduction tube. After stirring and dissolving uniformly, the ambient gas is replaced with nitrogen, and the temperature of the reaction system is reached 60°C in a warm water bath . Next, 63.9 g of 3.0% sodium persulfate aqueous solution was added to start the polymerization reaction. Two hours later, after adding 28.8 g of 3.0% sodium persulfate aqueous solution and maintaining at 60°C for two hours, the polymerization reaction was terminated. This was adjusted to pH 6 by adding 30% aqueous sodium hydroxide solution, and the concentration was adjusted to 40% with ion-exchanged water. Let this reactant be a copolymer (PC-1).

(2) Production Example 2 (Production of copolymer PC-2)

209.2 g of ion-exchanged water, 181.9 g of α-methyl-ω-methoxy-poly(n=45) oxyethylene, 15.8 g of methacrylic acid, and 2.0 g of 3-mercaptopropionic acid were prepared with The reaction vessel of the thermometer, stirrer, dropping funnel, and nitrogen introduction tube was dissolved while dissolving evenly while replacing the ambient gas with nitrogen, and the temperature of the reaction system was brought to 60°C in a warm water bath. Next, 27.7 g of a 1.0% aqueous hydrogen peroxide solution was dropped over 2.5 hours. Thereafter, 7.1 g of a 1.0% hydrogen peroxide aqueous solution was dropped over 3.5 hours, and the polymerization reaction was ended. This was adjusted to pH 6 by adding 30% sodium hydroxide aqueous solution, and the concentration was adjusted to 40% with ion-exchanged water. Let this reactant be a copolymer (PC-2).

(3) Production Example 3 (Production of copolymer PC-3)

Prepare 94.2 grams of ion-exchanged water in a reaction vessel with a thermometer, stirrer, dropping funnel, and nitrogen introduction tube. After stirring and dissolving uniformly, replace the ambient gas with nitrogen, and make the temperature of the reaction system reach 60 with a warm water bath. ℃. Next, 29.3 g of a 1.0% sodium persulfate aqueous solution was added and the solution was dropped for 3.5 hours. At the same time, 117.3 g of ion-exchanged water was dissolved with 11.7 g of methacrylic acid and 183.8 g of α-methyl-ω-methoxy-poly( n=113) An aqueous solution of oxyethylene and 1.6 g of 3-mercaptopropionic acid dripped in 3.0 hours. Thereafter, the temperature was maintained at 60°C for 2 hours, and the polymerization reaction was terminated. This was adjusted to pH 6 by adding 30% aqueous sodium hydroxide solution, and the concentration was adjusted to 40% with ion exchanged water. Let this reactant be a copolymer (PC-3).

(4) Production Example 4 (Production of copolymer PC-4)

Prepare 82.6 grams of ion-exchanged water and 175.7 grams of α-methallyl-ω-hydroxy-poly(n=113) oxyethylene in a reaction vessel with a thermometer, stirrer, dropping funnel, and nitrogen introduction tube, stirring After uniformly dissolving on one side, the ambient gas was replaced with nitrogen, and the temperature of the reaction system was brought to 60°C in a warm water bath. Next, 9.8 g of a 10.0% aqueous hydrogen peroxide solution was dropped in 3.0 hours, and at the same time, an aqueous solution of 11.7 g of acrylic acid and 7.8 g of hydroxyethyl acrylate dissolved in 97.6 g of ion-exchanged water was dropped in 3.0 hours. An aqueous solution in which 0.8 g of 3-mercaptopropionic acid and 1.0 g of ascorbic acid were dissolved in 7.0 g of ion-exchanged water was dropped in 4.0 hours. Thereafter, the temperature was maintained at 60°C for 0.5 hours, and the polymerization reaction was terminated. It was adjusted to pH 4 by adding 30% aqueous sodium hydroxide solution, and the concentration was adjusted to 40% with ion exchanged water. Let the reactant be a copolymer (PC-4).

(5) Production Example 5 (Production of copolymer PC-5)

Prepare 100.3 g of ion-exchanged water and 179.5 g of α-(3-methyl-3-butenyl)-ω-hydroxy-poly(n=57)oxyethylene in a thermometer, stirrer, dropping funnel and After the nitrogen gas was introduced into the reaction vessel of the tube, it was dissolved uniformly while stirring, the ambient gas was replaced with nitrogen, and the temperature of the reaction system was brought to 60°C in a warm water bath. Next, 9.8 g of a 10.0% sodium persulfate aqueous solution was dropped in 3.0 hours, and at the same time, an aqueous solution of 15.6 g of acrylic acid dissolved in 78.1 g of ion-exchanged water was dropped in 3 hours. At the same time, 9.4 g of ions An aqueous solution in which 1.4 g of 3-mercaptopropionic acid and 1.0 g of ascorbic acid were dissolved in the exchange water took 4.0 hours to drip. Thereafter, the temperature was maintained at 60°C for 0.5 hours, and the polymerization reaction was terminated. It was adjusted to pH 4 by adding 30% aqueous sodium hydroxide solution, and the concentration was adjusted to 40% with ion-exchanged water. Let this reactant be a copolymer (PC-5).

The mass average molecular weight of the copolymer is measured by gel permeation chromatography in accordance with the measurement conditions shown below.

Measurement conditions

Device: Shodex GPC-101 (Showa Denko)

Column: OHpak SB-806M HQ+SB-806M HQ (Showa Denko)

Detector: Differential Refractometer (RI)

Eluent: 50mM aqueous solution of sodium nitrate

Flow rate: 0.7mL/min

Column temperature: 40℃

Sample concentration: 0.5% by mass of eluent solution

Standard materials: polyethylene glycol, polyethylene oxide (Agilent)

Water was removed from the copolymers PC-1 to PC-5 produced in each of Production Examples 1 to 5, and the solution was adjusted to a concentration of 5% using heavy water, and measurement was performed with 300 MHz NMR. From this, it was confirmed that individual monomers had been polymerized into copolymers. Types of each component (component A, component B (component B1, component B2)) used in each of the copolymers PC-1 to PC-5 manufactured by Manufacturing Examples 1 to 5, and their respective masses (%) The values of the average molecular weights of the copolymers PC-1 to PC-5 measured above are shown in Table 3 below.

However, in the description of Table 3 above, the following terms are used to indicate the following meanings.

L-1: α-methyl-ω-methoxy-poly(n=9) oxyethylene

L-2: α-methyl-ω-methoxy-poly(n=45) oxyethylene

L-3: α-methyl-ω-methoxy-poly(n=113) oxyethylene

L-4: α-Methylallyl-ω-hydroxy-poly(n=113) oxyethylene

L-5: α-(3-methyl-3-butenyl)-ω-hydroxy-poly(n=57)oxyethylene

L-6: Hydroxyethyl acrylate

M-1: methacrylic acid

M-2: Acrylic

3. Preparation of carboxylic acid type polycarboxylic acid type dispersant

The copolymers PC-1 to PC-5 manufactured in the above 2. were diluted with ion-exchanged water and 30% aqueous sodium hydroxide solution at pH conversion to a concentration of 20% to be a carboxylic acid type polycarboxylic acid type dispersant. SP-1~SP-12. The copolymer used in the carboxylic acid type polycarboxylic acid type dispersant and the pH finishing are shown in Table 4 below.

4. Evaluation of compatibility between defoamer and carboxylic acid polycarboxylic acid type dispersant

(1) Test method

In 1. The antifoaming agents af-1~af-9, af-e1~af-e3 to be synthesized weighed 5 grams respectively, and 1000 grams of carboxylic acid polycarboxylic acid type dispersant SP prepared in 3. -1~SP-12. With this, the samples (mixed liquids) of Examples 1 to 20 and Comparative Examples 1 to 3 were completed. The types of samples (mixed solutions) of carboxylic acid-based polycarboxylic acid type dispersants and defoamers used in Examples 1 to 20 and Comparative Examples 1 to 3 are shown in Table 5 below. Furthermore, the sample (mixed solution) was stored in a state of being statically kept in a constant temperature room until the liquid temperature reached 30°C. In addition, after the sample that had been left to stand was taken out and sufficiently stirred, the compatibility was evaluated in a constant temperature room at 30°C.

(2) Evaluation method and evaluation result of compatibility

Here, the time immediately after the stirring is completed is 0 hours (start time counting). In Examples 1 to 20 and Comparative Examples 1 to 3, every 6 hours, 12 hours, and 24 hours from the start of the time counting The elapsed time is a time t until the mixed liquid, the carboxylic acid-based polycarboxylic acid type dispersant SP-1, etc., and the defoaming agent af-1 etc. are separated from each other.

The standard for evaluating compatibility is

A: No separation was confirmed more than 24 hours since the start of measurement (24≦t)

B: Separation is confirmed within 12 hours or more and less than 24 hours (12≦t<24)

C: Separation was confirmed within 6 hours or more and less than 12 hours (6≦t<12)

D: Separation was confirmed within 6 hours (t<6).

However, as long as it is C or more, there is no problem in practicality. The evaluation results of this compatibility are shown in Table 5 below.

table 5

According to this, the samples of Examples 1 to 20 using the defoamers af-1 to af-9 satisfying the first condition and the second condition of the present invention were not confirmed to be separated until 6 hours ( Evaluation C or higher). That is, it shows good compatibility with carboxylic acid type polycarboxylic acid type dispersants. In particular, it satisfies the first and second conditions, and uses a straight-chain structured unsaturated alcohol A1 with 16 to 18 carbons (refer to Table 2) and a branched-chain structure saturated alcohol A2 with 16 carbons (reference Table 2) The formed antifoaming agents af-1, af-2, af-3, af-4, and af-7, in the compatibility between the carboxylic acid polycarboxylic acid type dispersant and the antifoaming agent, are No separation was confirmed in "more than 24 hours", and it was Evaluation A. That is, it was confirmed that by using a linear-chain unsaturated alcohol or a branched-chain saturated alcohol, particularly good results were shown (Examples 1 to 15, Example 18).

On the other hand, in the case of the linear structure and saturated alcohols A3 to A5, separation was confirmed in "6 hours or more and less than 12 hours" or "12 hours or more and less than 24 hours" (Example 16, 17, 19, 20), although there is not much problem in actual use, it is Evaluation B or Evaluation C. From the above results, it shows the meaning of satisfying the first condition and the second condition of the present invention, and the use of alcohols having 14 to 22 carbon atoms and unsaturated and/or branched primary alcohols.

In addition, in the case of the defoamer af-e1 that did not satisfy the first condition and the defoamer af-e2 that did not satisfy the second condition, separation was confirmed in less than 6 hours, and this was Evaluation D. This shows that the antifoaming agent of the present invention, in the antifoaming agent (polyoxyalkylene compound) represented by the general formula (1), satisfies both the first condition and the second condition The meaning of compatibility between dispersants. However, although the defoamer af-e3 does not satisfy the first condition, the evaluation of compatibility is good (evaluation A). However, the evaluation of the defoaming efficiency described below is low, so it is classified as Comparative Example 3 here.

5. The effect of antifoaming effect caused by antifoaming agent

Next, the effect of the defoaming effectiveness of various synthesized antifoaming agents af-1 and the like (polyoxyalkylene compound) was confirmed. Initially, the concrete composition was prepared as shown below.

(1) Modulation of concrete composition

In the 55L forced twin-screw mixer, ordinary Portland cement (a blend of Pacific Cement, Ube Mitsubishi Cement, Sumitomo Osaka Cement, and the above three brands in equal amounts, specific gravity = 3.16) and fine bone as bone material The materials (Oikawa water system sand, specific gravity = 2.58) and coarse aggregate (Okazaki gravel, specific gravity = 2.66) were input at the mixing ratio shown in Table 6, and after 10 seconds of dry mixing, the fluidity became 18±2.5cm and the air volume becomes 4.5±0.5%, the AE agent "AE-300 (trade name of Takemoto Oil and Fats Co., Ltd.)" is 0.0025% by mass with respect to cement, and is of the carboxylic acid type described in Table 4. Dispersants SP-1, SP-3, SP-12, antifoaming agents af-1~af-9, af-e3 described in Table 2 are adjusted to the amount shown in Table 8 below and added with kneading water, And implement the kneading for 90 seconds. Here, the defoamer af-1 and the like and the carboxylic acid polycarboxylic acid type dispersant SP-1 and the like are considered to be a part of kneaded water. In the same manner, the carboxylic acid-based polycarboxylic acid type dispersants SP-5 and SP-9 described in Table 4 and the defoaming agents af-1 to af-9 described in Table 2 were mixed at the mixing ratio shown in Table 7 And af-e3 are kneaded in the types shown in Table 9 below.

(2) The effect of defoaming effectiveness

According to JIS-A1128, the "air volume (%)" was measured for the concrete composition immediately after kneading. The air volume (%) indicates the volume% of the hydraulic composition. Furthermore, while measuring the above-mentioned air volume (%), the "fluidity (cm)" was measured in compliance with JIS-A1101. With the air volume (%), the defoaming performance of the defoaming agent was confirmed. The measurement results of the air volume (%) and the fluidity (cm) are shown in Tables 8 and 9 below.

Table 8

According to this, it can be confirmed that the defoamers af-1 to af-9 satisfying the first condition and the second condition of the present invention can exert good defoaming performance (Examples 21 to 44). On the other hand, it was also confirmed that when the defoaming agent af-e3 synthesized for comparison was used, the defoaming effect was significantly reduced compared to af-1 to af-9 (Comparative Examples 4 to 8). In af-e3, even if the added amount (mass %/dispersant) to the carboxylic acid-based polycarboxylic acid type dispersant exceeds 1.00, the air amount (%) is 10% or more, so the amount is not added. That is, when it is confirmed that the defoamer of the present invention is used as one of the essential components of the hydraulic composition, in addition to the compatibility already described, even a small amount of the defoamer added can exert high Bubble efficiency.

Industrial availability

The antifoaming agent for hydraulic compositions of the present invention can be used as an antifoaming agent when preparing hydraulic compositions. Furthermore, the additive for a hydraulic composition of the present invention can be used as an additive when preparing a hydraulic composition. The hydraulic composition of the present invention is excellent in compatibility with a dispersant, and by using a defoaming agent that can exhibit high defoaming efficiency in a small amount of addition, it can be beneficially used in various building components or building components.

Claims (13)

A defoamer for hydraulic compositions is a polyoxyalkylene compound represented by the following general formula (1), RO-(AO)p-(EO)n-(AO)mH... (1), and Satisfy: The first condition: 0.16≦n/(p+n+m)≦0.40; and the second condition: 20≦p+n+m≦48; where R is an alkyl group with 8 to 30 carbon atoms or Alkenyl, and a straight-chain or branched structure; AO is the same or different alkylene oxide groups with 3 to 18 carbon atoms, EO is the oxyethylene group; p, n, m are the average addition Into Mohrs, and p is 0 or more, n is 1 or more, and m is 1 or more. The defoamer for a hydraulic composition according to claim 1, wherein R in the general formula (1) is an alkyl group or an alkenyl group having 14 to 22 carbon atoms, and is self-unsaturated and/or branched The hydroxyl group-removing residue of the primary alcohol contains 50% by mass or more with respect to the total amount of R. The defoamer for a hydraulic composition according to claim 1, wherein the AO of the aforementioned general formula (1) is an oxypropylene group. The defoamer for a hydraulic composition according to claim 2, wherein the AO of the aforementioned general formula (1) is an oxypropylene group. The defoamer for a hydraulic composition according to claim 1, wherein the first condition further satisfies the condition of 0.16≦n/(p+n+m)≦0.38. The defoamer for a hydraulic composition according to claim 2, wherein the first condition further satisfies the condition of 0.16≦n/(p+n+m)≦0.38. The defoamer for a hydraulic composition according to claim 3, wherein the first condition further satisfies the condition of 0.16≦n/(p+n+m)≦0.38. The defoamer for a hydraulic composition according to claim 4, wherein the first condition further satisfies the condition of 0.16≦n/(p+n+m)≦0.38. The defoamer for a hydraulic composition according to claim 1, wherein the second condition further satisfies the condition of 24≦p+n+m≦40. The antifoaming agent for a hydraulic composition according to claim 1, wherein the carbon number of R in the general formula (1) is 14-22. An additive for a hydraulic composition is a defoamer for a hydraulic composition described in claim 1, a carboxylic acid-based polycarboxylic acid type dispersant, and water as essential components. A hydraulic composition is a defoamer for hydraulic compositions described in claim 1, a carboxylic acid-based polycarboxylic acid type dispersant, and cement as essential components. A hydraulic composition comprising the defoamer for hydraulic composition described in claim 1, a carboxylic acid-based polycarboxylic acid type dispersant, cement, and aggregates containing fine aggregates and/or coarse aggregates as essential components .