JP2003265904A - Defoaming agent composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a defoaming agent composition showing satisfactory defoaming property and dispersibility with a small amount of addition and suitably used to reduce the separation time of cement and aggregates from water as a defoaming agent for slate. <P>SOLUTION: The defoaming agent composition contains 85 to 98 wt.% of a compound expressed by formula (I): R<SP>1</SP>O[(C<SB>3</SB>H<SB>6</SB>O)<SB>k</SB>(C<SB>2</SB>H<SB>4</SB>O)<SB>l</SB>]H and 2 to 15 wt.% of a compound expressed by formula (II): HO(AO)<SB>m</SB>H. In formula (I), R<SP>1</SP>represents a 12-22C hydrocarbon group, k ranges from 20 to 50 and l ranges from 1 to 25. In formula (II), AO represents a mixed polyoxyalkylene group obtained by randomly copolymerizing ethylene oxide and propylene oxide, the proportion of oxyethylene groups in the polyoxyalkylene group ranges from 20 to 50 wt.%, and m ranges from 5 to 25. <P>COPYRIGHT: (C)2003,JPO

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to an antifoaming composition used in the chemical industry, fermentation industry, synthetic rubber industry, civil engineering industry, paper industry, sewage treatment facility and the like. More specifically, the present invention relates to a defoaming agent composition which prevents foam troubles occurring in activated sludge treatment in sewage treatment facilities, reaction aging in fermentation industry, manufacturing process or distillation process in chemical industry, kneading of concrete and the like.

[0002]

2. Description of the Related Art Defoamers conventionally used in the chemical industry, fermentation industry, synthetic rubber industry, civil engineering industry, paper industry, sewage treatment facility, etc. Is being improved. For example, in recent sewage treatment facilities, seasonal fluctuations in treatment amount and water quality are large,
Depending on the driving conditions, a large amount of bubbles are generated, and there are problems that make driving difficult. Moreover, when concrete is kneaded in the civil engineering industry, there arises a problem that air bubbles are mixed, which causes deterioration in appearance quality and compression strength of the molded product.
In the paper industry, since wood is used as a starting material, foaming substances such as lignin, resin, and polysaccharides are mixed in water, and sizing agents, cleaning agents, deinking agents, and paper strengthening are added during the process. Since foaming substances such as agents are used, there is always the problem of damage due to bubbles. Antifoaming agents are widely used to solve the above problems. As a general defoaming agent, compounds such as silicone oil, mineral oil, vegetable oil, aliphatic alcohol, fatty acid, metal soap, fatty acid amide, polyoxyalkylene glycol, polyoxyalkylene alkyl ether, and polyoxyalkylene fatty acid ester are used. Has been done.

Since conventional antifoaming agents are insoluble or sparingly soluble in water, when the antifoaming agents were added to the system to be defoamed, they were sometimes separated or floated. Some of the conventional polyoxyalkylene-based antifoaming agents are slightly water-soluble, but these conventional water-soluble antifoaming agents are generally insufficient in defoaming effect. In order to improve the dispersibility and solubility of these polyoxyalkylene-based defoaming agents in the system to be defoamed, the main agent of the defoaming agent and water are mixed as disclosed in JP-A-9-117608. If necessary, nonionic solubilizers such as polyoxyethylene sorbitan monolaurate, polyoxyethylene sorbitan trilaurate, polyoxyethylene sorbitan monooleate, and polyoxyethylene stearate, fatty acid ammonium salts, and dodecylbenzene. A method of mixing an anionic solubilizer such as sulfonic acid / ammonium salt and dioctylsulfosuccinic acid sodium salt, and a cationic solubilizer such as octadecylamine acetate, stearyl dimethyl betaine, and sodium laurylaminopropionate are also considered. However, the defoaming agent in which the terminal hydroxyl group of the alkylene oxide adduct is esterified with a fatty acid is liable to generate scum, and when left for a long time, the defoaming agent separates in an aqueous solution to stain the equipment being used, or to obtain sufficient foam suppressing property. There are problems such as not being able to obtain foam breaking properties. Further, the use of the above-mentioned solubilizer has a drawback that it causes foaming and deteriorates the defoaming performance. As a cement additive, a water reducing agent that reduces the amount of water used when kneading concrete, a fluidizing agent that maintains fluidity after kneading, a setting accelerator that shortens setting time, and an amount of air in concrete AE agents and the like for adjustment are known. In the production of slate products, cement, aggregate and water are the main components, and the kneaded material for the object to be molded is placed on the perforated plate for draining placed on the lower mold of the press and dehydrated and pressed. A molded product is molded, but there is a problem in that the productivity of slate is lowered because the dehydration property in the draining process of the dehydration press is poor only by mixing these. However, the already known defoaming agents for cement have not been sufficiently effective against this problem, and especially the polyoxyalkylene-based defoaming agent has a defoaming performance and a system to be defoamed. There is a drawback that the dispersibility cannot be satisfied at the same time.

[0004]

From the above, there is a strong demand for the development of a polyoxyalkylene defoaming agent which simultaneously satisfies the defoaming performance and the dispersibility in the system to be defoamed. An object of the present invention is to provide a defoaming agent composition which can satisfy the defoaming property and dispersibility at the same time by adding a small amount, and can be suitably used as a defoaming agent for slate with cement and aggregate and shortening the separation time from water. To provide things.

[0005]

That is, the present invention is
(1) 85 to 98% by weight of a compound represented by the following formula (I), R ¹ O [(C ₃ H ₆ O) _k (C ₂ H ₄ O) ₁ ] H (I) [in the formula, R ¹ is a hydrocarbon group having 12 to 22 carbon atoms,
k is an average number of added moles of oxypropylene group and is 20 to 50.
And 1 is the average number of moles of oxyethylene groups added, which is 1 to
25. The oxypropylene group and the oxyethylene group are bonded in a block shape. ] An antifoam composition comprising 2 to 15% by weight of a compound represented by the following formula (II), HO (AO) _m H (II) [wherein AO is ethylene oxide and propylene oxide] It is a mixed polyoxyalkylene group copolymerized at random, the content of the oxyethylene group in the mixed polyoxyalkylene group is 20 to 50% by weight, and m is 5 to 2
It is 5. ], And (2) 1 to 20 parts by weight of water is further added to 100 parts by weight of the defoaming agent composition described in (1) 1 above.

[0006]

BEST MODE FOR CARRYING OUT THE INVENTION R ¹ of the compound represented by the formula (I) used in the present invention is a hydrocarbon group having 12 to 22 carbon atoms. Examples of R ¹ include a dodecyl group, a tridecyl group, a hexadecyl group, an octadecyl group, a docosyl group, and an oleyl group, and one or more of these can be used. From the viewpoint of defoaming property and dispersibility, hexadecyl group and oleyl group are preferable. When the number of carbon atoms is less than 12, hydrophilicity is increased and the defoaming effect is poor, and when the number of carbon atoms is more than 22, the viscosity is high and the hydrophobicity is increased, so that dispersibility in the system to be defoamed is poor.

The compound represented by the formula (1) is an adduct of alkylene oxide, in which the oxypropylene group and the oxyethylene group are bonded in a block form, and the defoaming performance is poor in the case of random addition. The compound represented by the formula (1) is usually obtained by subjecting an alcohol having a hydrocarbon group having 12 to 22 carbon atoms to an addition reaction of propylene oxide and then an addition reaction of ethylene oxide.
k is the average number of moles of oxypropylene groups added, 20
-50, preferably 35-45. 1 is the average number of moles of oxyethylene groups added, and is 1 to 25, preferably 2 to 10. When k is less than 20 mol, the hydrophilicity is increased and the defoaming performance is poor, and when it is more than 50 mol, the hydrophobicity is increased and the dispersibility in the system for defoaming is poor.
When 1 is less than 1 mol, the hydrophobicity is increased and the dispersibility in the system to be defoamed is poor. When it is more than 25 mol, the hydrophilicity is increased and the defoaming performance is poor. In the present invention, the content of the compound (I) is 85 to 98% by weight. 8
If it is less than 5% by weight, the defoaming performance is poor, and if it exceeds 98% by weight, the dispersibility in the system to be defoamed is unfavorable.

AO of the compound represented by the formula (II) of the present invention
Is a mixed polyoxyalkylene group obtained by randomly copolymerizing ethylene oxide and propylene oxide. The content of oxyethylene groups in the mixed polyoxyalkylene groups is 20 to 50% by weight. When the content of oxyethylene group is less than 20% by weight, the hydrophobicity is increased and the dispersibility in the system to be defoamed is poor, and when it exceeds 50% by weight, the hydrophilicity is increased and the defoaming performance is improved. Inferior.

M is the average number of added moles of mixed polyoxyalkylene groups, and is 5 to 25, preferably 7 to 20.
Is. When m is less than 5 mol, the hydrophilicity is increased and the defoaming property is poor, and when it exceeds 25 mol, the viscosity is high and the dispersibility in the system for defoaming is poor. In the present invention, the content of the compound represented by the formula (II) is 2 to 15% by weight.
Is. If it is less than 2% by weight, the dispersibility in the system to be defoamed is poor, and if it exceeds 15% by weight, the hydrophilicity is increased and the defoaming performance is poor.

It is preferable to add water to the antifoam composition of the present invention, since the dispersibility in the system to be defoamed can be enhanced by further containing water.
In that case, the content of water is 1 to 20 parts by weight, preferably 3 to 15 parts by weight, based on 100 parts by weight of the total amount of the compound represented by the formula (I) and the compound represented by the formula (II). . The content of 1 part by weight or more is preferable because the dispersibility in the system to be defoamed can be enhanced, and the content of more than 20 parts by weight is not preferable because bacteria are easily proliferated. As water, it is preferable to use tap water, industrial water, ion-exchanged water, or distilled water. The defoaming agent composition of the present invention contains a pH adjusting agent, an antiseptic agent, an anticorrosive agent, a pigment,
Metal soap and the like can be contained. As a method of using the defoaming agent composition of the present invention, it may be added directly to the system to be defoamed, or an antifoaming agent composition diluted with water may be added. In addition, other antifoaming agents such as mineral oils, vegetable oils, aliphatic alcohols, fatty acids, etc., higher alcohols, alkylene oxide adducts such as fatty acid alkylphenols, and nonionic surfactants within the range that does not impair the effects of the present invention. You may use together with an agent. The amount of the antifoam composition of the present invention added to the system to be defoamed is 0.0001 to 0.1.
Weight percent is preferred.

[0011]

The present invention will be described in more detail based on the following examples. Production Example 1 Production of Compound (I) 96.0 g of octadecenyl alcohol and 3.29 g of potassium hydroxide as a catalyst were placed in a reaction vessel, heated to 70 ° C. and dissolved, and then air in the system was removed. After sufficiently substituting with nitrogen gas, the temperature was raised to 85 ° C. and dehydration was performed under reduced pressure of 0.004 MPa or less. Then raise the temperature to 120 ° C,
888.5 g of propylene oxide was gradually injected at a pressure in the reaction vessel of 0.5 MPa or less. After press-fitting, until the pressure in the reaction vessel does not decrease, 3 hours, 120 ± 5 ℃
And kept the reaction. Then ethylene oxide 74.5
g is gradually injected at a pressure of 0.5 MPa or less in the reaction vessel, and until the pressure in the reaction vessel does not decrease, 1 hour,
The reaction was continued at 120 ± 5 ° C. 35% after completion of reaction
Neutralize the catalyst by adding 6.10 g of hydrochloric acid, 110 ± 5
Dehydration was performed at a temperature of 0.004 MPa or less. The obtained reaction product was filtered to obtain 1000 g of compound (I) a1. Compound (I) a2 obtained in the same manner as in Production Example 1
~ A8 is shown in Table 1.

Production Example 2 Production of Compound (II) 130.0 g of diethylene glycol and 3.29 g of potassium hydroxide as a catalyst were placed in a reaction vessel, heated to 70 ° C. and dissolved, and then air in the system was replaced with nitrogen gas. Was sufficiently replaced, the temperature was raised to 85 ° C., and dehydration was performed under a reduced pressure of 0.004 MPa or less. After that, the temperature is raised to 120 ° C., and 25
901.2 g of a mixture of ethylene oxide of 75% by weight and propylene oxide of 75% by weight was added to the reaction vessel at a pressure of 0.5M.
The pressure was gradually increased below Pa. After press-fitting, the reaction was continued at 120 ± 5 ° C. for 3 hours until the pressure in the reaction vessel did not decrease. After the reaction was completed, 6.10 g of 35% hydrochloric acid was added to neutralize the catalyst, and dehydration was performed at 110 ± 5 ° C. and 0.004 MPa or less. The obtained reaction product was filtered to obtain 1000 g of compound (II) b1. Table 2 shows compounds (II) b2 to b6 obtained in the same manner as in Production Example 2.

[0013]

[Table 1]

[0014]

[Table 2]

Examples 1-5 and Comparative Examples 1-9 Compounds (I) a1 to a8 in Table 1 and compounds (I in Table 2
I) Using b1 to b6, water was added as necessary to prepare an antifoam composition. The obtained defoamer composition and evaluation results are shown in Tables 3 and 4. Each evaluation was performed by the following method. <Dispersibility test> 100 ml of ion-exchanged water was put in a sample bottle with a lid of 150 ml, and 1 g of an antifoaming agent was added at 20 ° C. Shake it 5 times by hand,
The state at that time was visually observed. Evaluation of dispersibility ◎: Easy dispersion ○: Dispersion △: Difficulty in dispersion

<Defoaming Test> Using an aqueous solution of saponin (reagent) having a concentration of 400 ppm as a foaming liquid, the following test was performed. Measurement of foam height: 0.8% of a 1% by weight aqueous solution of an antifoaming agent was added to 200 mL of a foaming liquid in a 1 L measuring cylinder, and the concentration of the antifoaming agent was 4 with respect to the whole foaming liquid.
It was set to 0 ppm. This graduated cylinder was placed in a constant temperature bath of 20 ° C., the temperature of the sample liquid was adjusted to 20 ° C., and air was passed through a diffuser stone at an air flow rate of 500 ml / min by 1 minute, 3 minutes, and 5 minutes after the start of aeration. The foam height after minutes was measured. Measurement of foam disappearance time: 200 ml of the foaming liquid was placed in a 1 L graduated cylinder, placed in a constant temperature water bath at 20 ° C., and aerated through a diffuser stone until the amount of foam reached 500 ml. Then, 0.8 ml of a 1 wt% aqueous solution of an antifoaming agent was added to the surface of the foam, and the time until the foam disappeared was measured.

<Drainage test> 13 g of dry pulp, 800 g of water, 0.4 g of antifoaming agent (dry pulp,
0.0 for the total amount of water and Portland cement
4% by weight) was added and stirred. Add 187 g of Portland cement to this and stir for 60 seconds, then immediately add 0.0
Filtration was performed using a filter paper under a reduced pressure of 4 MPa, and the time at which 450 g of the filtrate was collected at room temperature was measured. Moreover, the number of bubbles on the surface of the filtrate was measured.

[0018]

[Table 3]

[0019]

[Table 4]

Comparing Examples 1 to 5 with Comparative Examples 1 to 9, the Examples are good in dispersibility, defoaming property and drainage property. Some of the comparative examples have inferior dispersibility, and also in terms of defoaming property, both foam height and foam disappearance time are poor. Also,
It can be seen that also in the drainage, the filtration time and the number of bubbles on the surface of the filtered material are increased.

[0021]

The antifoaming agent of the present invention can be added by adding a small amount.
It shows excellent foam breaking and foam suppressing properties regardless of the type of bubbles. Further, since the defoaming agent of the present invention has excellent dispersibility in the system to be defoamed, it can be easily dispersed and used even if it is directly added or added in a form diluted with water. In particular, it can be suitably used as a defoaming agent for slate to shorten the separation time between cement and aggregate and water.

Claims (2)

[Claims] 1. A compound represented by the following formula (I):
And 98 ^{wt%, R 1 O [(C} 3 H 6 O) k (C 2 H 4 O) l] H (I) [ wherein, R ¹ is a hydrocarbon group having 12 to 22 carbon atoms,
k is an average number of added moles of oxypropylene group and is 20 to 50.
And 1 is the average number of moles of oxyethylene groups added, which is 1 to
25. The oxypropylene group and the oxyethylene group are bonded in a block shape. ] An antifoam composition comprising 2 to 15% by weight of a compound represented by the following formula (II). HO (AO) _m H (II) [In the formula, AO is a mixed polyoxyalkylene group in which ethylene oxide and propylene oxide are randomly copolymerized, and the content of the oxyethylene group in the mixed polyoxyalkylene group is 20. ˜50% by weight, m is 5-2
It is 5. ] 2. A defoaming agent composition, wherein 1 to 20 parts by weight of water is further added to 100 parts by weight of the defoaming agent composition according to claim 1.