JPH01135510A - Defoaming agent - Google Patents

Abstract

PURPOSE:To obtain a sufficient defoaming characteristics over a wide temperature range, by using a defoaming agent consisting of a compound which is produced from an esterification of a higher alcohol added with an alkylene oxide thereto and a higher fatty acid. CONSTITUTION:A compound as shown in the general formula (1) is obtained by causing a catalytic esterification reaction using paratoluene sulfonic acid as a catalyst between a product resulting from the addition reaction of alkylene oxide and higher alcohols using an alkaline catalyst and higher fatty acids. The use of such compound as such or emulsified in water as a refoaming agent results in the attainment of a sufficient defoaming characteristics over a wide temperature range.

Description

[Detailed Description of the Invention] [Field of Industrial Application] The present invention relates to an antifoaming agent, and more specifically, the present invention relates to an antifoaming agent, and more specifically, an antifoaming agent that is effective at a low concentration and against harmful foaming generated in various industrial processes and wastewater. The present invention relates to an antifoaming agent having foam-breaking and foam-inhibiting properties.

Antifoaming agents are used in the paper industry, textile industry, fermentation industry, paint industry,
Synthetic resin industry, synthetic rubber industry, etc., wastewater (sewage, water supply,
It is used for processing (human waste, factories, etc.).

[Conventional technology]

Conventionally, mineral oils, higher alcohols, waxes, silicone resins, fatty acids, and mixtures thereof have been used as these antifoaming agents. However, these antifoaming agents are insoluble or poorly soluble in water, so in the paper industry, they cause stains on wires and uneven spotting on paper, and in the textile industry, they cause problems due to adhesion to cloth.
In the paint industry, problems such as pinholes or oil spots can occur on the coating surface.

There is also a method in which the antifoaming agent is made into an emulsified state using a solvent or an emulsifier, but in this case, the antifoaming effect is reduced.

[Problem that the invention seeks to solve]

In order to improve this drawback, it has been proposed to use polyoxyalkylene glycol derivatives (Japanese Patent Publication No. 4
5-7973, Special Publication No. 61-16484, etc.) However,
With the polyoxyalkylene glycol derivatives disclosed in these documents, the effect changes depending on the temperature of the foaming liquid to be defoamed, so a defoaming diameter cannot be obtained over a wide range of temperatures. The temperature of white water varies from about 20 to 60 degrees depending on seasonal changes and thermal conditions.
Fluctuations down to 0°C. With conventional antifoaming agents, the foam-breaking and foam-inhibiting properties change due to such temperature fluctuations, so it has been necessary to increase the amount used depending on the situation.

The present inventors have eliminated these drawbacks of conventional antifoaming agents,
The present invention was completed as a result of intensive research aimed at developing a self-emulsifying antifoaming agent that can form a stable emulsion in water.

[Means for solving problems]

That is, the present invention is based on general formula (1), or represents an alkenyl group, m represents an integer of 2 to 9, and n represents an integer of 4 to 15, provided that the ethyleneoxy group and propyleneoxy group in the formula are added in a random or block form. shall be. ] An antifoaming agent containing a compound represented by the following is provided.

The antifoaming agent of the present invention is limited to one having a well-balanced combination of hydrophilic groups and lipophilic groups. For example, if n is larger than the above-specified range, the hydrophilicity will increase and the polymer will be in a soluble state at room temperature, resulting in a marked decrease in antifoaming properties. Also,
If it is smaller than this range, the lipophilicity will increase, and the self-emulsifying property and diffusibility will deteriorate. On the other hand, if m is outside the above specified range, the effect will vary depending on the temperature of the foaming liquid to be defoamed, making it difficult to obtain sufficient defoaming properties over a wide range of temperatures.

-a In formula (I), R1 is an alkyl or alkenyl group having 12 to 22 carbon atoms, a nonylphenyl group, or an octylphenyl group, but other groups are not suitable. For example, when the number of carbon atoms is smaller than the above range has weak antifoaming properties, and if the number of carbon atoms is larger than this range, self-emulsifying property and diffusibility will be poor. When the number of carbon atoms is small, antifoaming properties are weak, and when the number of carbon atoms is larger than the range, self-emulsifying properties and diffusibility are poor.

The antifoaming agent of the present invention may be used as it is as a undiluted solution, or may be used after being emulsified in water, and its performance will not change due to this.Also, it may be used in combination with a solvent, etc. You can also do that.

The antifoaming agent of the present invention is produced by adding an alkylene oxide to a higher alcohol using an alkali catalyst or the like, and then adding an esterification catalyst such as para-toluenesulfonic acid to a compound obtained by adding an alkylene oxide to a higher alcohol. It is obtained by esterification reaction at high temperature with fatty acids.

Alternatively, it can also be obtained by dehydrochlorination reaction with higher fatty acid chloride or transesterification reaction with lower alcohol higher fatty acid ester. Regardless of these manufacturing methods, the performance of the antifoaming agent obtained is almost unchanged.

〔Example〕

Hereinafter, the present invention will be explained in more detail by giving synthesis examples and application examples of the antifoaming agent according to the present invention. However, these examples are not meant to limit the invention.

Synthesis Example 1 Using an alkali catalyst, a mixture of propylene oxide and ethylene oxide is blown into an alkyl alcohol or an alkenyl alcohol to cause a random addition reaction,
Alternatively, propylene oxide is blown in, then ethylene oxide is blown into the block, and the resultant compound is subjected to an esterification reaction at high temperature with a higher fatty acid using para-toluenesulfonic acid as an esterification catalyst to obtain a compound. Ta.

The composition and properties of the product thus obtained are shown in Table 1 below.

The following is a blank synthesis example 2 Synthesis obtained by blowing a mixture of propylene oxide and ethylene oxide into alkylphenol using an alkali catalyst and causing a random addition reaction, or by blowing propylene oxide and then blowing ethylene oxide into the block and causing an addition reaction. Using para-toluenesulfonic acid as an esterification catalyst, the compound was esterified with higher fatty acids at high temperature to obtain a compound.

The composition and properties of the obtained product are shown in Table 2.

Below is a margin application example The defoaming effects of the defoaming agent of the present invention and a comparative product were compared and studied using the following method.

Test method The test device π is a transparent glass column with a diameter of 64 m and a rolled length of 1000 mm, with a column on the outside to keep the foaming liquid warm.
A transparent glass column with a diameter of 95 mm and a length of 1000 mm was provided as a jacket for hot water. The test was conducted using a circulation method in which the foaming liquid was sent from the bottom of the column to the top of the column using a pump, and then dropped to the center of the bottom of the column.

In the test, an antifoaming agent was added to the foaming solution No. 11, and circulation was performed at a constant flow rate for 5 minutes, and the height of the foam was measured over time. Next, the circulation was stopped for 2 minutes, and the height of the bubbles was measured to see how the bubbles disappeared (foam suppression effect). Two cycles of circulation and stopping were performed (bubble breaking effect).

A comprehensive evaluation of each antifoaming agent was performed based on the above foam suppressing and foam breaking effects.

(1) Foaming WL: Rosin-based sizing agent (Company A product) 0.1%
Aluminum sulfate pl+4.5 (2) Foaming liquid amount: 11 (3) Circulating flow M: 4.5β/min (4) Antifoaming agent addition amount: 10 mg/f (5) Temperature = 15°C, 30°C and 45°C The antifoaming agents tested were a total of 10 types, including 5 synthetic products of the present invention and 5 comparative products shown in Tables 1 and 2, and detailed contents of these 5 comparative products are shown in Table 3.

Table 3 The results of the application examples are shown in Table 4, and the composite product of the present invention showed excellent antifoaming properties (foam suppressing properties, foam breaking properties) at any temperature.

Table 4 Bubble height (Kin) Bubble height (■) Bubble height (Kin) Procedural amendment (voluntary) March 7, 1985 Director-General of the Patent Office Kunio Ogawa 1, Indication of the case Showa 1962 Patent Application No. 293105 2, Name of the invention 4, Agent address: Shizuka Toranomon Building, 8-10 Toranomon-chome, Minato-ku, Tokyo 105 Tel: 504-07215, ``Details of the invention'' in the specification to be amended Explanation column 6, from line 10 on page 6 of the detailed statement of amendments to the bottom line on page 10, will be amended as follows.

[Examples] The present invention will be explained in more detail below with reference to synthesis examples and application examples of the antifoaming agent according to the present invention. However, these examples are not intended to limit the present invention.

Synthesis Example 1 134 g (1/2 mole) of oleyl alcohol and 1 g of caustic soda as a catalyst were placed in a 11 autoclave, and the atmosphere was purged with nitrogen. A mixed solution of 232 g (4 moles) of propylene oxide and 264 g (6 moles) of ethylene oxide was
Temperature 140~160℃, pressure 1~5kg/an! was blown into the solution to cause a random addition reaction. The catalyst was neutralized with phosphoric acid, dehydrated in vacuum, and the precipitated crystals were filtered off to obtain 621 g of a random adduct of oleyl alcohol with propylene oxide and ethylene oxide.

Next, 420 g (1/3
1 mole), 94 g (1/3 mole) of oleic acid, and 1 g of para-toluenesulfonic acid as an esterification catalyst were added, and a dehydration reaction was carried out at a temperature of 200 to 220 °C for 6 hours under a nitrogen stream to obtain -1 C+ 5) hso ( (C3111,0) s (CJ
40) + z) C-self, Hl.

508 g of Synthesis 1 was obtained, having the structure:

This synthetic product 1 had an acid value of 1.5 and a saponification value of 36.8, was a pale yellow transparent liquid at room temperature, and showed a stable emulsified state when diluted with water to 1%.

Synthesis Example 2 134 g (1/2 mol) of oleyl alcohol and 1 g of caustic soda as a catalyst were placed in a No. 11 autoclave.
After purging with nitrogen, 232 g (4 mol) of propylene oxide was added at a temperature of 140 to 160°C and a pressure of 1 to 5 kg/
Blow in with ct and react. Then ethylene oxide 2
64 g (6 mol) was blown into the block under the same conditions to cause an addition reaction. Neutralize the catalyst with phosphoric acid, perform vacuum dehydration,
The precipitated crystals were filtered to obtain 620 g of a propylene oxide and ethylene oxide block adduct of oleyl alcohol.

Next, 420 g (173
mol), 94 g (1/3 mol) of oleic acid, and 1 g of para-toluenesulfonic acid as an esterification catalyst were added, and a dehydration reaction was carried out at a temperature of 200 to 220 °C for 6 hours under a nitrogen stream to obtain C+allzsO(CJbO)s ( CJ40) +z
C-C+Jz: Composite product 2 shown by the structure of + is 508
It was obtained in the amount of g.

This synthetic product 2 had an acid value of 1.7 and a saponification value of 36.8, was a pale yellow transparent liquid at room temperature, and exhibited a stable emulsified state when diluted with water to 1%.

Similarly, synthetic products 3, 4, and 5 were obtained by changing the number of moles of alcohol, fatty acid, and alkylene oxide added and their combinations.

Synthetic products 1 to 5 of the present invention thus obtained are shown in Table 1 below.

Table 1 Outside 1 at a water temperature of 20°C.

As an antifoaming agent, the product of the present invention was emulsified to 1% with water at 20° C., and the liquid was left to stand for 24 hours.

Synthesis Example 3 103 g (1/2 mol) of octylphenol and 1 g of caustic soda as a catalyst were placed in a No. 11 autoclave.
After the atmosphere was replaced with nitrogen, a mixed solution of 232 g (4 moles) of propylene oxide and 264 g (6 moles) of ethylene oxide was blown into the reactor at a temperature of 140 to 160' C1 and a pressure of 1 to 5 kt/cd to cause random addition reactions. The catalyst was neutralized with phosphoric acid, dehydrated in vacuum, and the precipitated crystals were filtered off to obtain 590 g of a random adduct of octylphenol with propylene oxide and ethylene oxide.

Next, 399.3 g of this compound (
173 mol) and 94 g (1/3 mol) of oleic acid,
1 g of para-toluenesulfonic acid was added as an esterification catalyst, and a dehydration reaction was carried out at a temperature of 200 to 220° C. for 6 hours under a nitrogen stream to obtain 487 g of synthetic product 6 having the structure shown below.

This synthetic product 6 had an acid value of 2.0 and a saponification value of 38.3, and was a pale yellow transparent liquid at room temperature, and showed a stable emulsified state when diluted with water to 1%.

Synthesis Example 4 103 g (1/2 mol) of octylphenol and 1 g of caustic soda as a catalyst were placed in a No. 11 autoclave.
After purging with nitrogen, 174 g (3 mol) of propylene oxide was blown into the reactor at a temperature of 140 to 160°C and a pressure of θ to 5 kg/- to cause a reaction. Then ethylene oxide 242
g (5.5 mol) was blown into the block under the same conditions to cause an addition reaction. The catalyst was neutralized with phosphoric acid, dehydrated in vacuum, and the precipitated crystals were filtered off to obtain 510 g of a propylene oxide and ethylene oxide block adduct of octylphenol.

Next, 346 g (l/3
mol), 94 g (1/3 mol) of oleic acid, and 1 g of para-toluenesulfonic acid as an esterification catalyst were added, and a dehydration reaction was carried out at a temperature of 200 to 220°C for 6 hours under a nitrogen stream to form a product with the structure shown by Synthesis product 8 was obtained in an amount of 434 g.

This synthetic product 8 has an acid value of 2.2 and a saponification value of 43.0, is a pale yellow transparent liquid at room temperature, and exhibits a stable emulsified state when diluted with water to 1%.

In the same manner, synthetic products 7, 9 and 10 were obtained by changing the number of moles of alcohol, fatty acid and alkylene oxide added and the combination thereof.

Synthetic products 6 to 1O of the present invention thus obtained
are shown in Table 2 below.

Table 2 *Outside 1 at a temperature of 20°C 1 As an antifoaming agent, the product of the present invention was emulsified to 1% in water at 20°C, and the state of the liquid was observed after being left for 24 hours. J or more

Claims (1)

[Claims] 1. General formula (I), ▲ Numerical formula, chemical formula, table, etc.▼... (I) [In the above formula, R_1 is an alkyl or alkenyl group having 12 to 22 carbon atoms, nonylphenyl group or octylphenyl group, R_2 represents an alkyl or alkenyl group having 11 to 21 carbon atoms, m represents an integer of 2 to 9,
n represents an integer of 4 to 15, provided that the ethyleneoxy groups and propyleneoxy groups in the formula are added randomly or in blocks. ] An antifoaming agent characterized by containing a compound represented by these.