JPH0221907A - Defoaming agent - Google Patents

Abstract

PURPOSE:To obtain a defoaming agent having both initial and sustaining defoaming effects by introducing the chain of a polymer of hydrophilic ethylene oxide between the chains of polymers of lipophilic alkylene oxide. CONSTITUTION:A polyalkylene glycol defoaming agent is based on a compd. represented by formula I (where R1 is 1-18C alkyl, etc., each of R2 and R3 is 3-8C alkylene, X is 1 or 2, each of l and n is 5-25, m is 3-15 and an oxyethylene chain accounts for 5-30wt.% in the total mol wt.). Since the chain of a polymer of hydrophilic ethylene oxide is introduced between the chains of polymers of lipophilic alkylene oxide such as propylene oxide and the position and length of the ethylene oxide polymer chain are varied, the defoaming agent is applicable to various uses and has significant initial and sustaining defoaming effects.

Description

[Detailed description of the invention] [Industrial application field]

The present invention relates to antifoaming agents, and particularly to polyalkylene glycol antifoaming agents.

[Conventional technology]

Conventional polyalgylene glycol antifoaming agents include diol types such as polypropylene glycol, polyoxyethylene-polyoxypropylene block copolymer, and polyhydric alcohols such as glycerin with an average molecular weight of about 2,000 to 4,000. Many compounds have an alkylene oxide added to them, and as for the structure of alkylene glycol, homobolymer of propylene oxide, ethylene oxide, block copolymer of propylene oxide, and random copolymer of propylene oxide are known as antifoaming agents. Furthermore, compounds in which alkylene oxide is added to higher alcohols, higher fatty acids, etc. are also known as antifoaming agents. In addition, numerous patent applications have been filed for polyalkylene glycol antifoaming agents, and in most of them, the type of alkylene oxide, the position or order of addition of the alkylene oxide, etc. are described. (Refer to Japanese Patent Publication No. 16528/1970, Japanese Patent Publication No. 30189/1989, Japanese Patent Publication No. 44551/1983, Japanese Patent Publication No. 58125/1986, and Japanese Patent Publication No. 56159583)

[Problem to be solved by the invention]

However, such conventional polyalkylene glycol antifoaming agents are not always fully satisfactory in terms of antifoaming effects such as initial antifoaming effects or sustained effects, and improvements are desired. I'm there. In general, with ethylene oxide and propylene oxide block copolymer antifoaming agents, the larger the hydrophilic ethylene oxide chain is, or the closer the ethylene oxide chain is to the end of the molecule, the more effective the initial antifoaming effect is, but the longer it lasts. . Conversely, the smaller the ethylene oxide chain that exhibits hydrophilicity, the more
or the farther the ethylene oxide chain is from the end of the molecule,
The durability of defoaming is good, but the initial defoaming effect is poor. Therefore, various patents have been issued by changing the type of alkylene oxide, the addition position, addition amount, starting material, etc., but there is still a problem that the results are not fully satisfied.

[Means to solve the problem]

This invention was made by focusing on such conventional problems. That is, the general formula, R+ [0(RaO) 42-(C11,C1120
1m-(It* 0) n-II ] x (However, R
1 is an alkyl group having 1 to 18 carbon atoms, alkylene group, alkylene group, R2 and R3 are alkylene groups having 3 to 8 carbon atoms, the same or different, X is 1 or 2, and n is 5 to 25 , m is 3 to 15, and the total molecule is 11
The weight ratio of polyoxyethylene chains in ” is 5 to 3
It is 0%. It has been discovered that an antifoaming agent containing the compound shown in ) as a main component exhibits both initial and sustained effects. (Requirements constituting the means) The alkyl group of R1 used in the present invention is methanol,
Ethanol, isopropyl alcohol, n-butanol, isobutanol, hexanol, n-octanol,
It is an alkyl group moiety such as 2-ethylhexanol, and R
The alkylaryl group 1 is an alkylallyl group such as phenol, cresol, butylphenol, dibdelphenol, nonylphenol, bisphenol Δ, and the like. The alkylene group of R1 is an alkylene group moiety such as ethylene glycol, propylene glycol, butylene glycol, hexamethylene glycol, octamethylene glycol, and the like. Further, as the alkylene oxide having 3 to 8 carbon atoms used in the present invention, propylene oxide, butylene oxide,
Examples include isobutylene oxide, detrahydrofuran, and styrene oxide. The compound used in the antifoaming agent of the present invention is obtained by adding propylene oxide to a monohydric alcohol or alkylene glycol in the presence of an alkali catalyst at a temperature of 60 to 180°C and a pressure of 0.5 to 5.03g/7cm. , is obtained by adding ethylene oxide under the same conditions, and then adding propylene oxide under the same conditions.Next, the present invention will be specifically explained with reference to production examples and examples.(%, parts are Weight basis) "Production example" 76g of propylene glycol and 10g of potassium hydroxide as a catalyst were placed in an autoclave, and the temperature was 10 to 130.
Dehydrated for 2 hours under a vacuum of 50 mm and 11 g at a temperature of 50° C. to perform alcoholation. Next, propylene oxide - 870g
is introduced and reacted at a temperature of 110 to 160°C and a pressure of 1 to 5 cm, taking about 3 hours to react. Next, 660 g of ethylene oxide is introduced at a temperature of 110 to 160°C and a pressure of 1 to 5 cm.
It takes about 2 hours to introduce and react at a temperature of 67 cm to 5.
Approximately 5 g/cm2 at 0-160℃ and pressure 1-5
It takes time to introduce and react. Next, after neutralization with hydrochloric acid, the precipitated salt was filtered off to obtain the compound of the antifoaming agent sample No. I of the present invention shown in Table 1. Further, inventive antifoaming agent samples Nos. 2 to 6 and Comparative example samples Nos. 7 to 11 were synthesized by the same method as f. (Left below) Example 1 Sodium acetate 45g, urea 5g, K21+1”0
4] g, K112PO41g, MgSO4・7
11□00.4g, drunkenness extract 2g, vitamin 13.1
00μg, bithion 5μg'7 Fe'' and y n+
4 tljl'? each consisting of 2 ppm? Brevibacterium flavum No. 2247, which had been previously cultured on a bouillon agar medium at 30°C for 24 hours, was planted on the ground in a cultured pot, and further cultured with shaking at 30°C for 24 hours. Furthermore, the main culture medium prepared separately from this, namely 90 g of sodium acetate and 8 g of urea, was added to 2111'04] g, K.
ll□PO4] g, MgSO4・711□00.4
g, Noki I Reextract 0.2g, vitamin 13tlOOμg
, p c+ + and Mn+4 each 2 ppm and CaCf
120. Add 0.2% of the various antifoaming agents shown in the table below and 4% of the preculture medium shown in the table below to the main culture medium consisting of 1 g.
300 m<0>C of the fermentation solution with a l of 7 to 85 was placed in a 1 μ volume measuring cylinder, and while an antifoaming agent was added to prevent bubbles from overflowing, the mixture was aerated at 30<0>C through a ball filter for 2 hours. The airflow rate was 1Oρ/min, and the amount of antifoaming agent consumed during that time was measured to perform a defoaming power test. The results are shown in Table 2 below. Table 2 Example 2 300nl of fermentation liquid was added to IJ2 in the same manner as in Example 1.
Add 150 mg of antifoam to a volume measuring cylinder, and aerate at 30°C (10°C/min) until the foam overflows (i.e., until the foam volume exceeds 700ml!). A defoaming durability test was conducted by measuring . The results are shown in Table 3 below. (Left below) Table 3 Solid content: 30%, emulsifier during polymerization is a mixture of sodium stearate and sodium rosinate. The foam suppression test results are shown in Table 4. Table 4 Example 3 The test method was to attach a branch 30 mm below the bottom of a glass cylinder with an inner diameter of 45 mm and a height of 750 mm, and connect the branch to a vacuum line. A bubble suppression test device was used, with a marked line indicating the point at which 140 m2 of the test liquid was filled from the bottom of the cylinder, and a scale of 1 Omm up to 600 mm. Place 140 mj2 of the latex soaked into the tube up to the marked line in a hot water bath kept at 45°C in advance, and add 0.14 mj2 of antifoaming agent to this.
After adding g and adding 1 capillary tube, 83 parts 2 m
The test liquid was styrene-butadiene copolymer latex and was tested as a 211 foaming agent for coating liquids in the production of coated paper. went. (8) Coating liquid formulation Alumina Kai 1 Non I (10, [1 part pyroic acid powder 05 parts tap water 120.0 parts Milk casein 11.0 parts TI liquid urea
11 parts Caustic soda 0.44 parts II liquid water
60.0 Part S B
R Latex (manufactured by Naugatuck) 7.0 parts After each adjustment of Ill liquid 1 and II liquid, thoroughly mix I liquid, II liquid, III liquid and the composite with a tabletop mixer to make a uniform coating liquid. I made it and tested it using the following method. Test Method Circulation Falling Force (300g of the test liquid was placed in a 500mI2 cylinder, the pump was rotated at a constant speed, it was circulated at a rate of 1500cc per minute, and the center of gravity Jt was read as time F71 elapsed.Additional antifoaming agent 1 chome) 0.3 based on the solid content of the coating liquid
%used. Table 5 Example 5 A 1% aqueous solution of linear sodium dodecylbenzenesulfonate at 50 m°C was placed in a 200n+j2 meme cylinder.
After shaking 10 times, add 0.5 m of a 10% aqueous solution of antifoaming agent.
n was added, and the amount of foam was measured 1 minute later. (Hereinafter in the margin) (Hereinafter in the margin) Antifoaming agents for surface water treatment, antifoaming agents for paints, antifoaming agents for valves,
It can be applied in the fields of antifoaming agents for double-layer fibers, etc. Patent π1 Applicant Sorichi Kogyo Pharmaceutical Co., Ltd. Ne1

【Effect of the invention】

The compound used in the antifoaming agent of the present invention has a hydrophilic ethylene oxide polymer chain introduced between the propylene oxide polymer chains into the lipophilic algylene oxide W 1, and the compound is a 1,000-mer or diol compound. It is characterized by one thing. By changing the position and chain length of the hydrophilic ethylene oxide polymer chain of this compound, it can be applied as an antifoaming agent for various purposes, and shows good initial and sustained effects.

Claims (1)

[Claims] General formulas, ▲mathematical formulas, chemical formulas, tables, etc. an alkylene group, the same or different, X is 1 or 2, l and n are 5 to 25, n is 3 to 15;
Moreover, the weight proportion of oxyethylene chains in the total molecular weight is 5 to 30%. ) An antifoaming agent characterized by containing a compound represented by the following as a main component.