JPH0355166B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to an antifoaming agent with excellent antifoaming effect, compatibility, acid resistance, and alkali resistance for use in aqueous solutions containing foaming substances. Traditionally, in various industries that handle surfactants and water-soluble polymer compounds, such as the textile/dyeing industry, paper/pulp industry, synthetic resin industry, and paint industry, various types of products have been used to prevent problems caused by foaming in various processes. Antifoaming agents are used, such as silicone-based, mineral oil-based, oil-based, alcohol-based, polyether-based,
Antifoaming agents such as amide-based, metal soap-based, and fluorine-based antifoaming agents alone and combinations thereof are well known. However, although foaming can be suppressed by adding many of these antifoaming agents,
On the contrary, it brings about various harmful effects. For example, in the case of dyeing, it causes dye spots and contamination; in the case of paints and coatings, it causes pinholes and cissing; in the case of synthetic resins, it causes cissing, pinholes, reduced adhesion, and especially in the case of water-soluble polymers,
This is a cause of obstruction to the transparency of an aqueous solution or after film formation. On the other hand, since there is no defoaming agent that can satisfy this type of defoaming, such as its original defoaming effect is poor, there has been an increasing demand for an antifoaming agent that improves these drawbacks. In response to this demand, efforts have been made to develop water-soluble or self-emulsifying antifoaming agents.
For example, published patent No. 50492, published patent No. 56-
Oxyalkylene-modified compounds of silicone found in 139108, etc., published patents 1982-121807, 1982-
Higher fatty acid glycols found in 122807 etc.
There are POA, EOA adducts, urethanized and esterified polyethers as seen in Japanese Patent Publication No. 49-31873, Published Patent Application No. 48210-1982, Published Patent Application No. 119807-1982, etc., but these have not yet been satisfactory. In other words, published patents 1984-50492 and 1983-
The oxyalkylene-modified silicone described in No. 139108 has problems with repellency and is expensive, which limits its usage.
121807, 1982-122807, the higher fatty acid glycol and POA, EOA adducts have insufficient antifoaming properties, and are disclosed in Japanese Patent Publication No. 49-31873 and Published Patent Application No. 1982-122807.
Although it is clearly stated that a series of compounds applying isocyanates described in 119807 are effective as antifoaming agents for aqueous solutions containing water-soluble polymer substances, they are not effective as antifoaming agents for aqueous solutions or those with good transparency after film formation. Those with a poor foaming effect and, conversely, a good antifoaming effect tend to reduce transparency, and sufficient improvements have not yet been made. The esterified product described in Published Patent Application No. 1982-48210 has the fundamental drawback that it decomposes under alkaline or acidic conditions, which limits the fields in which it can be applied. The present inventors have made extensive efforts to improve these drawbacks, and as a result, have arrived at the present invention. That is, the present invention is based on the general formula (In the formula, R is hydrogen or a compound residue containing an active hydrogen atom, R' is a monovalent hydrocarbon group having 1 to 22 carbon atoms,
n is an integer from 2 to 4, m is an integer from 5 to 300, p is 1
An integer of ~6, l is an integer of 0 to 5, (however, p>l)
shows. ) is an antifoaming agent made of a compound having the structure represented by: General formula () in the present invention
The compound represented by may be a single compound, or may be a mixture of two or more kinds represented by this general formula (). R, one of the structural units of the compound represented by the general formula (), is usually hydrogen or a hydrocarbon residue having 1 to 22 carbon atoms, and may have a ring structure, linear or branched structure. Further, atoms other than carbon may be included in the carbon chain, such as sulfur, nitrogen, and oxygen. Specifically, it is a residue obtained by removing the H group from the terminal -OH group, -SH group, _-NH2 group, -NH group, etc. of the following compounds. (1) Monohydric alcohols such as methanol, ethanol, n-propanol, isopropanol, n
- Synthesis of butanol, isobutanol, hexanol, 1,2-ethylhexanol, n-octanol, decanol, dodecanol, tetradecanol, hexadecanol, octadecanol, alfol, dovanol, etc. 1st
Synthetic secondary alcohols such as alcohol, Tergitol S, softanol, oxo alcohol, aromatic alcohols such as benzyl alcohol, phenylethyl alcohol, cyclohexanol, inmitol, 2,2-bis(4-
(2) Residues obtained by removing active hydrogen from alicyclic alcohols such as (hydroxylhexyl) propane; (3) Phenols such as phenol, cresol, catechol, resorcinol, pyrogallol,
Residues obtained by removing active hydrogen from octylphenol, nonylphenol, dodecylphenol, dioctylphenol, etc. (4) Lower amines such as ethanolamine, triethanolamine, triisopropanolamine, ethylenediamine, trimethylenediamine, triethylenetetramine, etc. , higher amines such as laurylamine, laurylmethylamine, diurylamine, and dioleylamine (5) Thiols include residues from which active hydrogen has been removed such as laurylthiol and oleylthiol. Among these, preferred is 1 having 1 to 18 carbon atoms.
and dihydric alcohols, phenols, and amines, and particularly preferred are alcohols having 3 to 12 carbon atoms.
These are residues from alcohols, alkylphenols, and primary amines. Examples of the carbon hydrogen group represented by R' include methyl, ethyl, n-propyl,
Lower aliphatic hydrocarbon groups such as isopropyl, t-butyl, n-butyl, isobutyl, cyclohexyl, octyl, 2-ethylhexyl, lauryl,
Examples include higher aliphatic hydrocarbon groups such as oleyl and stearyl, and aromatic hydrocarbon groups such as phenyl and sec-butylphenol. Among these, hydrocarbons having 2 to 18 carbon atoms are preferred, and hydrocarbons having 3 to 12 carbon atoms are particularly preferred. If the number of carbon atoms is greater than 22, it is not preferable because it reduces transparency. In the general formula (), n is an integer indicating the number of carbon atoms in the oxyallene group, and examples thereof include an oxyethylene group, an oxypropylene group, and an oxybutylene group. Among these, preferred are oxyethylene group and oxypropylene group. The oxyethylene group, oxypropylene group, and oxybutylene group may be bonded in block form or randomly, but the weight ratio of oxyethylene group/oxypropylene group and oxybutylene group is 100/0 to 100/0. Ten/
90, preferably 70/30 to 30/70. If this weight ratio is less than 10/90, transparency will decrease. The polymerization degree m of oxyalkylene group is m when the weight ratio of oxyethylene group/oxypropylene group and oxybutylene group is 100/0 to 70/30.
is 5 to 50, preferably 10 to 30, and when the weight ratio of oxyethylene group/oxypropylene group and oxybutylene group is 70/30 to 30/70, m is 10 to 300,
It is preferably 20 to 250, more preferably 25 to 200, and the weight ratio of oxyethylene group/oxypropylene group and oxybutylene group is 30/70 to 10/90.
When m is 30 to 300, preferably 30 to 200, more preferably 30 to 150. If m exceeds this range, the antifoaming effect will decrease, which is not preferable. p is usually an integer of 1 to 6, preferably 1 to 4, and R
corresponds to the number of active hydrogen atoms. l is usually an integer of 0 to 5, preferably an integer of 0 to 2, and more preferably an integer of 0 to 1. However, the relationship between p and l is always p>l. As a method for producing a compound represented by the general formula (), for example, (a) a polyether alcohol represented by the general formula () R[-(C _o H _2o O) _n H] _p ...() and

A roughly equivalent amount of glycidyl ether represented by [Formula] is charged into a reaction vessel,
After nitrogen substitution, the reaction is carried out at a reaction temperature of 50 to 170°C for 2 to 8 hours with stirring in the presence of a catalyst such as an alkali, acid, or Lewis acid, and then unreacted glycidyl ether is removed under reduced pressure. ), (b) a polyether alcohol represented by the general formula ()R[-(C _o H _2o O) _n H] _p is reacted with epichlorohydrin according to a conventional method, and the following reaction is performed. And R′OM(M
is the alcoholate represented by Na or K) 40
It can also be produced by a method of reacting at ~180°C. The compound represented by the general formula () can be obtained by either method (a) or (b) above, but
Method (a) has a high yield and is relatively easy to synthesize. The antifoaming agent of the present invention is used for the purpose of preventing foaming in various processes in various industries that handle surfactants and water-soluble polymer compounds, such as the textile/dyeing industry, paper/pulp industry, synthetic resin industry, and paint industry. can. The amount of the antifoaming agent of the present invention to be used varies somewhat depending on the process to which it is applied, but for example, as an antifoaming agent for cleaning and dyeing textiles, it is usually 0.002 to 1% o.ω.f, preferably 0.005 to 0.5%. % o. ω. % by weight, preferably
It ranges from 0.05 to 1% by weight. The antifoaming agent of the present invention may be added directly to the aqueous solution of the foaming substance, or may be added after diluting with water 5 to 100 times in advance. The antifoaming agent of the present invention has superior antifoaming power to conventional polyoxyalkylene polyol, alkyl or alkenyl polyoxyalkylene polyol antifoaming agents. In addition, since the terminal of the polyoxyalkylene chain is bonded with an ether group or thioether group that is difficult to hydrolyze, it has increased acid and alkali resistance, and can be used in acidic or alkaline atmospheres compared to conventional polyoxyalkylene ester compounds. Since the antifoaming power can be maintained for a long time, it is suitable as an antifoaming agent for aqueous solutions of foaming substances containing acids and alkalis. In addition, like regular polyether defoaming agents, they are highly hydrophilic compared to silicone-based, mineral oil-based, and metal soap-based defoaming agents, so they are often the cause of trouble in the dyeing, paint, and synthetic resin industries. It can eliminate old staining spots, pinholes, and cissing. Furthermore, the antifoaming agent of the present invention has a structure in which an -OH group remains in the structural formula, so that, for example, -
It is presumed that this is because it has an affinity for water-soluble polymer substances containing OH, -CONH ₂ , -NH ₂ , -SO ₃ H, etc., thereby increasing its compatibility with water-soluble polymer substances. For example, it has the feature that it does not deteriorate the transparency of clear coats in the paint industry that require transparency, polyvinyl alcohol films, polyvinyl alcohol glues, etc. The present invention will be explained below with reference to production examples and examples, but the present invention is not limited thereto. Parts or % in the text mean parts by weight or % by weight. Production example 1 74.1 parts of n-butanol and caustic potassium as a catalyst
After charging 6.9 parts into a 10-unit stirring autoclave and purging the system with nitrogen three times, the temperature was raised to 120°C. A mixture of 2,205 parts of ethylene oxide and 2,324 parts of propylene oxide was introduced into the mixture at a temperature of 110 to 130° C. under a pressure of 2 to 5 kg/cm ² G to carry out an addition reaction. This product is CH ₃・CH ₂・CH ₂・CH ₂・
It was a random adduct of n-butanol ethylene oxide and propylene oxide having the structure O.[-(CH ₂ H ₄ O-) ₅₀ (-C ₃ H ₆ O)- ₄₀ -]H. Next, 400 parts of this random adduct and 12.0 parts of butyl glycidyl ether were placed in a glass four-necked colben equipped with a thermometer, a stirrer, and a reflux condenser, and heated at a temperature of 160 to 170°C in a nitrogen atmosphere. After carrying out the reaction under reflux for 8 hours, unreacted butyl glycidyl ether was removed under reduced pressure of 10 to 20 mm at a temperature of 110 to 130°C.
Distilled under Hg. Next, add 5 parts of activated clay.
After adsorption treatment for 30 minutes, the catalyst was removed by filtration to obtain 403 parts of product. The product was a pale yellow transparent liquid. Production Example 2 N-butanol ethylene oxide propylene oxide random adduct obtained in Production Example 1
400 parts and 2-ethylhexylglycyl ether
17.0 parts of the unreacted 2-
Ethylhexyl glycidyl ether was distilled off.
Next, 5 parts of activated clay was added, stirred for 30 minutes, and filtered to remove the catalyst, yielding 410 parts of a product. The product was a pale yellow liquid. Production Example 3 130 parts of 2-ethylhexanol and 4.2 parts of caustic potassium as a catalyst were placed in a 10 autoclave, and the system was purged with nitrogen three times, and then the temperature was raised to 120°C. Thereafter, a mixture of 1014 parts of ethylene oxide and 988 parts of propylene oxide was introduced at a temperature of 110 to 130° C. under a pressure of 2 to 5 kg/cm ² G to carry out an addition reaction. The product was a random adduct of 2-ethylhexyl alcohol with 23 moles of ethylene oxide and 17 moles of propylene oxide. The following 400 parts of this random adduct and 25.8 parts of butyl glycidyl ether were added in the same manner as in Production Example 1.
After reaction under reflux at a temperature of 170°C, unreacted butyl glycidyl ether was distilled off and treated with activated clay to obtain 415 parts of a product. The product was a pale yellowish brown liquid. Production Example 4 400 parts of polyethylene glycol (1000) obtained by a conventional method and butyl glycidyl ether
After reacting with 110 parts according to Example 1, topping treatment with activated clay was performed to obtain 490 parts of a product.
The product was a light yellowish brown solid. Production Example 5 184.2 parts of glycerin and 7.4 parts of caustic potassium as a catalyst were placed in 10 stirring autoclaves, and the system was purged with nitrogen three times, and then the temperature was raised to 120°C. 110
Ethylene oxide 1411 to this at a temperature of ~130 °C
parts, and 3370 parts of propylene oxide.
The mixture was introduced under a pressure of 5 kg/cm ² G to carry out an addition reaction.
The product was subjected to adsorption treatment by adding 30 parts of activated clay; the catalyst was removed. The product was a random adduct in which 16 moles of ethylene oxide and 29 moles of propylene oxide were randomly added to glycerin. Next, 600 parts of this random adduct and 0.7 parts of stannic chloride as a catalyst were placed in a two-glass four-necked colben equipped with a thermometer, a stirrer, and a reflux condenser, and epichlorohydrin was added in a nitrogen atmosphere.
70.5 parts were added dropwise to react at 70 to 90°C over 30 minutes. After the dropwise addition, the temperature was gradually raised to 120°C, and after aging for 2 hours to complete the reaction, unreacted epichlorohydrin was distilled off at 70-80°C under reduced pressure of 10-20 mmHg. Subsequently, 124 parts of sodium lauryl methylate was charged and reacted at 120 to 140°C for 4 hours. The residual catalyst and salt in the product were removed in the same manner as in Production Example 1. The product was a pale yellowish brown liquid. Production Example 6 In the same manner as in Production Example 1, a mixture of 2910 parts of ethylene oxide and 2965 parts of propylene oxide was introduced into 498 parts of dodecylphenol under a pressure of 3 to 5 kg/cm ² G for an addition reaction, and then the remaining catalyst was removed. It was removed in the same manner as in Production Example 1. The product was a dodecylphenol ether random adduct of 22 moles of dodecylphenol ethylene oxide and 17 moles of propylene oxide. This product 400
After reacting and purifying 18.3 parts of epichlorohydrin using 4 parts of tin chloride as a catalyst in the same manner as in Production Example 5, 56.2 parts of sodium isostearyl alcohol methylate was charged and the reaction was carried out at 120 to 140°C for 6 hours. The residual catalyst and salt in the product were removed in the same manner as in Production Example 1. The product was a yellowish brown viscous liquid. Examples 1 to 6, Comparative Examples 1 to 5 Using the products obtained in Production Examples 1 to 6 and the commercially available conventional products Comparative Examples 1 to 5, polyvinyl alcohol (Denka Poval B-17; hereinafter referred to as foaming material) was prepared.
(abbreviated as PVA) each antifoaming agent in a 5% aqueous solution
Table 1 shows the evaluation results for the transparency and antifoaming effect of PVA solutions added at 0.025%.

[Table] Antifoam test Collect 100ml of a 5% PVA aqueous solution preheated to 80℃ in a 200ml tall beaker, add 0.025g of each antifoaming agent as an active ingredient, and then use a test homogenizer (NISSEI AN-3 type). ) for 3 minutes at 4000 rpm. Foam height immediately after stopping (mm; foam suppression effect) and foam height after 3 minutes of standing (mm;
Measure the foam-breaking effect). Transparency of 5% PVA aqueous solution After cooling each sample to room temperature after the defoaming test described above, the transmittance (% ) to measure. Spectrophotometer adjustment is 5%
The PVA aqueous solution was used as 100%. Examples 7 to 12, Comparative Examples 13 to 14 Production Examples 1 to 6 using the prepared alkaline cleaning liquid
Table 2 shows the results of measuring the defoaming effect of commercially available conventional products (Comparative Examples 13 and 14).

[Table] That is, 100 ml of an aqueous solution of 0.04% of commercially available nonylphenol EO 10 moles and 0.2% caustic soda 50 c.c.
Immediately after adding each antifoaming agent to a volumetric flask with a stopper and keeping it at 60℃ for 20 hours or 40 hours, 60
Shake up and down 10 times at a temperature of °C, foam height immediately after (mm; foam suppression), foam height after 3 minutes of standing (mm; foam breaking)
Measure. As is clear from Tables 1 and 2, the antifoaming agent of the present invention has excellent antifoaming properties, compatibility (transparency), and alkali resistance.

Claims (1)

[Claims] 1. General formula [In the formula, R is hydrogen or a compound residue containing an active hydrogen atom, R' is a monovalent hydrocarbon group having 1 to 22 carbon atoms,
n is an integer from 2 to 4, m is an integer from 5 to 300, p is 1
An integer of ~6, l is an integer of 0 to 5 (however, p>l)
shows. ] An antifoaming agent comprising a compound having a structure represented by: 2 In the general formula (), R' is an alkyl group or an alkenyl group, n is an integer of 2 to 3, and p is 1 to 4
An antifoaming agent comprising the compound according to claim 1, wherein l is an integer of 0 to 3 (where p>l). 3 In the general formula (), n is an integer of 2 to 3, and the weight ratio of oxyethylene group/oxypropylene group is in the range of 100/0 to 10/90, p is an integer of 1 to 4, and l is an integer of 0 to 3. An antifoaming agent comprising the compound according to claim 1, which exhibits an integer (where p>l). 4 Antifoaming comprising the compound according to claim 2, wherein in the general formula (), n is an integer of 2 to 3, and the weight ratio of oxyethylene group/oxypropylene group is in the range of 100/0 to 10/90. agent.