JPS62237912A - Antifoamer - Google Patents

Abstract

PURPOSE:To prepare an antifoamer of high transparency and antifoaming properties used for water-soluble high molecular compound by using an alkylene oxide additive of specific polyol. CONSTITUTION:An antifoamer is constituted with a compound shown in Formula I. First, 3-40mol of EO is added to a compound containing 1-24 carbon atomic number and 1-6 hydroxyl groups, and then an alkylene oxide mixture of EO and PO or EO and BO is added and synthesized. Said adding order is characteristic. The first addition of EO secures adequate water solubility and next addition of alkylene oxide mixture retains antifoaming effect, and terminal hydroxyl group can be deformed properly. Said antifoamer has a superb effect for water soluble high-molecule and is used in a quantity of around 0.1-3wt% against foaming liquid.

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to an antifoaming agent that has both excellent antifoaming properties for various water-soluble polymer foams and the property of being uniformly soluble in water.

[Prior Art] Water-soluble polymer foams include various cellulose derivatives such as methylcellulose, carboxymethylcellulose, and hydroxyethylcellulose, polyvinyl alcohol,
Examples include synthetic water-soluble polymerized polymers such as sodium polyacrylate, and natural water-soluble polymers such as starch, gum arabic, and casein. These water-soluble polymer foams are used in a wide range of applications, including the textile industry, dyeing industry, pulp and paper industry, paint industry, synthetic resin emulsion, and latex industry. Examples of antifoaming agents used in these cases include various antifoaming agents such as silicone-based, fatty acid ester-based, polyalkylene glycol-based, mineral oil-based, and multiple types thereof.

[Problems to be Solved by the Invention] However, none of the above-mentioned antifoaming agents are fully satisfactory as antifoaming agents for water-soluble polymers.

In the water-soluble polymer industry, the essential requirements for an antifoaming agent include excellent antifoaming properties and uniform dissolution of a water-soluble polymer compound in a water solution. Although conventional antifoaming agents satisfy one of these two requirements, they do not satisfy both at the same time.
There has been a long-awaited antifoaming agent that is superior to that in the industry.

[Means for Solving the Problems] The present inventors conducted intensive studies to develop an antifoaming agent that satisfies the two requirements described in -1- above, and as a result, completed the present invention.

Namely, the present invention is based on the general formula % Formula %] In the formula E, R is a residue obtained by removing a hydroxyl group from a hydroxyl group-containing Q − compound having 1 to 24 carbon atoms, and XO is ethylene oxide (hereinafter referred to as EO). It is a mixed polyoxyalkylene group formed by copolymerizing propylene oxide (hereinafter referred to as PO) and/or butylene oxide (hereinafter referred to as BO) in a random or block form. E of mixed polyoxyalkylene group with
O:P O and/or BO weight ratio is 20 + 80
~80.20, Y is a hydrogen atom or an organic group that can form an ester bond, ether bond, or urethane bond with the oxygen atom of XO bonded to Y, l has a value of 1 to 6, m has a value of 10 to 200, and 1 has a value of 3 to 40].

The antifoaming agent of the present invention has 1 to 24 carbon atoms and 1 to 24 hydroxyl groups.
It can be synthesized by first adding 3 to 40 moles of EO to a compound having 6 atoms, and then adding an alkylene oxide mixture of EO and PO and/or BO, and this addition order has specificity.

It is believed that the initial addition of EO (EO) ensures appropriate water solubility, and the subsequent addition of the alkylene oxide mixture maintains the defoaming effect.

In this case, since the alkylene oxide has the initial EO, the subsequent alkylene oxide can be made more hydrophobic, resulting in a balance between higher antifoaming properties and water solubility.

In the present invention, the number of carbon atoms is 1 to 24 and the number of hydroxyl groups is 1 to 24.
Examples of compounds having 6 groups include monohydric alcohols, polyhydric alcohols up to hexahydric, fatty acids, and alkylphenols.

Examples of the above-mentioned monohydric alcohols include various natural and synthetic alcohols such as methanol, ethanol, propatool, isopropatool, octatool, dodecanol, and octadecyl alcohol, and examples of polyhydric alcohols include propylene glycol and ethylene glycol. , glycerin, sucrose, trimethylolpropane,
Examples include pentaerythritol. Examples of the alkylphenols include phenol, cresol, xylenol, tertiary-butylphenol, nonylphenol, dodecylphenol, and styrenated phenol. Furthermore, examples of fatty acids include acetic acid, propionic acid, lauric acid, and oleic acid. In the present invention, it should be understood that compounds having 1 to 24 carbon atoms and 1 to 6 hydroxyl groups are not necessarily limited to the above-mentioned compounds.

EO addition is first carried out in a conventional manner on the above-mentioned compound having 1 to 24 carbon atoms and 1 to 6 hydroxyl groups. EO addition ensures the basic hydrophilicity necessary for water solubility of the antifoam. The number of moles of EO added is 3 to 40 moles, preferably 3 to 30 moles, per hydroxyl group. When the number of moles added is less than 3 moles, sufficient water solubility cannot be obtained, and when it exceeds 40 moles, antifoaming properties are deteriorated, which is not preferable.

Next, the alkylene oxide mixture to be added is EO and P.
Consists of O and/or BO. These mixtures may be in a random state or in a block state. In the above-mentioned alkylene oxide mixture, it is necessary that EO is definitely added, and the weight ratio of EO:PO and/or BO in the alkylene oxide mixture is limited within the range of 20:80 to 80:20. . E
If the weight ratio of O is less than 20%, it becomes water-insoluble, which is undesirable, and if it exceeds 80%, antifoaming properties decrease, which is not preferred. The other copolymerized alkylene oxide is PO and/or BO, and either one may be used alone or as a mixture. The number of moles added to the alkylene oxide mixture is E per hydroxyl group.
The total amount of O, PO and/or BO is within the range of 10 to 200 moles. If the self-measured amount is less than 10 moles, it is not preferable because sufficient antifoaming properties cannot be obtained;
If the amount exceeds the molar amount, water solubility and water dispersibility will become insufficient, which is not preferable.

The polyether-polyol compound obtained as described above is the antifoaming agent of the present invention.

Furthermore, the antifoaming agent of the present invention also includes a polyether-polyol compound obtained by appropriately modifying the terminal hydroxyl group of the polyether-polyol compound. Examples of modification include esterification with aliphatic acids such as acetic acid and lauric acid, etherification with various alcohols,
Examples include glycidyl etherification using an alkyl glycidyl ether, and urethanization using isocyanates such as propyl isocyanate and octadecyl isocyanate. Such esterification, etherification, glycidyl etherification, urethanization, etc. can be carried out by conventional methods, and by such modification, antifoaming agents most suitable for various cases can be obtained.

The antifoaming agent of the present invention may be used as a compound having the above general formula as it is, or may be used in the form of a solution by dissolving it in water or a solvent. Furthermore, the antifoaming agent of the present invention can also be used in combination with other known antifoaming agents.

The amount of the antifoaming agent used in the present invention varies depending on the purpose of use and the solution to be applied, but it is generally 0.1 to 0.1 to
The amount is about 3% by weight.

Although the antifoaming agent of the present invention is particularly effective for water-soluble polymers, it should be understood that it can also be used for other applications.

[Examples] The present invention will be further explained by referring to Examples (hereinafter simply referred to as "examples" unless otherwise specified).

In the following examples and comparative examples, all additions of alkylene oxide were carried out by conventional methods.

1-6. [LL211 A 4% aqueous solution of completely saponified PVA was prepared, and 50 ml of it was weighed into a graduated cylinder with a 100 MN stopper. To this, 500 ppm of antifoaming agent of the present invention (Examples 1 to 6) or known (Comparative Examples 1 to 7) listed in Table 1 below was added, and after observing the transparency and uniformity of the liquid, It was shaken up and down 20 times, and after shaking was finished, it was allowed to stand still and the amount of bubbles was measured.

Foam volume - total volume after shaking - 50 increments I The experiment was conducted at 25°C. The obtained results are also listed in Table 1.

Example 1 Glycerin-7EO- (60PO/40EO random addition) (*1) Example 2 Dodecyl alcohol-1
,5EO-(50PO150EO Landano, 11 Canada),
Example 3 C++~, 52-valent alcohol (*2)-13
EO-(501”0150EO random addition) Example 4
Nonylphenol-20EO-(60PO150EO random addition) Example 5 Nonylphenol-20EO-(
60PO150EO random addition) Methyl etherified product example 6 Nonylphenol-20EO-(50PO/6
0EO random addition) phenyl urethane Comparative example 1 Pluronic L-61 (*3) Comparative example 2 Butanol-(60PO/70EO random addition) Comparative example 3 Nonylphenol-3EO Comparative example 4 Glycerin-25PO-23EO Comparative example 5 Dodecyl alcohol-10EO -7PO Comparative Example 6 Dodecyl Alcohol -25PO-7EO Comparative Example 7 Anti-foaming agent-free measure - Y 2 1 child 2 grand trial results Example 109865 Example 2 0 10 8 5 3 Example 3087
63 Example 4 0 1.0 7 6
2 Example 509776 Example 6 0 1.0 8 7 5 Comparative Example LX 8 7 5 2 Comparative Example 20 15 1.1 8 6 Comparative Example 3X 25 22 21 13
Comparative example 4X 16 17 15
1.1 Comparative example 50 28 25 20
15 Comparative Example 6x 5 5 5
4 Comparative example 70 45 43 43 4
3 Note: (*1) Number of moles added per hydroxyl group (*2) Softanol D (manufactured by Nippon Shokubai Co., Ltd.) (*3) PO-EO Bu O
Tsukukopoli? -(EOIO%) 7~13・Jwon 2
44 Prepare a 0.5% aqueous solution of methylcellulose (#4.0OO) and transfer 40t*1 to a graduated cylinder with a 100-mm stopper.
was weighed. In addition to this, the products of the present invention listed in Table 2 below (
Examples 7 to 13) or known antifoaming agents (Comparative Examples 8 to 14) were added at 100 ppn+, and after observing the transparency and uniformity of the liquid, it was shaken up and down 20 times, and after shaking was finished, it was allowed to stand still. The amount of foam was measured.

Foam volume - Total volume after shaking - 40 m1 The experiment was conducted at 25°C. The obtained results are also listed in Table 2.

Example 7 Dodecyl alcohol-25EO-(70PO/
40EO random addition) Example 8 Dodecyl alcohol-
3EO-(45PO/65EO Landano, addition) Example 9
Dodecyl alcohol-15EO-(20PO-50E
O-30PO block) Addition example 10 Dodecyl alcohol-J5EO- (40PO/70EO random addition) Lauric acid ester example 11 Dodecyl alcohol-15EO- (20B
O/70EO random addition) Example 12 Dodecyl alcohol-3EO- (IOPO15EO random addition) Example 13 Lauric acid-10EO- (50PO150E
Random addition) Comparative Example 8 Bruronikshi-61 Comparative Example 9 Dodecyl alcohol = (40PO/70EO random addition) Comparative Example 10 Dodecyl alcohol - (40P
O/]OEO random addition) Lauric acid ester comparative example 11 Dodecyl alcohol-5EO-(IOPO1
55EO Random Addition> Comparative Example 12 Dodecyl Alcohol-5F,0-(65PO/20EO Random Addition) Comparative Example 13 Dodecyl Alcohol-9EO-10PO Addition Comparative Example 14 No Antifoam Addition Example 70 9764 Example 8010765 Example 9 0 13 12 10 9 cases 10
0 6 5 3 1 example 1 i
0 1.1 9
7 4 cases 12 0
7 5 5 3 cases 13 0 9
8 7 7 Comparative example 8x 12
11 10 1.0 Comparative example 90 25 2
4 23 20 Comparative Example 10 X 7
6 4 2 Comparative example 11x
35 35 34 33 Comparative example 12 0
15 13 12 11 ratio teaching example 13x
10 9 8 8 Comparative example 1
4 0 38 37 37 35 [Effects of the Invention] The antifoaming agent of the present invention is an antifoaming agent with excellent transparency and antifoaming properties, and can be used as an antifoaming agent for water-soluble polymerized sound products and other uses. I'm looking forward to using ノ＼.

Claims (1)

[Claims] General formula R-[O(CH_2CH_2O)_n(XO)_mY]
_l [In the formula, R is a residue obtained by removing the hydroxyl group from a hydroxyl group-containing compound having 1 to 24 carbon atoms, and XO is a random or block copolymer of ethylene oxide and propylene oxide and/or butylene oxide. The mixed polyoxyalkylene group has a weight ratio of ethylene oxide:propylene oxide and/or butylene oxide of 20:80 to 80:20, and Y is a hydrogen atom or It is an organic group that can form an ester bond, ether bond, or urethane bond with the oxygen atom of XO to which it is bonded, l has a value of 1 to 6, and m has a value of 10 to 2.
00, and n has a value of 3 to 40].