DE1289037B - Process for stabilizing aqueous solutions or dispersions of compounds containing oxalkylene or polyoxyalkyl groups - Google Patents

Description

stabilization products by additives in such a way that no or only minimal losses through decomposition enter.

There has now been a method for stabilizing water-containing solutions or dispersions of oxyalkylene or compounds containing polyoxalkylene groups found, which is characterized is that compounds of the general formulas are used as stabilizers

OH

HO R ₃

OH II

R ₄

(CH ₂ ) _n -COOR ₆

For numerous processes in the context of the commercial manufacture or processing of products,
as they are, for example, in the textile, petroleum, detergent or paper industries, especially in the
Manufacture and finishing of fibers and textiles, are carried out, are used in many ways
surface-active products based on addition compounds of alkylene oxides. These alkylene oxide adducts are predominantly
Addition products of alkylene oxide to connection _I0
fertilize the groups with reactive hydrogen atoms, such as. B. OH, SH groups contain.
Examples of such compounds may be mentioned
Alcohols, organic and inorganic acids or
their esters and amides, ring-alkylated phenols, ₅
Naphthols, etc., are particularly suitable as alkylene oxides
Ethylene oxide and propylene oxide mentioned. Even
Homo- or copolymers of alkylene oxides,
such as polyethylene glycol ether or polyethylene propylene glycol ether, come for the tech ₂ o
niche use under consideration. Get industrial
For example, preference is given to using reaction products of alkylene oxide with fatty acids, fatty acid amides, fatty acid alkylolamides. Fatty alcohols, alkylphenols, alkylnaphthols, etc. The oxäthylie- 25 _{0 (} j _er
The degree of efficiency fluctuates within wide limits and is directed
depending on the intended use of the products mentioned.
The alkylene oxide adducts come as such or
in the form of their aqueous solutions or dispersions for use. The application to the _30th
The material to be treated can be, for example, by dipping,
Spraying, pouring on, etc. take place. Most of them
eligible procedures it is in view
Required for a rational working method, with one used in which Ri stands for hydrogen or the amount of methyl in the treatment solution or dispersion to 35 groups, R- stands for hydrogen, an alkyl radical with 1 to, which is used for the short-term application to the 9th Carbon atoms, a cycloalkyl radical with 5 to be treated good just required amount at 6 carbon atoms or an aryl, preferably far exceeds. For example, in the case of a phenyl radical, Ri and Ri for hydrogen treatment of a fabric or an endless thread or an alkyl radical with 1 to 9 carbon atoms, the fabric web 40 Rr proceeding according to the padder, for hydrogen or an alkyl radical with 1 to or the thread bundle is passed through a larger container containing 4 carbon atoms, Rn for hydrogen, an Al treatment liquor with 1 to 18 carbon atoms or one and then the excess liquor is removed one or more times through hydroxyl groups by pressing between two rollers. The tuierten alkyl radical of 2 to 6 carbon atoms and pressed liquor is continuously returned to the immersion 45 η stands for 0 or an integer from 1 to 3, container and comes there again in the above formulas can, for example

Mission. Theoretically, R- should stand for hydrogen, an alkyl radical from 1 to 9, from the outside of the immersion bath, only as much fresh liquor are added as, preferably, 1 to 4 carbon atoms, as there are the pressed material is continued. For example, methyl, ethyl, propyl, isopropyl, butyl, In practice, however, the consumption of treatment 50 hexyl, octyl, nonyl, a cycloalkyl radical, is preferred liquor significantly higher, since the surface-wise cyclopentyl or cyclohexyl, an aryl radical, active, alkoxylated compounds containing preferably a phenyl radical, this ge liquor In an unknown manner, after some time it can still be substituted if it decays, as is buried and so useless for the treatment purpose, for example Tolyl, R-.i and; Ri each for hydrogen, will. It must be removed and replaced by a freshly prepared 55 alkyl radical with 1 to 9 carbon atoms, such as fleet to be replaced. There is therefore a right, for example, methyl, ethyl, propyl, isopropyl, considerable economic interest, such butyl, tert-butyl, amyl, heptyl, octyl, nonyl, to stabilize treatment baths and so the by R5 for hydrogen, an alkyl radical from 1 to Avoid decomposition losses. 4 carbon atoms, such as methyl,

The progressive decomposition of an oxalkylic ethyl, propyl, isopropyl, butyl, R «for water products containing treatment lotto is on substance, an alkyl radical of 1 to 18, preferably recognizable by the drop in pH. With disperse 1 to 8 carbon atoms, such as mesions It also leads to a relatively short ethyl, ethyl, propyl, isopropyl, butyl, hexyl, octyl, Time to break the dispersions, making them dodecyl, heptadecyl, octadecyl, one or more for further use likewise unusable 65-fold alkyl group substituted by hydroxyl groups will. from 2 to 6 carbon atoms such as

The main object of the invention is therefore 2-hydroxyethyl, 2,3-dihydroxypropyl, 2,2-di- (hydarin, Solutions or dispersions of oxalkydroxy-methyl) -3-hydroxy-propyl.

«5

20th

Examples of compounds which can be used for the process according to the invention are:

Bis (2-hydroxy-5-methyl-phenyI) methane. Bis (2-hydroxy-3-methyl-phenyi) -phenylmethane,

Bis- (2-hydroxy-5-octyl-phenyl) -propane- (2), bis- (2-hydroxy-3-methyl-5-octyl-phenyl) -

methane,
Bis- (2-hydroxy-3-tert-butyl-5-nonyl-pheny!) -

propane (2),
Bis- (2-hydroxy-3-methyI-5-ethyi-phenyl) -phenyl-methane,

Bis- (4-hydroxy-phenyl) -propane- (2), bis- (4-hydroxy-3-methyI-phenyl) -phenyl-

methane,
Bis- (4-hydroxy-3-tert-butyl- (phenyl) -hydro-

hexane,
Bis- (4-hydroxy-3-tert-butyl-6-methyI-phenyl) -butane,

4,4-bis (4-hydroxyphenyl) pentanoic acid, 3,3-bis (4-hydroxy-3-methyI-phenyl) -

butanoic acid,
4,4-bis (4'-hydroxyphenyl) pentanoic acid

methyl ester,
4,4- bis- (4-hydroxyphenyl) pentanoic acid

butyl ester,
3,3-bis- (4-hydroxy-3-methyl-phenyl) -butane

butyl acid ester,
3,3-bis- (4-hydroxy-3-methyl-phenyl) -butane

octyl acid ester,
3,3-bis- (4-hydroxy-3-methyl-phenyI) -butane

acid dodecyl ester,
3,3-bis- (4'-hydroxy-3-tert-butyl-phenyl) -butane

butyl acid ester
4,4-bis (4'-hydroxyphenyl) pentanoic acid

octadecyl ester,
4,4-bis (4'-hydroxyphenyl) pentanoic acid

glycol ester,
4,4-bis (4'-hydroxyphenyl) pentanoic acid

glycerol ester or the

4,4-bis- (4'-hydroxyphenyl) -pentanoic acid pentaerythritol ester.

The phenols used according to the invention of the general Formulas I and II can be used in a manner known per se, for. B. by condensation of phenols or alkylphenols with aldehydes or ketones in the presence of acidic condensing agents, will echo. Compounds of the general formula III can be based, for example, on the in J. Or «. (hem., 23 (1958). pp. 1004 to 1006).

It is generally sufficient to add the solutions or dispersions of alkylene oxide addition compounds to be stabilized the compounds which can be used for the process according to the invention in amounts of about 0.05 to about 1 ", preferably 0.1 to 0.4 "A), based on the Alkylenoxydanlagiingsverbindungen, to add. Even at the very low stabilizer concentrations at the lower limit a clear effect can be observed. Due to the fact that stabilization can already be achieved by adding the above If quantities are achieved, the properties are those contained in the treatment bath Alkylene oxide addition compounds not affected. The stabilizing phenols can use the treatment baths as such, in both

35 play as water or an organic solvent dissolved or dispersed form or customary additives may be added in admixture with other for a particular use of the fleet. It is also possible to mix the stabilizers with the alkylene oxide addition compounds before they are added to the treatment bath. The stabilizing phenolic compounds can be added as such or in the form of their salts, for example the alkali metal salts, in particular the sodium or potassiumate.

It is already known to use chlorinated phenols, preferably pentachlorophenol, as antifouling agents to be used in treatment baths. However, halophenols are incapable of those discussed above To prevent decomposition of solutions or dispersions of alkylene oxide adducts. With knowledge With this last-mentioned fact it must therefore be regarded as surprising that phenols of the According to the invention used type show a stabilizing effect. Compared to simple phenols, from which some of the solutions or dispersions mentioned can also give a certain stability, the phenols used according to the process of the present invention are distinguished on the one hand by this from the fact that they do not suffer discoloration in the air and so there is no risk of treatment baths becoming unusable in this way. Another A major advantage of their use is that they are used in accordance with the invention Coming concentrations are physiologically practically harmless and the stabilizing effect does not affect certain alkylene oxide addition products is limited, but occurs regardless of their degree of alkylation.

example 1

The lO'Voige aqueous emulsion of a technical Stearic acid 1,4-butanediol ester polyglycol ether of a molecular weight of about 600 is refluxed heated to 60 to 70 C, while at the same time air is passed through by means of an inlet pipe will. At the same time, an identical batch with 0.2 g / l is used as one of the ones listed in the table below Additive added and treated in the same way.

At the beginning of the treatment described, the (with dilute Sodium hydroxide solution to pH values between 8.5 and 8.9 [cf. Table] set) pH value measured and followed for several hours or days. The time it takes to reach pH 7 is a measure of the Effectiveness of the additive.

The table below shows the excellent stabilizing effect of the invention Phenols used can be seen.

Zugcsel / les phenol

Without addition

Pentachlorophenol

2,4,6-Tribroni-1,3-dioxy-

benzene

3,5-dichlorophenol
phenol

Anlaiigs pH

8.6
8.6

8.5
8.6
8.6

pH 7 reached
after hours

• η 24

27 22nd

45

continuation

Added phenol Initial pH pH 7 reached
after hours Bis (2-hydroxy-3-methyl- 5-octyI-phenyl) - methane 8.6 > 150 Bis (2-hydroxy-3-tert .- butyl-5-methyl- phenyl) methane > 150 4.4-bis- (4'-hydroxy- phenyD-pentanoic acid > 150 4,4-bis (4'-hydroxy- phenyl) pentanoic acid methyl ester > 150 3,3-bis (4-hydroxy- 3-methyl-phenyl) - butanoic acid butyl ester 8.8 > 150 3,3-bis (4'-hydroxy- 3 '-tert .butyl-phenyl) - butanoic acid butyl ester > 150 4,4-bis (4'-hydroxy- phenyl) pentanoic acid glycol ester > 150 4,4-bis (4'-hydroxy- phenyl) pentanoic acid glycerol ester > 150 4,4-bis (4'-hydroxy- phenyl) pentanoic acid pentaerythritol ester > 150

The decrease in the pH value can be seen in the following table:

5
Additional milk Initial pH pH
8th
S. value
80
lunde after
100
η Without 7.0
7.0 6.6
6.8 3.1
4.8 3.0
4.6 io 3,3-bis (4-hydroxy-
3-methyl-phenyl) -
butyl bulanate

The percentages given above represent percentages by weight.

Claims (2)

Claims: Example 2 Instead of the 10 (> / <> igen stearic acid 1 ^ -butanediol ester polyglycol ether emulsion used in Example 1, a 10% aqueous solution of a copolymer of propylene and ethylene oxide was used and treated with 3.3-bis (4- Hydroxy-3-methyl-phenyl) -butanoic acid butyl ester, which was added in an amount of 0.2 g / l, stabilized. The decrease in the pH value is shown in the following table: Added phenol without additive 3,3-bis- (4-hydroxy-3-methyl-pheny-D-butanoic acid bulk ester initial pH 7.3 7.3 pH value after 15 I 60 I 150 hours 4.8 5.6 3.8 5.2 3.2 5.0 Example 3 Instead of that used in Example 1 10 "igen Siearinätireesterpolyglykoläther emulsion was a 10", uige aqueous solution of the reaction product of 1 mol of orthophosphoric acid. hydroxy-3-methyl-phenyl) -butanoic acid butyl ester stabilized. 1. Process for stabilizing aqueous solutions or dispersions of oxalkylene or compounds containing polyoxyalkylene groups, characterized in that compounds of the general formulas R ₃ OH ill HO HO —n: ¹ OH II or HO wherein R] represents hydrogen or the methyl group. Ri stands for hydrogen, an alkyl radical with 1 to 9 carbon atoms, a cycloalkyl radical with 5 to 6 carbon atoms or an aryl, preferably a phenyl radical, Ra and Ri each for hydrogen or an alkyl radical with 1 to 9 carbon atoms, Rn for hydrogen or an alkyl radical with Ί to 4 carbon atoms. Rn represents hydrogen, an alkyl radical having 1 to 18 carbon atoms or an alkyl radical of 2 to 6 carbon atoms which is mono- or polysubstituted by hydroxyl groups and η is θ "or an integer from 1 to 3, or salts thereof are used. 2. The method according to claim 1, characterized in that that the amount of stabilizer 0.05 to Γ'- «, based on the Alkylenoxydadditionsprodukl. amounts to.