DE2104202A1 - - Google Patents

Description

Monocarboxylic acid esters of polyethylene glycol ethers

The invention relates to monocarboxylic acid esters of polyethylene glycol ethers the formula

R ₁ R ₂

-CH,

(CH ₂ -CH ₂ -O) _n H.

(D

(CH ₂ -CH ₂ -O) _n H.

in the

R ₁ and R ₂ independently of one another are hydrogen, a halogen

atoto, a C ^ C ^ -alkyl radical or a given "

if substituted by lower alkyl groups

Mean phenyl radical and
m for a number from 2 to 20 and η for a number from 2 to 20, preferably 3 to 12,

stand

a process for their production and their use as a dispersing and embedding aid.

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The monocarboxylic acid esters according to the invention are obtained by using the polyethylene glycol ethers of the formula (I). ait containing 10-22 carbon atoms, preferably 12-20 carbon atoms Esterified monocarboxylic acids, the proportions between monocarboxylic acids and polyethylene glycol ethers is chosen so that there are 0.1 to 1, preferably 0.4 to 0.8 carboxylic acid molecules for each OH group.

Examples of representatives of the monocarboxylic acids containing 10 to 22 carbon atoms are: saturated aliphatic Carboxylic acids, such as capric acid, lauric acid, palmitic acid, stearic acid or earthquake acid, unsaturated aliphatic carboxylic acids, such as oleic acid, undecenoic acid, ricinoleic acid, ricinic acid, linoleic acid or linolenic acid, or mixtures of saturated and / or unsaturated aliphatic carboxylic acids, such as those used in paraffin oxidation and the oxo synthesis or as they are obtained in the saponification of vegetable and animal fats Fatty acid mixtures, e.g. in the lineal oil fatty acid, are present, also aromatic carboxylic acids, such as p-tert-butylbenzoic acid or p-nonyl benzoic acid.

The esterification can be carried out according to the usual esterification processes; In the present case, the esterification process, in which the esterification agent and the product to be esterified are heated on the water separator, optionally with the addition of an entrainer, until esterification is complete, has proven particularly successful.

The polyethyleneglycol ethers of the formula (I) to be esterified according to the invention can be prepared by processes known per se, e.g. B. by adding the phenols on which the polyethyleneglycol ethers are based

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aldefciyd condensed in the presence of acids and the resulting Condensation products (novolaks) are then ethoxylated, or by first ethoxylating the phenols and the ethoxylation products are then condensed with formaldehyde.

The manufacture of phenol-formaldehyde condensation products (Novolak) is described, for example, in Houben-Weyl "Methods of Organic Chemistry", Vol. XVI / 2, pp. 272-275. To produce the novolaks, phenols and formaldehyde are used in a molar ratio of 2: 1-1.6.

As phenols, which are the polyethylene glycol ethers of the formula (I) may be based, in particular phenol, o-, m-, p-methy! Phenol, 2,4-dimethylphenol, o-, m-, p-butylphenol, 2,4-tert-dibutylphenol, 2-tert-butyl-4-methylphenol, o-, m-, ß-chlorophenol, 2,4-dicblophenol, p-tert-octylphenol, p-iso-nonylphenol, p-pheny! phenol and p- (methylphenyl) phenol and mixtures thereof.

The ethoxylation of novolaks or phenols is carried out in a known manner in the presence of alkaline catalysts; the amount of ethylene oxide is calculated so that 2 to 20, preferably 3 to 12, molecules of ethylene oxide fall on each OH group.

The products according to the invention have valuable properties:

they are excellent dispersants for pigments and lime soaps, but especially for dyes. They are suitable both for dispersing water-insoluble dyes in aqueous media and for dispersing dyes that are sparingly or sparingly soluble in organic solvents which are immiscible with water in these solvents,

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e.g. in trichlorethylene, tetrachlorethylene, petroleum ether, Xylene and the like are obtained by adding relatively small amounts of the monocarboxylic acid esters according to the invention Solubilisates of the dyes, e.g. in perchlorethylene, which are excellent for dyeing from solvents are suitable.'

Furthermore, the esters according to the invention are good emulsifiers for the production of aqueous emulsions of hydrocarbons, vegetable oils and fats, and silicone oils. The water or oil solubility can be varied within wide limits by the degree of ethoxylation on the one hand and by the type of carboxylic acid and the degree of esterification on the other hand, and can thus be adapted to the particular intended use. If, for example, 50 # of the OH groups of a novolak ethoxylated with 15 molecules of ethylene oxide OH group are esterified with lauric acid, a water-soluble ester is obtained which has excellent lime soap dispersibility. On the other hand esterifying 60 i "of the OH groups of the same ethoxylated novolak having oleic acid, we obtain a water-insoluble ester, which is excellent for dispersion of dyes, such as disperse dyes or anionic dyes such as acid wool dyes, metal complex dyes in organic water-immiscible solvents , for example perchlorethylene, is suitable. Furthermore, the monocarboxylic acid esters according to the invention have the property of making continuous colorations from organic solvents immiscible with water more uniform and of accelerating the fixation of the dye on the fiber in the subsequent heat treatment.

Furthermore, the monocarboxylic acid esters according to the invention have also proven to be valuable detergents with excellent dirt resistance.

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Proven carrying capacity.

The parts given in the following examples are parts by weight; the dye numbers given relate to refer to the information in the Color Index, Vol. 3, 2nd edition (1956).

example 1

194 parts of the by ethoxylating a novolak (phenol; Formaldehyde = 2: 1.6) with 6.65 mol of ethylene oxide polyethylene glycol obtained per mole of OH-G group ether,

70.5 parts of oleic acid and

350 parts of xylene (

are cooked while stirring on the water separator, until no more water separates out. The xylene is then distilled off. 258 parts of a viscous yellowish color are obtained Liquid (acid number 10).

0.5 g of the dye CI 12100 are rubbed inaig with 1 g of the polyester described above in a mortar. The homogeneous preparation is poured into water and the mixture is stirred intensively. A stable dye dispersion is obtained. ™

1 part of the dye CI 12 790 is mixed with 1.5 parts of the Sodium salt of 1,1'-dinaphthylmethane-2,2'-disulfonic acid Grind in a ball mill to a 10-6 aqueous dye paste. 50 parts of this fast are made with 2 parts of the ester and 2000 parts of water mixed. A further 7 parts of the ester are added and the mixture is then diluted with water

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to 7000 parts. Ια this dye bath, the pH is adjusted with acetic acid to 5, one part brings at 50 ⁰ G of a pre-purified polyester fabric a, warms the bath in a closed apparatus within 30 minutes at 120 ⁰ C and stained for one hour at this temperature. The fabric is then carefully rinsed. A yellow dyeing of excellent rub fastness is obtained.

An equivalent dispersant was obtained if the equivalent amount of linoleic acid was used instead of the 70.5 parts of oleic acid or p-tert-butylbenzoic acid was used.

Example 2

202 parts of the polyethylene glycol obtained by ithoxylating a novolak (phenol: formaldehyde = 2: 1.6) with 13 moles of ethylene oxide per mole of OH group are used with
25 parts of lauric acid and

350 parts of xylene

Esterified as described in Example 1. 224 parts of a viscous yellow-brown liquid (acid number 14) are obtained.

The ester is suitable, for example, as a dispersant for azo pigments in the developing baths of the naphthol-AS staining.

4 parts of 2-oxy-napbtboesäure- (3) -ß-naphtbalid are in 4 Share ethanol made into a paste. After that, the paste will be 2 parts Sodium hydroxide solution (Diobte 1.308) added. Then dilute it with 8 ropes of softened water, add 2 parts of formaldehyde ($ 30) and give it for half an hour resulting solution in 1000 parts of water to which 5 parts of sodium hydroxide solution have been added beforehand.

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Ια this liquor cotton piece goods are treated for half an hour at Zitnmerteniperatur, squeezed and then Treated for 30 minutes with a liquor containing 7.5 parts of the diazonium salt of 4-chloro-2-aminotoluene and 10 parts per liter of the ester. Then it is rinsed and soaped. The development liquor has one due to the addition of the ester improved durability; the red color obtained is extremely resistant to rubbing.

An equivalent dispersant was obtained if, instead of the 25 parts of lauric acid, the equivalent amount of myristic

acid was used. ^

Example 3

211 parts of the polyethylene glycol ether obtained by ethoxylating novolak (p-chlorophenol: formaldehyde = 2: 1.4) with 13 mol of ethylene oxide ^ e mol of OH group are used
12.5 parts of lauric acid and

350 parts of xylene

Esterified as described in Example 1.

The ester is ideally suited to the precipitation of

To prevent lime soaps in hard industrial water. M.

If you want 10 g of sodium oleate with the addition of 4 $> ester - based on the oleate - in one liter of water of 30 ° German hardness, a translucent colloidal solution is obtained; If no ester is added, the lime soap flocculates.

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Example 4

328 parts of that obtained by ethoxylating a novolak (p-nonylpnenolformaldehyde = 2: 1.3) with 8 moles of ethylene oxide per mole of OH group obtained polyethylene glycol ether are with 28 parts of oleic acid and

200 parts of xylene

Esterified as described in Example 1. 354 parts of a yellow viscous oil (acid number 4) are obtained.

The ester is an excellent dispersant for Dyes in organic solvents that are immiscible with water, e.g. hydrocarbons, halogenated carbons ~ Hydrogen and Esters. In the solution of 10 parts of the ester in 990 parts of perchlorethylene, adjusting agents are free Acid dyes dispersed in the form of their color acids. Deeply colored, stable dispersions are obtained, which can be used for dyeing wool using the exhaust process without the addition of any water.

Example 5

315 parts of the polyethylene glycol obtained by ethoxylating a novolak (p-cresol: formaldehyde «2: 1.5) with 3 moles of ethylene oxide per mole of OH group are used with

141 parts of oleic acid and

200 ml of xylene

Esterified as described in Example 1.

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10 parts of the dye

UH ₉ O OH

t * ■ II I

t Il

OH O

are pasted with 15! parts of the ester. The paste is diluted with 975 parts of perchlorethylene. A pre-cleaned polyester fabric is impregnated with this liquor, then pressed off and dried. Then the tissue is divided into 3 parts. The first portion is heated for 90 seconds, 120 ⁰ C, the second part 90 seconds to 150 ⁰ G, and the third member 90 seconds 180 ⁰ C. After washing out the unfixed portion of the dye, uniformly colored and well-colored fabrics are obtained.

The comparison with a dyeing carried out in the same way but without an auxiliary shows that the fixation yield and the levelness are greatly improved by the auxiliary. It is noteworthy that the liquor containing the ester impregnated fabric with a post-treatment temperature of 150 ⁰ C is already a deeper staining shows as impregnated with the comparison liquor without Esterzugabe fabric which had been treated at 180 ⁰ C.

Example 6

315 parts of the ethoxylation of a novolak (phenol: Formaldehyde ■ 2: 1.6) old 3 moles of ethylene oxide each Hol OH group obtained Folyäthyleaglykolätbers are with

141 parts of oleic acid and

200 ml of xylene

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are esterified in the manner described in Example 1.

1 part of the dye described in Example 5 is now Pasted with 4 parts of the ester and then with 625 parts of perchlorethylene were added. A homogeneous dye liquor is obtained.

50 g of a fabric of polyethylene terephthalate are treated with this liquor for one hour at 120 ⁰ C. After dyeing, the fabric is rinsed in pure perchlorethylene and dried. A fabric which is uniformly dyed blue is obtained.

A. Under the same conditions, but without the addition of the The coloration produced by ester is significantly weaker. Even with longer dyeing times, less dye is absorbed than the dye produced in the presence of the ester. Through the aid both the dyeing speed increases as well as the dye uptake im Dye balance shifted in favor of the fiber.

Example 7

230 parts of the novolak (phenol:

Formaldehyde »2: 1.6) with 3 moles of ethylene oxide per mole of OH group Polyätbylenglykolätaers are with

113 ropes oleic and

130! Hurry xylene

Esterified in the manner described in Example 1. Man receives an ester soluble in perchlorethylene (acid number 3).

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The ester is excellent as a dispersant for the preparation of stable dye dispersions in organic Suitable for solvents that are not miscible with water. The following is the preparation of some such dye dispersions described:

10 parts of ester are in

70 parts of perchlorethylene dissolved; the solution is 20 parts of the monoazo dye 4-aminobenzoic acid ethyl ester - ^ 1-Phenyl-5 ~ pyrazolone-3-carboxylic acid added.

The mixture obtained is ground with the agitator ball mill to a dye particle size <1 / λ (grinding time: 30 minutes). The dye dispersion thus obtained is pourable and stable on storage; it can be diluted with perchlorethylene as required without causing a solvent shock. 3 $ dye dispersions in tetrachlorethylene are still stable at 120 °.

10 parts of the ester are in

60 parts of petroleum (boiling point / ^ 160 ⁰ C) dissolved; the solution

will
20 parts of the above dye added.

The mixture is processed into a dye dispersion as described above. This also has good ones Stabilities.

7.7 parts of esters in 84.6 parts of petroleum ether (boiling point * - 80 ⁰ C) dissolved; the solution

will 7 * 7 parts of the dye indicated above were added.

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The mixture becomes one as described above Dye dispersion processed; this also has good stabilities.

15 parts of ester are in

Ib parts of xylene (mixture of isomers) dissolved; 10 parts of the above dye were added to the solution.

This mixture is processed into a dye dispersion as described above. The dispersion is arbitrary Can be thinned with xylene and remains after a short time Stable boil.

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Claims (8)

Claims '1. Esters from polyethylene glycol ethers of the formula - CH (CH ₂ -CH ₂ -O) _n H. (CH ₂ -CH ₂ -O) _n H. in the R ₁ and R ₂ independently of one another are hydrogen, a halogen atom, a Cj-Cg-alkyl radical or a phenyl radical optionally substituted by lower alkyl groups and
m is a number from 2 to 20 and η is a number from 2 to 20, and monocarboxylic acids containing 10 to 22 carbon atoms. 2. Esters according to claim 1 from polyethylene glycol ethers given formula in the η stands for a number from 3 to 12. 3. Esters according to claim 1 or 2 from 0.1 to 1 mol of monocarboxylic acid per mole of OH group in the polyethylene glycol ethers. 4. Process for the preparation of polymeric monocarboxylic acid esters », characterized in that one polyethylene glycols the formula Le A13 494 - 13 - 209833/1239 - CH (CH ₂ -CH ₂ -O) _n H. O t in the R ₁ and R ₂ independently of one another are hydrogen, aiii halogen atom, a C.-Cp ^ alkylreat or oition given * if phenyl radical substituted by lower alkyl groups and
in stands for a number from 2 to 20 and η for a number from 2 to 20, esterified with 10 to 22 carbon atoms containing monocarboxylic acids. 5. The method according to claim 4, characterized in that polyethylene glycols of the formula given are used in which η stands for a number from 3 to 12. 6. The method according to claim 4 or. 5, characterized in that that one per mole of OH group in the Polyäthylenglykoleη 0.1 to 1 hol monocarboxylic acid used. 7. The method according to claims 4 or 5, characterized by that one per mole of OH = group in the polyethylene glycols 0.4 to 0.8 mol of monooarboxylic acid is used. 8. Use of polyethylene glycol monoarboxylic acid esters according to claims 1 to 3 as dispersing and emulsifying agents. Ie A 13 494 - 14 - 209133/1239