EP0000137B1 - Polyglycol esters; process for preparing them and their use as surface-active agents - Google Patents

Description

in welcher R ein offenkettiger aliphatischer Rest mit 9 bis 19, vorzugsweise 11 bis 17 C-Atomen ist, Z für Wasserstoff und Methyl steht, wobei das Verhältnis H : CH₃ 2 : 1 bis 4 : 1, vorzugsweise 2,5 : 1 bis 3,5 : 1 beträgt, a Null oder 1 ist, b 1 bis 1,5 ist und (4-a) n 150 bis 300, vorzugsweise 200 bis 250 ist.The invention relates to polyglycol esters of the formula I.

in which R is an open-chain aliphatic radical having 9 to 19, preferably 11 to 17 C atoms, Z is hydrogen and methyl, the ratio H: CH _{3 being} 2: 1 to 4: 1, preferably 2.5: 1 to 3.5: 1, a is zero or 1, b is 1 to 1.5 and (4-a) n is 150 to 300, preferably 200 to 250.

Particularly preferred are polyglycol esters in which the radical R-CO is oleyl, the ratio of H: CH ₃ in the radical Z 3: 1 is random, a is zero, b is 1.1 and (4-a) n is about 210.

in der a Null oder 1 ist, mit der 150-300-fach, vorzugsweise 200-250fach, insbesondere etwa 210- fach molaren Menge eines Gemisches aus Äthylenoxid und Propylenoxid im Molverhältnis 2 : 1 bis 4 : 1 oxalkyliert und das Oxalkylat mit einem den Rest R-CO einführenden Acylierungsmittel partiell verestert. Als solche Acylierungsmittel kommen natürliche oder synthetische Fettsäuren wie beispielsweise Stearinsäure, Palmitinsäure, Ölsäure, Linolensäure, Talgfettsäure, Tallölfettsäure, Isostearinsäure, Kokosfettsäure oder Mischungen solcher Säuren sowie die entsprechenden Säurechloride in Betracht.The invention further relates to a process for the preparation of said polyglycol esters, which is characterized in that a compound of the formula

in which a is zero or 1, with 150-300 times, preferably 200-250 times, in particular about 210 times molar amount of a mixture of ethylene oxide and propylene oxide in a molar ratio of 2: 1 to 4: 1 and the oxalkylate with a The rest of the R-CO-introducing acylating agent is partially esterified. Such acylating agents are natural or synthetic fatty acids such as, for example, stearic acid, palmitic acid, oleic acid, linolenic acid, tallow fatty acid, tall oil fatty acid, isostearic acid, coconut fatty acid or mixtures of such acids, and the corresponding acid chlorides.

The invention further relates to the use of the new polyglycol esters as surface-active agents.

The new polyglycol esters are particularly suitable for increasing or stabilizing the viscosity of aqueous systems, in particular as an additive to printing pastes or padding liquors. For this purpose, the polyglycol esters are added in amounts of about 0.1 to about 10%, based on the weight of the finished preparation, that is to say about 1 to 100 g, preferably 2 to 30 g, of polyglycol ester per kg of printing paste.

Aqueous preparations of the polyglycol esters according to the invention can already be used as thickeners without further additives. However, the new polyglycol esters are particularly advantageous as additives to other known thickeners, and not only can they increase the viscosity of aqueous systems, but above all they can also stabilize them.

It is known that, in particular, printing pastes based on synthetic thickeners or oil-in-water emulsions and mixtures of these emulsions with native thickeners lose their viscosity in whole or in part when electrolytes are added and thus become unusable. Since the commercially available dyes and printing aids are usually electrolyte-containing, it cannot be avoided in practice to introduce electrolytes into the printing pastes. It is therefore generally necessary to carry out a series of preliminary tests in which the compatibility of the printing paste components must be ascertained before a usable and storable printing paste is obtained. Despite these precautionary measures, however, it is often unavoidable that the printing pastes lose their viscosity after some time, especially in the warm, i.e. especially in warmer countries or during the summer.

As is well known, a whole series of tasks are assigned to a thickener: it must counteract the outflow of dye solutions caused by the capillary forces of the tissue. It also prevents the tendency of the printing inks to roll out of the engravings of the rotating printing roller following the law of gravity. The thickening agent furthermore offers the possibility of accommodating different reactants in a printing ink, which in its absence would react with one another prematurely, ie already in the printing ink and not only on the fiber. The thickening agent acts as a "spacer" and prevents the premature interaction of reactive components. For example, tannin can be accommodated in a printing ink of a cationic dye without the formation of the tannin varnish, which should only take place when the fibers are steamed. If pigments such as kaolin or zinc oxide are accommodated in a printing paste, the thickener also has the task of dissolving such substances in high to keep mogeneous dispersion and to ensure that the pigment does not get stuck in the engraving of the rollers, but reaches the goods homogeneously with the printing ink.

Accordingly, the selection of a thickener is directed by a variety of factors. Among other things, by the type of printing process, by the composition of the printing ink, by the depth of the roller engraving and the required depth of color of the print by the quality of the goods, especially if there is a requirement for a print run, and also by the type of pattern, i.e. Whether small or large patterns (register or decker) should be printed determines. The polyglycol esters according to the invention are particularly suitable as an addition to purely synthetic thickeners, in particular those which contain carboxyl groups. As such, primarily copolymers of maleic anhydride and a vinyl alkyl ether or other copolymerizable monomers, which can be crosslinked with polybasic amines, polyhydric alcohols or amino alcohols, are furthermore polymers of acrylic acid, maleic acid or their anhydrides, such as those with divinylbenzene or unsaturated diesters, such as Dialkylmaleinester or _Äth_ylenglykoldimethacrylestern can be cross-linked.

Furthermore, the polyglycol ethers according to the invention are suitable as additives for oil-in-water and water-in-oil emulsions and their mixtures with native thickeners. In all of these systems, the polyglycol esters according to the invention can not only increase or stabilize the viscosity, but also allow the viscosity to be restored to a system which has been damaged, for example, by the influence of electrolytes.

It has also been found that the compounds of the formula I can also be used as emulsifiers. The compounds of the formula I are preferably used for the preparation of dye emulsions which are used for dyeing and printing textiles. These emulsions show an extraordinarily good penetration into the textiles, so that uniform, deep dyeings with good fastness properties result.

The most labor-intensive step in the coloring of textiles is the washing process, in which thickeners, dye and auxiliary residues are removed from the textile goods. Rationalization efforts therefore understandably begin with the washing process. Emulsion thickeners are therefore used in textile printing pastes, since this eliminates the additional removal of the thickener residues. Even where only half emulsions are used instead of full emulsions, the rationalization effect is still remarkable. Common emulsion thickeners for textile printing are made from water, a water-immiscible organic solvent or solvent mixture and an emulsifier. However, the emulsion thickenings customary hitherto have a number of disadvantages: due to the relatively low emulsifying action of the conventional emulsifiers, quite large amounts of these surface-active agents were required, which often led to excessive foaming when the emulsions were prepared. Common defoamers, such as those used in the textile industry, can change the stability and effectiveness of the printing pastes. In particular, there is a risk that the addition of defoaming components can cause the emulsion to split, i.e. the already finished emulsions are broken again. This effect is often only a question of the quantity ratio, i.e. Up to a certain amount, surface-active agents can act as emulsifiers and above that as emulsion breakers. The added defoamers therefore have a negative synergistic effect. Another related disadvantage is the deterioration in rubbing fastness of pigment prints.

Because of the high emulsifying action of the compounds of the formula I, considerably smaller amounts can be used to produce a stable emulsion. In addition, the compounds of the formula produce little foam per se. The addition of defoamers is therefore unnecessary for the emulsions according to the invention. In the preparation of emulsion thickenings according to the present invention, no precautions are required as with the conventional foaming emulsifiers, for example the use of disproportionately large vessels. Because of the small amounts of surface-active agents, the fastness to rubbing of the pigment prints produced therewith is also improved because the plastic film contains fewer foreign components in the form of the low-volatility emulsifier. This also results in a softer handle for the goods printed using the pigment printing process, because the amount of binder required to compensate for the emulsifiers which are harmful to rubbing fastness, but which leads to a stiff handle, can be considerably reduced.

Even in the so-called semi-emulsion thickeners, in which the printing pastes contain water-swellable thickeners in addition to water and the solvents mentioned, the emulsifiers according to the invention show significant advantages compared to the commercially available products: the customary water-swellable thickeners, namely alginates, corn meal ether, starch ether or carboxymethyl cellulose, contain more or less significant amounts of alkali ions that can break down as electrolytes emulsions. Since half-emulsion thickenings are mostly used for printing pastes with reactive, disperse and acid dyes and these dyes are either themselves electrolytes or contain electrolytes in their commercially available preparations, this problem has been attempted to date by using correspondingly large amounts of emulsifiers. These high amounts of emulsifier not only brought with them the disadvantages already described above, but also often led to a reduction in the brilliance of the prints. In contrast, they are invented Emulsifiers according to the invention are much less sensitive to electrolytes than the previously common products. In the case of half emulsions, small amounts of emulsifier are therefore sufficient.

An emulsion thickening obtained in accordance with the present invention contains, based on the weight of the finished emulsion thickening, 0.1 to 2, preferably 0.2 to 1% of compounds of the formula I, 50 to 70% of the water-immiscible solvents and 28 to 49, 9% water. Solvents which are immiscible with water are mainly hydrocarbons such as hexanes, heptanes, nonanes, cyclohexylbenzene, toluene, xylene, tetrahydronaphthalene and gasolines or mixtures of such solvents.

The printing pastes produced with such emulsion thickenings also contain colorants, in particular pigments, and binders. If necessary, these printing pastes can also contain acid donors such as diammonium hydrogen phosphate.

The printing pastes prepared with the emulsions according to the invention result in very level and brilliant prints with very good stability. These printing pastes are particularly suitable for pigment printing on cotton, rayon and other natural and also synthetic fibers and their mixtures, in particular on mixtures of natural and synthetic fibers. The emulsion thickeners according to the invention are also suitable in a mixture with water-swellable thickeners such as alginates, core meal ethers, starch ethers or carboxymethyl celluloses for printing pastes with dyes, for example disperse dyes, reactive dyes and acid dyes.

The emulsions according to the invention can be prepared by stirring the oily and aqueous phases together with the emulsifier or by other customary processes known from the literature (P. Becker, Emulsions: Theory and Practice, Reinhold Publishing Corp., New York, 1957, p. 209, Houben-Weyl, Vol. I 2, p. 97). It proves to be advantageous here that the compounds of formula 1 are water-soluble so that they can be used as aqueous solutions for the preparation of the emulsions.

A particular advantage of the compounds of the formula I is that generally only simple stirrers have to be used in the preparation of the emulsions. This also results in considerable process simplifications compared to other emulsifiers.

The emulsions according to the invention have excellent stability. Should creaming nevertheless occur after prolonged storage under unfavorable conditions, these are reversible and can generally be converted back into the original emulsion by gentle stirring.

A wide variety of emulsions can be produced with the emulsifiers according to the invention. In addition to the organic, water-immiscible solvents mentioned, preference is given to using anti-aging agents, plasticizers and other auxiliaries for the rubber sector, biological active ingredients in the crop protection sector, auxiliaries in the dyeing, textile and leather processing sectors and in polymerization technology, in particular for emulsion polymerizations, as the oily phase.

From aer DE-OS 1 595 369 block copolymers of ethylene oxide and propylene oxide are known which are derived from glycerol, pentaerythritol and trimethylolpropane and are - if appropriate partially - esterified. These compounds are suitable as foam preventers.

DE-OS 1 619053 discloses water-insoluble reaction products of polyols with ethylene oxide and propylene oxide, which are completely esterified. These compounds substantively attach to the polyester fiber and prevent the escaping of ester oligomers from the fiber material.

From DE-OS 2 102 899 completely esterified block copolymers of ethylene oxide and propylene oxide are known which act as defoamers.

From US Pat. No. 2,457,139, optionally partially esterified polyglycols are known which are obtained by polymerizing mixtures of ethylene oxide and propylene oxide. These compounds are suitable as emulsifiers and as metal lubricants.

In the following examples, parts and percentages are by weight unless otherwise specified.

example 1

• 25 Gewichtsteile des Pigments C. I. 74160 in handelsüblicher Flüssigeinstellung
• 50 Gewichtsteile eines Binders auf Basis einer selbstreaktiven copolymeren Acrylat-Dispersion
• 50 Gewichtsteile eines Binders aus einer selbstvernetzenden Mischpolymerisatdispersion auf Butadien-basis
• 15 Gewichtsteile Hexakis-(methoxy-methyl)-melamin
• 20 Gewichtsteile eines Weichmachers auf Silikonbasis
• 35 Gewichtsteile eines hochpolymeren synthesichen Verdikkungsmittels auf Basis Acrylsäure-. Maleinsäureanhydrid im Molverhältnis von 1 : 1 und vom Molgewicht von 2 000 000
• 795 Gewichtsteile Wasser
• 990 Gewichtsteile

hergestellt und in 3 gleiche Teile zu je 330 g aufgeteilt.
Zu Teil 1 werden 2 ml Wasser (Druckpaste A), zu Teil 2 werden 2 ml einer 33 prozentigen wäßrigen Lösung von Ammoniumsulfat (Druckpaste B) und zu Teil 3 werden 2 ml einer 33 prozentigen wäßrigen Lösung von Ammoniumsulfat und 2,5 g des nachstehend definierten erfindungsgemäßen Produktes (Druckpaste C) zugegeben und gut verrührt.It becomes a printing paste with the following composition

• 25 parts by weight of pigment CI 74160 in a commercially available liquid setting
• 50 parts by weight of a binder based on a self-reactive copolymeric acrylate dispersion
• 50 parts by weight of a binder made from a self-crosslinking copolymer dispersion based on butadiene
• 15 parts by weight of hexakis (methoxy-methyl) melamine
• 20 parts by weight of a silicone-based plasticizer
• 35 parts by weight of a high polymer synthetic thickener based on acrylic acid. Maleic anhydride in a molar ratio of 1: 1 and a molecular weight of 2,000,000
• 795 parts by weight of water
• 990 parts by weight

manufactured and divided into 3 equal parts of 330 g each.
Part 1 is 2 ml of water (printing paste A), part 2 is 2 ml of a 33 percent aqueous solution of ammonium sulfate (printing paste B) and part 3 is 2 ml of a 33 percent aqueous solution of ammonium sulfate and 2.5 g of the following defined product according to the invention (printing paste C) added and stirred well.

• Die Punkt-Strich-Kurve wurde mit Druckpaste A, die durchgezogene Kurve mit Druckpaste B und die Strich-Strich-Kurve mit Druckpaste C erhalten.

Rheological comparative measurements of the viscosity of these 3 printing pastes using a Searle-type rotary viscometer (Rheomat 30 from Contraves, measuring system HS 25) at a shear rate D of 481 to 34,000 sec- ', a temperature of 20 ° C and a torque of 0 to 200 cmp (0-1.96 cNm) show the viscosity-stabilizing effect of the product according to the invention. The measurement results in the form of flow curves can be found in the rheogram:

• The dot-dash curve was obtained with printing paste A, the solid curve with printing paste B and the dash-dash curve with printing paste C.

The rheogram shows that the viscosity of printing paste A with the dash-dot flow curve decreases sharply due to the addition of an electrolyte (printing paste B with the continuous flow curve).

Printing paste C with the dash-dash flow curve shows the viscosity-improving effect of the product of the invention.

• Pentaerythrit wird mit einem Gemisch aus Äthylenoxid und Propylenoxid im Molverhältnis 3 : 1 bis zu einem Molgewicht von 10 000 oxalkyliert. 1 Mol dieses Oxalkylats wird dann mit 2,9 Mol Ölsäure bei einem Temperatur von 160-165°C 15 Stunden in einer Stickstoffatmosphäre verestert.

Production of the product according to the invention:

• Pentaerythritol is oxalkylated with a mixture of ethylene oxide and propylene oxide in a molar ratio of 3: 1 to a molecular weight of 10,000. 1 mol of this oxalkylate is then esterified with 2.9 mol of oleic acid at a temperature of 160-165 ° C for 15 hours in a nitrogen atmosphere.

This product is referred to briefly as "polyglycol ester" in the following examples. These examples described the use of the polyglycol ester as an emulsifier.

Example 2

• 790 Teile einer Öl-in-Wasser-Emulsion, die aus 75% Benzin mit einer Siedetemperatur zwischen 120 und 200°C, 0,4% Polyglykolester und
• 24,6% Wasser besteht, rührt man nacheinander ein:
  • 150 Teile einer 40 prozentigen wäßrigen Dispersion eines Copolymerisates aus
  • 55% n-Butylacrylat,
  • 23% Acrylnitril,
  • 17% Vinylchlorid und
  • 5% N-Methylolmethacrylamid,
• 30 Teile einer 25 prozentigen wäßrigen Anteigung von C. I. Pigment Red 5, C. I. Nr. 12490 und
• 30 Teile Diammoniumphosphat, 30 prozentig, in Wasser. Man erhält eine gut verarbeitbare, schaumarme Pigment-Druckpaste.

In

• 790 parts of an oil-in-water emulsion consisting of 75% petrol with a boiling temperature between 120 and 200 ° C, 0.4% polyglycol ester and
• 24.6% water, stir in one after the other:
  • 150 parts of a 40 percent aqueous dispersion of a copolymer
  • 55% n-butyl acrylate,
  • 23% acrylonitrile,
  • 17% vinyl chloride and
  • 5% N-methylol methacrylamide,
• 30 parts of a 25 percent aqueous paste of CI Pigment Red 5, CI No. 12490 and
• 30 parts of diammonium phosphate, 30 percent, in water. An easily processable, low-foaming pigment printing paste is obtained.

A cotton poplar fabric is printed with this printing paste, dried and fixed at 150 ° C for 7 minutes. You get brilliant red prints with very good rub fastness.

Example 3

• 600 Teilen einer 4 prozentigen wäßrigen Lösung von Natriumalginat,
• 10 Teilen Natrium-m-nitrobenzolsulfonat,
• 2 Teilen Polyglykolester,
• 28 Teilen C. I. Reactive Yellow C. I. 18972,
• 10 Teilen Natriumhydrogencarbonat und
• 200 Teilen Wasser emulgiert man unter hochtourigem Rühren
• 150 Teile eines Benzins vom Siedepunkt 140 bis 200°C.

In a mix of

• 600 parts of a 4 percent aqueous solution of sodium alginate,
• 10 parts of sodium m-nitrobenzenesulfonate,
• 2 parts polyglycol ester,
• 28 parts CI Reactive Yellow CI 18972,
• 10 parts of sodium hydrogen carbonate and
• 200 parts of water are emulsified with high-speed stirring
• 150 parts of gasoline with a boiling point of 140 to 200 ° C.

This low-foam, easy-to-process printing paste is used to print a fabric made of cellulose, dry it, fix it in saturated steam for 5 minutes and wash it. After a short rinsing and washing process, the fabric no longer contains any thickener residues. After drying, the high brilliance of the yellow prints becomes clearer.

Example 4

• 40 Teilen einer 20 prozentigen wäßrigen Anteigung von C. I. Disperse Orange, C. I. 26080 und
• 960 Teilen einer Halbemulsion mit einem Gehalt an 350 Teilen Benzin,
• 648 Teilen einer 6 prozentigen wäßrigen Lösung eines Kernmehläthers und
• 2 Teilen Polyglykolester bedruckt, getrocknet, 1 Minute in Heißluft bei 200°C fixiert und nach einer reduktiven Behandlung gewaschen.

A fabric made of polyethylene glycol terephthalate is made with a printing paste

• 40 parts of a 20 percent aqueous paste of CI Disperse Orange, CI 26080 and
• 960 parts of a semi-emulsion containing 350 parts of gasoline,
• 648 parts of a 6 percent aqueous solution of a meal ether and
• 2 parts of polyglycol ester printed, dried, fixed in hot air at 200 ° C for 1 minute and washed after a reductive treatment.

You get brilliant orange prints with a very good stand.

In a mixture from Example 5

• 20 parts of water and
• 0.1 part of polyglycol ester are at room temperature with a turbo stirrer
• 20 parts of dibenzyl ether stirred in. The mixture is then stirred for 5-10 minutes at room temperature. The emulsion obtained is very stable and shows no signs of separation for months.

In a mixture from Example 6

• 20 parts of water and
• 0.2 parts of polyglycol ester are stirred at room temperature using a turbo stirrer
• 20 parts of dibenzyl ether stirred in. The mixture is then stirred for 5-10 minutes at room temperature. The emulsion obtained is very stable and shows no signs of separation for months.

Example 7

• 20 Teilen Toluol,
• 20 Teilen Wasser und
• 0,1 Teil Polyglykolester. Die erhaltene Emulsion ist sehr stabil und zeigt über Wochen keinerlei Trennerscheinungen.

An emulsion is produced from stirring for 5-10 minutes with a turbo stirrer at room temperature

• 20 parts of toluene,
• 20 parts of water and
• 0.1 part polyglycol ester. The emulsion obtained is very stable and shows no signs of separation for weeks.

Example 8

• 20 parts of a commercially available spindle oil are included
• 20 parts of water and
• 0.6 parts of polyglycol ester mixed and stirred for 5-10 minutes with a turbo stirrer at room temperature. A very stable oil-in-water emulsion is obtained.

Example 9

• 20 parts of the rubber anti-aging agent Vulkanox KSM @ (mixture of aralkylated phenols; commercial product from Bayer (AG) are included
• 0.5 parts of polyglycol ester and 20 parts of water combined. The mixture is stirred at room temperature with a turbo stirrer for 5-10 minutes. A very stable emulsion is obtained which shows no separation effects for months.

Example 10

• 200 g Methacrylsäuremethylester,
• 400 g entmineralisiertes Wasser und
• 10 g Polyglykolester vorgelegt. Der Kolbeninhalt wird mit Stickstoff gespült und danach auf 95°C aufgeheizt und mit einer Lösung von
• 0,2 g Kaliumperoxidisulfat in
• 10 g entmineralisiertem Wasser aktiviert. Nach Anspringen der Reaktion wird eine halbe Stunde gerührt und danach werden innerhalb einer Stunde bei 95°C innentemperatur folgende Lösungen gleichmäßig zudosiert:
  • 1) Eine Lösung von 0,4 Kaliumperoxidisulfat in 100 g Wasser und
  • 2) eine Lösung von 0,2 g Triäthanolamin in 80 g Wasser.

Man läßt nach beendetem Zulauf noch 2 Stunden bei 95°C nachrühren.In a two liter three neck flask with stirrer and reflux condenser

• 200 g methyl methacrylate,
• 400 g demineralized water and
• 10 g of polyglycol ester submitted. The flask contents are flushed with nitrogen and then heated to 95 ° C and with a solution of
• 0.2 g of potassium peroxydisulfate in
• 10 g of demineralized water activated. After the reaction has started, the mixture is stirred for half an hour and then the following solutions are metered in uniformly at an internal temperature of 95 ° C. within one hour:
  • 1) A solution of 0.4 potassium peroxydisulfate in 100 g water and
  • 2) a solution of 0.2 g triethanolamine in 80 g water.

After the feed has ended, the mixture is stirred at 95 ° C. for a further 2 hours.

A polymer emulsion is obtained which is practically free of coarse and fine coagulate. The conversion of the monomers is 95%.

Example 11 1

• 200 g Styrol,
• 400 g entmineralisiertes Wasser,
• 8 g Polyglykolester und
• 2 g eines geradkettigen C₁₂―C₁₈-Alkylsulfonsäureäthanolamidgemisches vorgelegt. Der Kolbeninhalt wird mit Stickstoff gespült und danach auf 95°C aufgeheizt und mit einer Lösung von 0,2 g Kaliumperoxodisulfat in 10 g entmineralisiertem Wasser aktiviert. Nach Anspringen der Reaktion wird eine halbe Stunde gerührt und danach werden innerhalb einer Stunde bei 95°C Innentemperatur folgende Lösungen gleichmäßig zudosiert:
  • 1) Eine Lösung von 0,4 g Kaliumperoxodisulfat in 100 g Wasser und
  • 2) eine Lösung von 0,2 g Triäthanolamin in 80 g Wasser.

Man läßt nach beendetem Zulauf noch 2 Stunden bei 95°C nachrühren.In a two liter three-necked flask with stirrer and reflux condenser

• 200 g styrene,
• 400 g demineralized water,
• 8 g polyglycol ester and
• 2 g of a straight-chain C ₁₂ -C ₁₈ alkylsulfonic acid ethanol amide mixture are introduced. The contents of the flask are flushed with nitrogen and then heated to 95 ° C. and activated with a solution of 0.2 g of potassium peroxodisulfate in 10 g of demineralized water. After the reaction has started, the mixture is stirred for half an hour and then the following solutions are metered in uniformly at an internal temperature of 95 ° C. within one hour:
  • 1) A solution of 0.4 g potassium peroxodisulfate in 100 g water and
  • 2) a solution of 0.2 g triethanolamine in 80 g water.

After the feed has ended, the mixture is stirred at 95 ° C. for a further 2 hours.

A polymer emulsion is obtained which is free of coarse or fine deposits, the monomer conversion is 100%.

Claims (10)

1. Compounds of the formula

in which R is an open-chain aliphatic radical having from 9 to 19 carbon atoms; Z stands for hydrogen and methyl, the ratio of H:CH₃ being from 2:1 to 4:1

a is zero or 1,

b is 1 to 1.5, and

(4-a) n is 150 to 300.

2. Compounds according to claim 1, characterized in that R-CO- represents the acyl radical of a fatty acid having from 11 to 17 carbon atoms in the radical R.

3. Compounds according to claims 1 and 2, characterized in that the ratio of H:CH₃ in the radical Z is from 2.5:1 to 3.5:1.

4. Compounds according to claims 1 to 3, characterized in that (4-a) n is from 200 to 250.

5. Compounds according to claim 1, characterized in that RCO is oleyl; the ratio of H:CH₃ in the radical Z is 3:1 in random distribution, a is zero, (4-a) n is about 210, and b is 1.1.

6. Process for the preparation of the compounds according to claim 1, characterized in that a compound of the formula

in which a is zero or 1, is oxalkylated with a mixture from ethylene oxide and propylene oxide in a molar ratio of from 2:1 to 4:1 and partially esterifying the oxalkylation product with an acylating agent introducing the radical R-CO-.

7. Use of the compounds according to claim 1 as surface active agents.

8. Use of the compounds according to claim 7 for enhancing respectively stabilizing the viscosity of aqueous systems.

9. Use of the compounds according to claim 7 as emulsifiers.

10. Use of the compounds according to claim 7 as additives to printing pastes or padding liquors.

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