DE2137942A1 - POLYAETHER - Google Patents

Description

Badische Anilin- & Soda-Fabrik AG 2137942

Our mark G.Z. 27 6jO Ze / Wil

6700 Ludwigshafen, July 28, 1971 -

Polyether

The invention relates to new polyethers attached to the free hydroxyl groups are fully or partially esterified with carboxylic acids.

It also relates to a process for their production and their use as an essential component in dyeing auxiliary preparations.

It is known prior art to convert hydrophobic fatty substances into surfactants by introducing hydrophilic groups it by oxethylation, iminoethylation, be it by reaction with inorganic or organic acids, such as sulfuric, phosphoric, halocarboxylic or sulfonic acids, among others. Instead of fat bodies It is also possible to start from synthetic hydrophobic compounds with higher molecular weight hydrocarbon radicals, for example of higher molecular weight alcohols, such as those obtainable according to the oxo synthesis or according to Ziegler.

Another known group of surface-active compounds is represented by block copolymers of 1,2-propylene oxide and ethylene oxide, which _{correspond to the formula HO (C 2} H _{2 {} .O) ^ (C ₅ HgO) _x (C ₂ H2 _i O) ^ H. The use of higher ethers in such block copolymers and the use of these block copolymers as textile auxiliaries, which are used specifically for leveling and foam dampening, have been common property of technology for many years. German Patent 1,027,178, for example, describes the use of trimethylene oxide alcohols with polyethylene side chains as wetting agents, emulsifying agents, dispersing agents, leveling agents, dyeing auxiliaries or cleaning agents.

A special process for the production of polyethers contain a polymerized tetrahydrofuran as middle blocks ^, is described in German Auslegeschrift 1 302 652, Die Literature teaches, among other things, as a property that

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foam-suppressing effect of such a product.

Disadvantages of all the compounds discussed so far, however, are their still strong hydrophilic effect. In many cases namely In textile technology, means are required that are outside of their own hydrophilic also have more or less strongly hydrophobic properties. In the case of block copolymers made of ethylene and / or Naturally, however, this is not yet sufficiently the case for propylene oxide. The last-mentioned reference comes to the solution this problem a little closer, since it proposes a polymeric tetrahydrofuran as the middle block.

In textile technology, e.g. B. in dyeing, it is particularly important that products are used, their hydrophilic and there is a balanced relationship between lipophilic properties, d. H. that the affinity of the hydrophilic groups is of the order of magnitude correspond to the affinity of the lipophilic groups for the corresponding partners.

According to the teaching of DAS 1 j5O2 652 one came closer to the goal, when the central block of the copolymers now consisted of monomer units containing 4 carbon atoms in a straight chain. The hydrophilicity could then be determined by a more or. regulate fewer large numbers of polyethylene oxide units. the The foam-absorbing properties of these compounds in particular were not yet completely sufficient, because despite the longer ones hydrophobic chains are still sufficient free hydrophilic groups present in the interior of the molecules. The foam-suppressing effect could therefore not be satisfactory in many cases.

A new class of compound has now been found which, surprisingly, is an essential component in low-foam Dyeing auxiliaries can play the paramount role. These are compounds of the formula T.

Y-Z-X 'I,.

in which X is the remainder of a fatty acid with 8 to 30 carbon atoms, Y is a hydrogen atom or the radical X and Z the radical

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of a polyether of the formula II

-A-B-A- II

means in which A stands for a polyethylene oxide block with 4 to 100 monomer units and B stands for a polymer block which is based on a homopolymer of a cyclic ether with 3 to 12 linearly linked carbon atoms and at least 4 carbon atoms in the molecule or a copolymer of a mixture of cyclic ethers or a cyclic ether with ethylene and / or Propylene oxide is based, the polymer block B being built up from 4 to 100 monomer units, and the sum of the monomer units A + B is equal to or greater than 10.

The preparation of these compounds is known per se Methods possible and based, as far as it relates to the middle block, on the cationic polymerization of a cyclic ether, subsequent oxethylation and esterification of the oxyalkylation product obtained with a carboxylic acid mixture in a molar ratio of 1: 1 or 1: 0.5 · If the middle block B is a copolymer of mixtures of cyclic ethers or a copolymer of one of the cyclic ethers with ethylene or propylene oxide is to be represented, then one proceeds in a known manner suggest that these mixtures after one of the usual polymerization mechanisms first establishes.

Starting materials for the preparation of the compounds according to the invention are cyclic ethers or mixtures of cyclic ethers and finally mixtures of cyclic ethers with ethylene and / or Propylene oxide. The cyclic ethers contain 3 to 12, preferably 4 to 8, carbon atoms in a straight chain with the proviso that at least 4 carbon atoms are present in the molecule. That in other words, that the straight carbon chains can also be substituted. Suitable substituents are here preferably alkyl groups with 1 to 5 carbon atoms or aryl groups, preferably the phenyl group. As starting compounds recommend in the sense of the invention, for. B. tetrahydrofuran, pentamethylene oxide, hexamethylene oxide, heptamethylene oxide or octamethylene oxide. Also suitable is the dodecamethylene

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oxide, especially when polymers with longer hydrophobic chains are desired. Technically of particular interest here the tetrahydrofuran. If the middle block: B through copolymers is represented, mixtures of the cyclic ethers come into consideration, as they are named by definition. About that In addition, ethylene oxide and / or propylene oxide can be used as mixed components, the former compound being a preferred one Mixing component represents. In the context of the invention, a middle block B consisting of ethylene oxide and tetrahydrofuran is particularly valuable is present in several blocks or alternately copolymerized.

The middle block B should contain 4 to 100 bound monomer units, it does not matter whether the monomer units are the same or different, d. i.e. if block B is a copolymer represents, the numerical conditions must nonetheless be met.

The middle block B is then oxethylated in a manner known per se. Here are to be represented by the ethylene oxide groups flanking blocks A also contain 4 to 100 monomer units each. However, the condition is that the sum of the Monomer units A and B does not fall below the number 10.

Functional as fatty acids or their usual esterifications Derivatives are all those which, by definition, have 8 to 30 carbon atoms, preferably 12 to 28 carbon atoms contain, or mixtures thereof, and this to a preferred extent. If mixtures are used, the result is products of Formula I, which in turn represent a particularly effective mixture of substances within the meaning of the invention.

Fatty acids can be saturated or unsaturated and are, for example, oleic acid, erucic acid, rapeseed oil fatty acid, tall oil fatty acid, stearic acid, Tallow fatty acid, oil hard fatty acid, myristic acid, palmlatinic acid, tranhard fatty acid, palm oil hard fatty acid, ricinoleic acid, Linolenic acid, linoleic acid, or mixtures thereof. These fatty acids come as esterification components for those according to the invention Substances of the formula I are suitable, where the fatty acids either esterify both flanking hydroxyl groups or only one,

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where Y in formula I then denotes the radical of a hydrogen atom The partial esterification before the total esterification offers no further advantages over the properties according to the invention,

In detail, these connections are made in several stages in a manner known per se. The polymerization of the monomeric cyclic ethers or copolymerization takes place by cationic polymerization. In general, acidic or, when using lower molecular cyclic ethers, alkaline catalysts are also used. The acidic catalysts used are Lewis acids, such as boron fluoride etherate, in a manner known per se, Antimony pentachloride, tin tetrachloride, aluminum chloride, Titanium tetrachloride, Eisenlll chloride and other catalysts, such as those used, for. B. known as Friedel-Crafts catalysts, in Consideration.

The polymerization is carried out so that in the end 4 to 100, preferably 15 to 65 monomer units are present in a straight chain.

Ethylene oxide is then added to the middle block in a manner known per se, the reaction in this case being statistical expires, d. That is, at both ends of the central polymer there is approximately the same number of ethylene oxide units in a row. The blocks A must also be 4 to 100, preferably contain 15 to 65 monomer units. These polymers are then completely or partially with the fatty acids or fatty acid mixtures mentioned in a known manner implemented.

The new compounds or compound mixtures are essential components of a highly effective, low-foam dyeing aid. A cheap dyeing auxiliary preparation consists z. B. from 10 to 50 percent by weight, based on the dyeing aid, one of the products or product mixtures according to the invention, preferably an esterified copolymer of tetrahydrofuran with ethylene oxide, esterified with stearic or rapeseed oil fatty acid, and to 10 to 50% by weight of a customary nonionic and / or an anionic or cationic surfactant, Such a composition contains about "20 to 80 percent by weight,

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based on the dyeing aid, water and / or an organic solvent. The application of these liquid components depends on the length of the hydrophobic residue in the component represented by the compound according to the invention will.

It is surprising that these products according to the invention can be used in such a problem-free manner as low-foam dyeing auxiliaries allow. It would have been to be expected that the accumulation of hydrophobic residues, namely the long alkyl chains in the middle block and in addition the long hydrophobic fatty acid residues at the ends of the molecule a strong intolerance with the dye liquors. So it certainly existed a prejudice in technology that the length of the hydrophobic residues should be increased too much by the order of magnitude. That this is in On the contrary, an improvement in the products would result, and that the compatibility with an aqueous dye liquor with the aid simple common anionic surfactants would be guaranteed, it therefore represents a real invention and advancement this area.

The dyeing auxiliary preparations which contain the substances according to the invention can be prepared by simply stirring them together Mixtures of oil and fatty acid esters with surfactants and water are obtained as clear homogeneous mixtures that are obtained at room temperature are very stable in storage. If the hydrophobic residues no longer allow a clear solution by default, it is possible to produce stable emulsions in this way, which also surprisingly do not tend to "cream".

These dyeing auxiliaries can also be used with water-soluble organic solvents, such as butyl diglycol, butyl triglycol, Isopropanol, dipropylene glycol, butyrolactone, M-methylpyrrolidone or add dimethylformamide. The storage stability of the dyeing aid preparations can be significantly improved as a result.

Surfactants that are used as admixing components for the inventive Compounds come into consideration are, for example, non-ionic

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gene compounds, such as addition products of ethylene oxide, Propylene oxide, butylene oxide or mixtures of these epoxides saturated fatty acids, fatty alcohols, fatty amines, fatty amides, Alkylphenols, glycols and other compounds whose active hydrogen atoms enable epoxy to attach.

Anion-active compounds., Z. B. by sulfation or Sulphonation can occur, are z. B. sulfuric acid half esters of the above nonionic products, which are obtained by oxethylation or oxpropylation or by simultaneous or alternating addition of ethylene oxides in several steps and propylene oxide, sulfuric acid half-esters of fatty alcohols, sulfated Castor oil and its derivatives, sulfated or sulfonated oleic acid and its derivatives, alkylbenzene, sulfonic acids and alkyl sulfonic acids.

Cation-active compounds provide z. B. Salts of the alkylpyridinium ion of the methylalkylpiperidinium ion or tetraalkylammonium, in which an alkyl radical has at least 10 carbon atoms Contains in the main chain. These compounds mentioned are known washing, wetting and leveling aids, which, when used on their own, cause a very strong foam, which causes the usual disadvantages in the dyeing process, such as those caused by excessive foaming.

A finished dyeing auxiliary preparation has, using the agents according to the invention, for. B. the following composition: 10 to 70 percent by weight, based on the dyeing auxiliaries, preferably 20 to 50 percent by weight, of one or a mixture several of the above-mentioned surfactants, also 10 to 70, preferably 20 to 50 percent by weight, based on the dyeing auxiliary on products according to the invention. They also contain 20 to 80, preferably 55 to 70 percent by weight, based on the dyeing auxiliary, in water and / or an organic solvent, according to the stipulation - as mentioned above - the length of the hydrophobic residues. The compounds according to the invention can be used as dyeing auxiliary preparations described above in all dye and padding liquors in which the pH ■ Value is between 2 and 8, in caustic alkaline liquors

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. They are not used, since the inventive Defoamers are esters that are saponified and inactivated in an alkaline medium.

The following settings are recommended for the individual fiber types of the preparations according to the invention: For dyeing wool and synthetic polyamide fibers with 1: 2 and 1: 1 metal complex dyes can be oxyethylated fatty alcohols, saturated fatty acids, fatty amines or fatty acid amides and their sulfation products be used. Mixtures of these compounds, the effects of which sometimes exceed those of the individual components also suitable for the production of low-foam auxiliary mixtures.

Acid dyes can also be produced with these dyeing auxiliaries dyeing on wool and polyamide fibers, especially poorly e galizing types, which usually have good wet fastness. Furthermore, wetting products can also be added, for example fatty and oxo alcohols with a low degree of oxyethylation as well as alkyl phenols. Connections to which. Alternating propylene oxide and ethylene oxide Steps are attached.

For dyeing synthetic polyamide fibers with acid dyes are mainly used as surfactants a) anion-active products that are absorbed by the polyamide fibers and thereby partially block. This slows down the absorption of the anionic acid dyes and there are differences balanced in the dye affinity of individual fibers.

For dyeing with disperse dyes on synthetic ones Polyamide fibers and polyester fibers, especially polyester fibers based on glycol terephthalate, are used as surfactants Ethylation products of saturated fatty alcohols, fatty acids, castor oil, alkylphenols and mixtures of these products. When working with the dyes mentioned, agents are added to the dyeing auxiliaries to improve stability improve the dye dispersion, for example reaction products of formaldehyde with naphthalenesulfonic acid. Furthermore can

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organic solvents which act as carriers are added when dyeing polyester fibers, such as, for example, halobenzenes; Esters of salicylic acid or homosalicylic acid with Methanol, ethanol or propanol; Addition products of one mole of ethylene oxide with chlorophenols, such as p-chlorophenol or mixtures of o- and p-chlorophenolj diphenyl or hydroxydiphenyl.

In some cases, especially with the admixture of carriers that are necessary for dyeing polyester fibers, the addition of water can be dispensed with if these carriers are at room temperature are liquid and can thus serve as organic solvents. In this case, it is preferable to use 20 to 80j 55 to 70 percent by weight, based on the dyeing aid, add this · solvent to the dyeing aid immediately. Halogenated derivatives of, for example, are used as carriers Benzene, toluene, naphthalene or methyl naphthalenes, monoglycol ethers of phenol, cresols, xylenols, naphthols or chlorine derivatives of these compounds and esters of salicylic acid with methanol, ethanol, propanols or butanols. In addition to these mixtures, such detergents must be added, which emulsify these carriers when they are poured into water and keep the defoamers in solution. For example, are preferred here oxethylated fatty acids, fatty alcohols or alkylphenols are used.

For dyeing anionically modified polyacrylonitrile fibers with cationic dyes are surface-active as detergents quaternary amines used, e.g. B. Alky! Pyridinium salts, in which the alkyl group has between 10 and 18 carbon atoms possesses, N-alkyl-.N-methyl-piperidinium or morpholinium salts, in which the alkyl group also has between 10 and 18 carbon atoms, as well as N-Benzy! pyridinium salts. These connections have an affinity for anionically modified polyacrylonitrile fibers and thereby slow down the absorption of the cationic dyes or promote their equalization.

In general, anionic compounds such as salts can be used as surfactants the sulfosuccinic acid dialkyl ester, salts of sulfated esters or amides of ricinoleic acid or oleic acid, salts of alkyl

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benzenesulfonic acids or alkylnaphthalenesulfonic acids, which act as wetting agents, are used.

Oxethylation products of castor oil, fatty alcohols, Oxo alcohols, the alkylphenols, the fatty acids and the Fatty amides are added. Mixtures of anionic and nonionic products are particularly advantageous. For dyeing of polyester fibers with disperse dyes, which are generally produced at high temperatures in short reaction times (thermosol process) is carried out, are also polyacrylic acid derivatives particularly advantageous because they suppress the migration of the padded dye pigments.

The parts mentioned in the following examples are parts by weight.

General manufacturing instructions for the products according to the invention;

a) oxethylation stage;

_{1 part of polyether (polytetrahydrofuran, polyhexamethylene oxide) or a copolymer of polytetrahydrofuran and polyethylene oxide is placed in the V 2} A stirred autoclave together with 1 to 2 percent by weight, based on the polyether, of a catalyst such as sodium methylate, sodium hydroxide or potassium hydroxide. A number of parts of ethylene oxide corresponding to the desired molecular weight is then injected in portions at 125 ° C. and a pressure of 6 to 8 atmospheres for several hours under nitrogen and with stirring. After constant pressure has been reached, the reaction product is characterized by determining its OH number.

b) esterification

1 mole of the compound prepared under a), 1 percent by weight, based on the compound, of a conventional esterification catalyst, such as p-toluenesulfonic acid, and 1 to 2 moles of a fatty acid are heated together for ~ 5 hours with stirring and nitrogen at 15O ⁰ C. Then within 3 hours at 15O ⁰ C under reduced pressure of about 10 to

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20 mm Hg removed the water of reaction. However, the esterification may also descending condenser for 4 to 5 hours by continuous treatment under reduced pressure at 150 ⁰ C, or by means of heat (without added catalyst) for 5 to 6 hours at a reaction temperature of l80 to 200 ⁰ C under reduced pressure be effected, wherein the pressure can be adjusted depending on which residual fatty acid content is desired, which has often proven to be favorable for the effectiveness in terms of application technology.

The reaction products are usually thicker, more pasty or more of a waxy consistency, and depending on the starting product, colorless to brown; you can use the following key figures are characterized: saponification number, acid number, OH number.

The respective melting points are not very characteristic.

The following examples use individual reaction products shown.

Mixtures were used to test the foam-absorbing properties

40 parts of fatty acid esters of ethoxylated polyethers or polyether copolymers,

20 parts of adduct of 47 moles of ethylene oxide with castor oil and

40 parts of water

optionally mixed with heating. The result is viscous pastes or solutions that are diluted with warm water there is a solution to be defoamed. The viscosity of the abovementioned mixtures can be increased by adding 10 to 20 parts of isopropanol effectively reduced, making the mixtures in water better can be solved.

The foam-suppressing effect was diluted according to DIN 53902 determined aqueous solutions of the following surfactants: A: Na salt of the sulfuric acid half ester of an addition product of 80 moles of ethylene oxide on stearyl alcohol, B: adduct of 47 moles of ethylene oxide on castor oil,

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C: 80 % sulfated castor oil,

D: adduct of 10 moles of ethylene oxide with nonylphenol,

E: adduct of 5 moles of ethylene oxide with oleic acid,

P: diethanolamine salt of dodecylbenzenesulfonic acid,

G: Na salt of a sulfated oleic acid butylamide,

H: adduct of 12 moles of ethylene oxide with oleylamine.

Very good foam absorption can be achieved with the following products, if you look at products A to C, E and G approx. 0.2 to 0.4 g / l of products according to the invention are added to solutions of 0.5 to 1 g / l of these surfactants. For D and F are with 0.2 to 0.4 g / l of products according to the invention, solutions with 0.2 up to 0.4 g / l of these surfactants defoams or reduces foam formation.

The defoaming effect can of course also be achieved with aqueous solutions of other anionic, cationic and nonionic surfactants can be observed.

With z. B. The following products result in good to very good defoaming of the surfactant solutions:

Table I.

Polytetrahydrofuran, molecular weight 2000

Example Amount deposited AO No. (parts by weight, based on

on poly-tetrahydrofuran - 1) ■

Fatty acid per mole of oxyethylation product

0.1 0.1 0.2 0.2

0.3 0.3 0.4 0.4 0.5 0.5

1 Mole Stearic acid 2 η Il 1 ti dd 2 ti ti 1 ti ti 2 It It 1 η Il 2 H It 1 It It

2 ^fl

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Example Amount of 'Ao fatty acid deposited per mole of ox-

No. (parts by weight, based on ethylation product

to poly-tetrahydrofuran Ü_1J,

11 0.6 1 mole of stearic acid

12 0.6

13 ■ 0.7

14 0.7

15 0.8

16 0.8

17 0.9

18 0.9

19 1,

20 1

21 1.5

22 1.5

23 2

24 2

25 2.5

26 2.5

27 3.1

28 -3.1

29 3.5

30 3.5

31 5.5

32 5.5

33 0.1

34 0.1

35 0.2

36 0.2

37 0.3

38 0.3

39 0.4

40 0.4 '

41 0.5

42 0.5

43 0.6

44 0.6

45 0.7

46 0.7 2 "

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2 Il It 1 If ti 2 ti ft 1 Il dd 2 It ti 1 ti It 2 It Il 1 ti It 2 ti ti 1 ti It. 2 dd dd 1 H Il 2 Il H 1 dd Il 2 dd It 1 dd ti 2 ti t! 1 Il Il 2 It dd 1 It ti 2 Il It 1 MoI Ts 2 dd It 1 ti It 2 ti It 1 It ft 2 It It 1 dd If 2 It It 1 It If 2 Il If 1 It st 2 It 91 1 dd I!

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example
No. Trapped amount of AO
(Parts by weight, based
to poly-tetrahydrofuran
- D Fatty acid, per mole of ox-
ethylation product Sebum fatty acid 47 0.8 1 mole It 48 0.8 2 " It 49 0.9 1 " η 50 0.9 2 " « 51 1 1 " ti 52 1 2 " η 53 1.5 1 " ti 54 1.5 2 " η 55 2 2 ⁿ Rape oil hard fatty acid 56 0.5 2 moles It 57 1.0 2 ^lf It 58 2.0 2 " It 59 4.0 2 " It 60 8.0 2 " Myristic acid 61 2.0 2 moles It 62 4.0 2 " Palmitic acid 63 2.0 2 moles Il 64 4.0 2 " Tranhart fe 11 acid 65 0.5 2 moles It 66 1.0 2 " It 67 2.0 2 " ti 68 4.0 2 " If 69 6.0 2 ^lf Palm oil fatty acid 70 0.5 2 moles It 71 1 2 ^fl Il 72 2 2 " Palm oil hard fatty acid 73 0.5 2 moles It 74 1 2 " It 75 2 2 " η 76 4th 2 ⁿ

Polytetrahydrofuran, molecular weight 1000 77 0.6

1.3 2.5

2 moles of stearic acid ο w tf

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example
No.

Amount deposited AO (parts by weight, related on polytetrahydrofuran)

Fatty acid per mole of oxyethylation product

0.6

1.3

2 moles of tallow fatty acid

polytetrahydrofuran, molecular weight 28OO

82 0.6 83 1.2 84 2.5 85 0.6 86 1.2

2 moles of stearic acid

ο 11 11

p tt tt

2 moles of tallow fatty acid

p 11 ti

Polytetrahydrofuran, molecular weight 4650

87 0.6 2 moles of stearic acid 88 1.2 CVl 89 2.5 CVl example
No. Affair. Quantity Ä * 0
(Parts by weight, based
on poly-THF = 1 or
other polyether) Fatty acid per mole
Ethylation product 90 0.6 2 moles of tallow fatty acid 91 1.5 CVl 92 2.5 CVl

Copolymer of hexamethylene oxide and ethylene oxide 1: 1, Molecular weight 2200

1 mole of stearic acid

2 moles of stearic acid, 2 moles of tallow fatty acid

1 H Il

2 Ii ti 1 It Η ρ It It

93 3 94 3 95 1.1 96 '2 97 2 98 3 99 3

The following products also have anti-foam effects:

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Example Amount deposited AO No. (parts by weight, based on »On polytetrahydrofuran

- D L

Fatty acid per mole of oxyethylation product

Polytetrahydrofuran, molecular weight 2000

100 0.5 101 1.0 102 2.0 103 4.0 104 0.5 105 1.0 io6 2.0 107 3.1 io8 3.5 109 5.5 110 2.0 111 2.0 112 2.0 113 2.0

2 moles of oleic acid

ο tt ti

ο it ti

ο ti «ι

2 moles of rapeseed oil fatty acid

2 ti ti

2 ι »ι»

2 moles of tallow fatty acid

ο ti ti

2 it ti

2 moles of ricinoleic acid

2 moles of linoleic acid

2 it ti

2 moles of tall oil fatty acid

Polytetrahydrofuran, molecular weight 1000

114 0.6

115 1.3

116 2.5

117 2.5

Polytetrahydrofuran, molecular weight 2800

118 0.6

119 1.2

120 2.5

121 2.5

2 moles oleic acid 2 ti ti 2 it it 2 moles tallow fatty acid

2 moles of oleic acid 2 » 2 ti ti 2 moles of tallow fatty acid

Polytetrahydrofuran, molecular weight 4650

122 0.6 2 moles of oleic acid

123 1.2 2 ""

124 2.5 2 ""

2 0 9 8 8 6/108 -17-

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In the following Table II, by way of example, dyeing auxiliary preparations with the products according to the invention are given to be shown:

TABLE II Examples of aid mixes

1. 50 parts product No. 31 " ¹ ^ 20" A ⁺⁺⁾

50 "water viscose paste, clearly soluble in water Foam: 1 g / l RT ⁺⁺⁺ '27 2 g / l RT

60 ⁰ C 18 60 °

2. 30 parts of Product No. 51 '20 "A 50" water

Viscous paste, clearly soluble in water. Foam: 1 g / l RT 15 2 g / l RT. 6O ⁰ C 7 6O ⁰ C

3. 30 parts of Product No. 20 "A 50" water

Viscous paste, clearly soluble in water. Foam: 1 g / l RT 21 2 g / l RT 60 ⁰ C 9 60 ⁰ C

4. 30 parts of product # 20 "A 50" water

Viscose paste, clearly soluble in water. Foam: 1 g / l RT 11 2 g / l RT 60 ° C 7 6O ⁰ C

5. 30 parts of product no.

20 "A *

50 "water

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Viscous paste, clearly soluble in water, foam: 1 g / l RT 9 2 g / l RT 22 60 ° C 4 60 ° C 4

+) serial number according to table I.
++) Surfactants, see pages 11 and 12
+++) RT = room temperature

These auxiliaries are for dyeing wool with 1: 2 metal complex dyes suitable.

Dyeing example for wool;

Add 1 part of C.I. Acid Red 296

2 parts of ammonium sulfate

2 parts of tools 1

in 2000 parts of water at 50 ⁰ C, which are in a reel vat. In this liquor 100 parts of wool flannel be dyed, by contacting the product at 50 ⁰ C in the winch, heats up in 45 minutes to boiling temperature, and dyeing is 1 1/2 hours at this temperature.

During the entire dyeing process, the liquor remains foam-free and the goods are removed from the reel without any disruptions it stays well below the surface of the fleet and does not float.

The result is a very level, rubbing-fast bluish-red coloration.

Examples of auxiliaries for dyeing polyester fibers

6. 40 parts of product # 96
50 parts B
10 parts of water

Viscous paste, clearly soluble in water, foam disintegration (method DIN 53 902)
0.5 g / l RT 14 seconds 60 ° C 4 seconds

1 g / l RT 8 "6O ⁰ C 5"

2 g / l RT 6 "6O ⁰ C 10"

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7. 20 parts of product # 97 30 parts B
50 parts of water

Viscous paste, clearly soluble in water, foam disintegration (DIN 53 902) 0.5 g / l RT 9 seconds 60 ° C 4 seconds

1 g / l RT 20 "60 ° C 7"

2 g / l RT 12 "60 ° C 23

ti

8. 30 parts of product # 95 -32.5 parts B

37.5 parts of water

Viscous paste, clearly soluble in water. Foam disintegration (DIN 53 902) 0.5 g / l RT 13 seconds 60 ° C 3 seconds

1 g / l RT 11 "60 ° C 8"

2 g / l RT 8 "60 ° C 6"

9. 40 parts of product # 38 50 parts B

10 parts of water

Viscous paste, clearly soluble in water, foam disintegration (DIN 53 902) 0.5 g / l RT 20 seconds 60 ° C 7 seconds

1 g / l RT 27 "60 ° C 6"

2 g / l RT 20 "- 60 ° C 7" '

10. 40 parts of product # 40 50 parts B
10 parts of water

Viscous paste, clearly soluble in water, foam disintegration (DIN 53 902)

0, VJI g / l RT 6th Seconds 60 "C 4th Seconds 1 g / i RT 8th η 60 ⁰ C 5 It 2 g / l RT 20th ti 60 ⁰ C 6th ti

11. 30 parts of product # 33 32.5 parts B
37.5 parts of water

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Viscous paste, clearly soluble in water, foam disintegrates (DIN 53 902) 0.5 g / l RT 40/0 60 ° C 5 seconds

1 g / l RT 50/0 60 ° C 7 "

2 g / l RT 110/40/0 60 ° C 9 "

12. 40 parts of product # 36 50 parts B
10 parts of water

Slightly viscous paste, clearly soluble in water, foam disintegration (DIN 53 902) 0.5 g / l RT 5 seconds - 60 ° C 3 seconds

1 g / l RT 6 "6O ⁰ C 4"

2 g / l RT 8 "60 ° C 5 V

13. 40 parts of product # 50 50 parts B
10 parts of water

Slightly viscous liquid, clearly soluble in water Foam disintegration (DIN 53 902) 0.5 g / l RT 10 seconds 60 ° C 3 seconds

g / l
g / l

RT 12 "RT 13"

6O ⁰ C 6o ° C

l4. 40 parts of product no. 49 50 parts B
10 parts of water

Slightly viscous liquid, clearly soluble in water Foam disintegration (DIN 53 902) 0.5 g / l RT 10 seconds

1 g / 1 RT 12 "

2 g / l RT 15 "

60 ⁰ C 5 seconds 60 ⁰ C 6 "6O ⁰ C 7"

Dyeing example for polyester fibers

1 part of auxiliary 6, 0.5 part of dye CI 26 090 and 0.5 part of dye CI 11 100 are added to 2000 parts of water at 50 ^{° C. and knitted fabrics made from textured polyester fibers are dyed at 125 °} C. for 1 hour yellowish brown coloring of very good levelness. The fleet

209886/1085 -21-

- 21 - c.z. 27

shows practically no foam formation in the course of the coloration.

In an analogous way, the same result can be used instead of the Auxiliaries 6, the auxiliaries 7 to 14 can be used, with 40 to 50 parts. Auxiliaries containing water approx. 0.75 to 1 part to 2000 parts of water or 100 parts of knitted fabric made of textured polyester fibers used.

The following auxiliaries can also be used for dyeing polyester fibers with disperse dyes.

15. 15 parts of product # 96 15 parts B

15 parts E

35 parts of water

20 parts isopropanol Clear, slightly viscous solution, clearly soluble in water.

Foam disintegration (DIN 53 902) in seconds

1 g / l RT 24 6O ⁰ C 22

2 g / l RT 27 60 ° C 25

16. 30 parts of product # 97 30 parts B

30 parts of E

10 parts of water

Paste, clearly soluble in water, foam disintegration (DIN 53 902) in seconds 0.5 g / l RT 13 60 ⁰ C 3

1 g / l RT 15 6O ⁰ C 8

2 g / l RT 1.6 60 ° C 12

17. 30 parts of product # 95. 30 parts of product B 30 parts of product E 10 parts of water

Viscous, homogeneous paste, clearly soluble in water Foam disintegration (DIN 53 902) in seconds 0.5 g / l RT 6 60 ⁰ C 4 .1 g / l RT 9 ^{60 0} C 4 2 g / l RT 11 60 ⁰ C 11

209886/10 85 ~ ²² '

- 22 - O.Z.

18. 30 parts of product # 39 30 parts B

30 parts of E

10 parts of water

Viscous paste, clearly soluble in water. Foam disintegrates in seconds (DIN 53 902) 0.5 g / l RT 9 60 ° C 3

1 g / l RT 4 6O ⁰ C 6

2 g / l RT 7 60 ° C 9

19. 25 parts of product No. 35 25 parts B

25 parts E

25 parts of water

Viscous paste, in water clearly soluble foam collapse (DIN 53 902) 0.5 g / l RT 9O / 3O / IO 6O ⁰ C 6 seconds

1 g / l RT 40/0 6O ⁰ C 9 "

2 g / l RT 20/0 6O ⁰ C 11 "

20. 25 parts of product # 40 25 parts of B

25 parts E

25 parts of water

Viscous paste, clearly soluble in water, foam disintegration (DIN 53 902) in seconds 0.5 g / l RT 3 60 ⁰ C 4

1 g / l RT 6 6O ⁰ C 3

2 g / l RT 5 60 ° C 3

21. 30 parts of product # 52 30 parts B

30 parts of E

Slightly viscous paste, clearly soluble in water, foam disintegration (DIN 53 902) in seconds 0.5 g / l RT 17 60 ⁰ C 8. 1 g / l RT 24 6O ⁰ C 2 2 g / l RT 17 6O ⁰ C 9

209886/1085 -23-

- 23 - G. Z, 27

Dyed in a manner analogous to that with auxiliary 6, auxiliary mixtures 15 to 21 also give when dyeing with disperse dyes Level dyeing and foam-free dye liquors on polyester fibers.

22. 10 parts of product # 94 20 parts D

Waxy mass, clearly soluble in water, foam disintegration (DIN 53 902) 0.5 g / l RT 50/40/30 6o ° c 70/30/10

1 g / l RT 40/10/10 60 ° C 40/20/10

2 g / 1 RT 60/10/10 6O ⁰ C 150/40 / 2p

23. 50 parts of product # 98

-50 parts product D -

Waxy mass, clearly soluble in water. Visual tissue breakdown (DIN 53 902) 0.5 g / l RT 60/10/10 60 ^{0 C 40/20/10}

1 g / l RT 20/10/10 6O ⁰ C 20/10/10

2 g / l RT 30/10/10 60 ° C 8O / 3O / IO

24. 50 parts of product # 1
50 parts of product D

Viscose paste, clearly soluble in warm water Foam disintegration (DIN 53 902) 0.5 g / i RT 70/30/10 6o ° c 30/10/0

1 g / l RT 90 / 3O / IO 6O ⁰ C 70/20/10

2 g / l RT 70/20/10 60 ° C 40/10/10

25. 30 parts of Product No. 98 30 parts of Product D

30. Parts of product E

Slightly viscous paste, clearly soluble in water, foam disintegration (DIN 53 902) 0.5 g / i RT 30/10/0 6o ° c 60/20/10

1 g / l RT 8O / IO / O 60 ° C 7O / IO / O

2 g / l RT 100/20/10 6O ⁰ C 8O / IO / O

209886/10 85 -24-

ο. ζ. 27-630

26. 30 parts of product No. 30 parts of product D 30 parts of product E

Slightly viscous paste, clearly soluble in water

Foam breakdown (DIN 53 902)

0.5 g / l RT 70/10/0 60 ° C 100/10/0

1 g / l RT ■ 110/20/0 60 ° C 120/10/0

2 g / l RT 190/40/0 60 ° C 300/10/0

27. 30 parts of product # 30 parts of product D 30 parts of product E

Slightly viscous paste, soluble in water to be clear-opaque

Foam breakdown (DIN 53 902)

0.5 g / l RT 100/60/30 6O ⁰ C 60/40/20

1 g / l RT 120/70/40 6O ⁰ C 40/10/0

2 g / l RT 10/0 6O ⁰ C 7O / 2O / O

28. 50 parts of product # 50 parts of product D

Yellowish, slightly viscous paste, clearly soluble in water, foam disintegrates (DIN 53 902)

■ 0.5 g / i RT 170/60/20 6o ° c i4o / 4o / io

1 g / l RT 110/20/10 60 ⁰ C 20/10/10

2 g / l RT I3O / IO / IO 6O ⁰ C 5O / IO / O

29. 30 parts of product No. 30 parts of product D 30 parts of product E

Yellowish, slightly viscous paste, clearly soluble in water

Foam breakdown (DIN 53 902)

0, 5 g / l RT 3O / O ] g / i RT 10/0 C. g / 3 RT 20 ⁷ O ! Ji 1 f ε «ι -te.!. '2 I. ij ?:> bej-p , - ■: j Ti ,, : Much

60 ⁰ C 60 ⁰ C

60 ⁰ C

10/0
20/10/0

40 ⁷ 20/0

in; = ji -: * lr »£ er Wej. ·: <: ■ like Hi" I fr: red] .'1 rl'v ^ f'ej. aun PES fibers vt ·· '---' ί: η < " 1

- 25 - O. Z. 27 6 ^ 0

Example: "".

2000 parts of water, 4 parts of auxiliary 32, 2 parts of 60 % acetic acid and 2 parts of sodium acetate are placed in a reel vat and 100 parts of knitted fabric made of textured polyamide 6.6 fibers are treated with them at 60 ° C. for 10 minutes. Then 1 part of Acid Yellow 25 and 0.5 part of Acid Blue 72 are added, the mixture is heated to boiling temperature in 30 minutes and dyed at this temperature for 1 hour. It is then cooled, rinsed and dried. A green dyeing of excellent levelness is obtained.

30. 40 parts of product # 25 parts of product F 10 parts of product H 25 parts of water Viscous paste, soluble in water to be clear-opaque, foam disintegration (DIN 53 902) 0.5 g / i RT 20/10/10 6o ° c 190/150/130

1 g / l RT I8O / 15O / IIO 60 ° C 220/190/150

2 g / l RT 70/40/30 60 ° C 5O / 3O / 5O

31. 40 parts of product No. 25 parts of product F 10 parts of product H 25 parts water viscose paste, clearly soluble in water foam disintegration (DIN 53 902)

0, 5 g / l RT 19 seconds 6o ^u C. 10/0 1 g / l RT 6O / 3O / IO 60 ° C. 19 seconds 2 g / l RT 80/30/20 60 ° C. 24 "

32. 40 parts of product no. 25 parts of product F 10 parts of product H 25 parts of water, viscose paste, clearly soluble in water. Foam disintegration (DIN 53 902) 0.5 g / l RT 40/50/20 60 ° C 40/30/20

1 g / l RT 50/30/20 6O ⁰ C 30/20/10

2 g / l RT 28O / 18O / 8O 60 ° C 10/10/0

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- 26 - O. Z; 27

33- ¹ ^ O parts Product no. 25 parts of Product C Product 10 parts 25 parts Water H viscous paste, in water clearly soluble foam collapse (DIN 53 902) 0.5 g / l RT 2 seconds 6o ° C 2 seconds

1 g / l RT 4 "60 ° C 3"

2 g / l RT 3 "60 ° C 4"

34. 40 parts of product # 4l 25 parts of product C 10 parts of product H 25 parts of water Viscous paste, clearly soluble in water. Foam disintegration (DIN 53 902) 0.5 g / l RT 1 second 60 ° C 3 seconds

1 g / l RT 2 seconds 6o ° C 2 "

2 g / l RT 2 "60 ° C 4"

35. 40 parts of product No. 61 25 parts of product C 10 parts of product H 25 parts of water Viscous paste, clearly soluble in water. Foam disintegration (DIN 53 902) 0.5 g / l RT 1 second 60 ° C 1 second

1 g / l RT 2 seconds 60 ° C 2 seconds

2 g / l RT 4 "60 ° C 10/10/0

36. 40 parts of product No. 25 parts of product C 10 parts of product H 25 parts water viscose paste, clearly soluble in water foam disintegration (DTN 53 902) 0.5 g / l RT 11 seconds 60 ° C 15 seconds

1 g / l RT 13 "6O ⁰ C 10"

2 g / l RT 8 "6O ⁰ C 10/10/0

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- 27 - O · ζ. 27

^ 137942

37-4θ parts of product no. 25 parts of product C 10 parts of product H 25 parts of water viscose paste, clearly soluble in water Foam disintegration (DIN 53 902) 0.5 g / l RT 1 second 60 ° C 1 second

1 g / l RT 1 "6O ⁰ C 1"

2 g / l RT 1 "60 ° C" 2 seconds

38. 40 parts of product no. 25 parts of product G 10 parts of product H 25 parts of water viscose paste, clearly soluble in water foam disintegration (DIN 53 902) 0.5 g / l RT 20/10/0 6O ⁰ C 10/10 / 0

1 g / l RT 10/0 6O ⁰ C 20/10/0

2 g / l RT 25 seconds 60 ° C 3Ο / 2Ο / Ο

Auxiliaries 30 to 38 are used as leveling agents when dyeing synthetic polyamide fibers.

2 ü 9 B ü f /

Claims (4)

- 28 - Point 27 of the claims 1. Compounds of formula I Y-Z-X I, in which X is the remainder of a fatty acid with 8 to ^ O carbon atoms, Y is a hydrogen atom or the radical X and Z is the radical of a polyether of the formula II -A-B-A- II means in which A stands for a polyethylene oxide block with 4 to 100 monomer units and B for a polymer block, on a homopolymer of a cyclic ether with 3 to 12 linearly linked carbon atoms and at least 4 carbon atoms in the molecule or a copolymer a mixture of the cyclic ethers or a cyclic ether with ethylene and / or propylene oxide is based, the Polymer block B is built up from 4 to 100 monomer units, and the sum of the monomer units A + B is the same or greater than 10. 2. Compounds of formula I according to claim 1, in which B is for a polymer block is on a homopolymer a cyclic ether with j5 to 12 linearly connected carbon atoms and at least 4 carbon atoms in Molecule is based. J>. Compounds according to claim 1 or 2, in which B stands for a polymer block in which tetrahydrofuran is used as monomer units. 4. Use of compounds according to Claims 1 to 2 as low-foam dyeing auxiliaries. Aniline & Soda Factory in Baden 209886/1085