CH666480A5 - NOVOLAK CONNECTIONS. - Google Patents

Description

DESCRIPTION It has been found that the compounds of the formula I

(I),

0R.

OR,

25 wherein the two R, each an isooctyl, nonyl or dodecyl radical, the two R2 independently of one another hydrogen or, if all R5 present mean a group S03R6, also a group of the formula -S03R6

R3 is a group of the formula - (CH2CH-> 0) m-R5, 30 - (C3H50) m-R5 or - (C4H80) m-R5,

R4 is hydrogen or a group of the formula - (CH2CH20) n-R5, - (C3H60) n-R5 or - (C4H80) n-R5,

an R5 a group of the formula -S03R6, the possibly present second R5 hydrogen or a group of the formula S03R6,

all R6 is hydrogen, an alkali metal, an alkaline earth metal equivalent or a nitrogen base,

m is 0, 1, 2 or 3 and n is 0, 1 or 2, where the sum m + n in the molerò kül is at least 1, at most 4, is excellently suitable as a dyeing aid, in particular for streak-free dyeing of textile material made of synthetic polyamides .

In preferred compounds of the formula I, the 45 two R | Nonyl radicals, one R2 hydrogen, the other hydrogen or, preferably, a group of the formula ~ S03R6,

R3 is a group of the formula - (CH2CH20) m-R5, - (CHCH20) m-R5 or - (CH2CH2CH2CH20) m-R5, preferably

CH3

assign a group of the formula -CHCH2OR5,

CH3

R4 is hydrogen or a group of the formula - (CH2CH20) n-R5, - (CHCH20) "- R5 or I.

CH3

- (CH2CH2CH2CH20) n-R5, preferably hydrogen,

an R5 a group of the formula -S03R6, the other hydrogen or a group of the formula -S03R6, preferably hydrogen all R6 hydrogen, a sodium, potassium or ammodi), nium ion, preferably a group of the formula -®NH4 65 or -® NH3CH2CH2OH,

m is 0, 1, 2 or 3, preferably 1 and n is 0, 1 or 2, the sum m + n being 1, 2, 3 or 4, preferably 1.

50

55

60

3rd

666 480

The preparation of the new compounds is characterized in that one mole of a compound of formula II

(II),

20;

10th

where the two R | one isooctyl, nonyl or dodecyl residue, 15

R7 is a group of the formula - (CH2CH20) m -H, - (C3H60) m-H or - (C4H80) m-H

R8 is a group of the formula - (CH2CH20) n-H,

- (C3H60) n-H or ~ (C4H80) n-H,

m denotes 0, 1, 2 or 3 and n denotes 0, 1 or 2, the sum m + n in the molecule being a maximum of 4, reacting with 1.5 to 2.5 mol of sulfur trioxide, sulfuric acid, aminosulfonic acid or, preferably, chlorosulfonic acid and optionally neutralizing the sulfonic acid group (s) with an alkali or alkaline earth hydroxide or with a nitrogen base.

The compounds of formula II can easily be prepared analogously to known methods for the preparation of novolak compounds, e.g. by condensation of two moles of an appropriately R, substituted phenol with 30 moles of formaldehyde (preferably in the presence of acidic catalysts) and addition of 1 to 4 moles of ethylene, propylene or butylene oxide. The reaction of the compounds thus obtained with sulfur trioxide, sulfuric acid, aminosulfonic acid or chlorosulfonic acid (1.5 to 2.5 mol per 35 mol novolak compound) is carried out in a generally known manner. If necessary, the acidic reaction product is finally treated with e.g. an alkali or alkaline earth hydroxide, ammonia or a basic amine, e.g. Monoethanol amine, di- or triethanolamine or morpholine, neutralized.

When reacting with sulfuric acid, sulfur trioxide, amino or chlorosulfonic acid, the aliphatically bound hydroxyl groups are first sulfated (esterified). If there is an excess of sulfuric acid etc., sulfonation 45 of the benzene nuclei takes place.

The compounds of formula I are poorly soluble in water, without solubilizers they form an opalescent mixture in water. However, if the new auxiliaries are dissolved in a so-called co-surfactant, which in the present case preferably includes one or more C3_6 aliphatic alcohols, e.g. Isopropanol, cyclohexanol, butanol, isobutanol, 2-methyl-2,4-diolpentane or l-butoxy-2-hydroxyethane are to be understood, the mixture completely dissolves in water at any dilution ratio used in practice. The mixing ratio of compounds of formula I to surfactant can e.g. fluctuate between 15:85 and 85:15, preferably 60 to 80 parts of the compounds of the formula I are dissolved in 40 to 20 parts of butanol, isobutanol or butylene glycol. However, solutions containing water can also be produced as a storable (commercial) form, e.g. from 15 to 30 percent compound of formula I, 5 to 30 percent of one or more of the above-mentioned cosurfactants and the rest water.

65

Dyeing and printing in the presence of the compounds of the formula I are carried out in the usual way. In general, between 0.02 and 20, in particular 0.1 to 15, weight percent of the new compounds, based on the weight of the substrate, are used.

The compounds of the formula I are particularly suitable as auxiliaries for dyeing fabrics (and knitted fabrics) made of synthetic polyamides with different dye affinities (compensation for streakiness). They can also be applied to textile blends containing synthetic polyamides. They also cause very level staining of mixtures of synthetic and natural polyamides. In their effect, they outperform similar known means very considerably. In their capacity as excellent dispersing and emulsifying agents, they can also be used wherever e.g. sulfonated castor oil, Turkish red oil etc. can be used. They are also suitable as auxiliaries for dyeing all other textile fiber materials, especially for dyeing polyester fibers. The new compounds also provide valuable services in leather dyeing and in the formulation of agrochemicals. In particular, the sulfonated products are also suitable, preferably in the presence of water glass, as stabilizers of H202 in the peroxide bleaching of cotton.

In the following examples, parts are parts by weight, percentages are percentages by weight. The temperatures are given in degrees Celsius.

example 1

In a suitable flask, 880 parts of nonylphenol are heated to 50 ° while stirring and introducing nitrogen gas, with 13.2 parts of oxalic acid dihydrate, 8.4 parts of demineralized water, 4.4 parts of sodium dodecylbenzenesulfonate (wetting agent) and finally, in portions, with 63.2 parts of paraformaldehyde. The paraformalde hydrate is added so that the temperature in the flask rises to values between 85 and 95 '. Thereafter, the mixture is slowly heated to 120 to 125 °, the water contained in the reaction mass is distilled off under a continuously increasing vacuum to about 660 Pa, the mixture is heated further to 160 °, stirred for a further 3 hours, the vacuum is released by the addition of nitrogen, and the mixture is added slowly add 5 parts of solid sodium hydroxide, evacuate again with stirring (to approx. 2400 Pa) and introduce 264 parts of ethylene oxide below the surface. 584 parts (about half) of the novolak-ethylene oxide reaction product obtained are placed in a suitable flask, 861 parts of methylene chloride are added with stirring, the mixture is cooled to 2-5 °, and the mixture is mixed very slowly with 233 parts of chlorosulfonic acid, the Temperature may rise to a maximum of 20 °. The resulting hydrochloric acid gas is absorbed in aqueous sodium hydroxide solution. After the chlorosulfonic acid addition has ended, the mixture is stirred for about 3 hours, the reaction mass is cooled to room temperature and slowly, in 190 parts, monoethanolamine cooled to 2 to 5 ° is added, the temperature not exceeding 20 °. The mixture is stirred for a further 2 hours at room temperature, the methylene chloride is distilled off (at approx. 65 ° and a vacuum which increases towards 8000 Pa towards the end). Finally 590 parts of active ingredient of the formula remain in the flask

C9H19

C9H19

a ©

0 CH2CH20S03 NH3CH2CH20H 0 (CH2CH20) 2S0® ° NH3CH2CH20H

666 480

which are mixed with 300 parts of isobutanol and stirred at about 40 ° to a clear solution. Instead of the 190 parts of monoethanolamine, the equimolecular amount of di-

ódé? Mikaiiòto, Möhlin adle Ammmìé m New.

tralisation can be used.

Analogously to this working procedure, the amounts (in moles) of the starting substances given in the following table can also be converted into new auxiliaries. In all cases, the condensation product from 2 moles of alkylphenol and 1 mole of formaldehyde is used.

table

E.g.

Alkyl

Mol

Mol

No.

R.

Alkylene oxide

Chlorosul

fonic

2nd

Nonyl

3 propylene oxide

2nd

3rd

Dopdecyl

3 ethylene oxide

2nd

4th

Nonyl

2 ethylene oxide

2nd

5

do.

1 ethylene oxide

1.5

6

Nonyl

1 propylene oxide

2nd

7

do.

4 ethylene oxide

2nd

8th

do.

4-propylene oxide

2nd

9

do.

3-propylene oxide

2.5

10th

do.

1 ethylene oxide

2nd

11

Dodecyl

2 ethylene oxide

1.5

12

do.

do.

2nd

13

Isooctyl do.

1.5

14

do.

do.

2nd

15

Nonyl

1 propylene oxide +

2nd

2 ethylene oxide

16

do.

do.

2.5

17th

do.

2 propylene oxide +

2nd

18th

do.

do.

1.5

19th

do.

1 propylene oxide +

2nd

3 ethylene oxide

20th

do.

do.

2.5

21st

do.

do.

1.5

22

do.

1 butylene oxide

2.25

Application example 1

100 parts of a streaky nylon 6 fabric are made in 1500 parts of a monosodium

pliöspliat and on flH 8 ptâ

ten dye bath, which contains 0.6 parts of a commercial product from C.I. Acid Red 57 and 2 parts of the compound of Example 6 neutralized with monoethanolamine from the table, treated for 90 minutes at cooking temperature. After rinsing and drying, the result is an excellent level red color.

With similar success, instead of C.I. Acid Red 57 the dyes C.I. Acid Blue 80, C.I. Acid Orange 148, C.I. Acid Orange 127 or a similar dye, or a combination of such dyes can be used.

Example of use 2

100 parts of a nylon 6 wool blend 60:40 are mixed in 3000 parts of a pH 8 liquor containing 1 part of a commercial product from C.I. Acid Blue contains 80 and 4 parts of the compound of the first example neutralized with monoethanolamine, dyed at 98 ° for 90 minutes, rinsed and dried. You get a perfectly level, deep blue color.

Instead of the compound of Example 1, the (equal amount of) compound of Example 8 or 10 can also be used.

Instead of C.I. Acid Blue 80 can also be one of the dyes C.I. Acid Orange 145, C.I. Acid Orange 127, C.I. Acid Red 299, C.I. Acid Red 57, C.I. Acid Red 263, C.I.

Acid Violet 48, C.I. Acid Blue 126 or C.I. Acid Blue 271 can be used with virtually the same success.

Example of use 3

A commercially available polyester fabric is treated with 0.5% of the dye C.I. Disperse Red 13, 2 g / 1 ammonium sulfate and 2 g / 1 of the compound of Example 6 in the table, at pH 5 (adjusted with formic acid) and a liquor ratio of 1:20 20 min. Under pressure, colored at 130 in a conventional manner. A perfectly dyed fabric is obtained after washing and rinsing.

4th

5

10th

15

20th

25th

30th

35

40

C.

Claims (5)

666 480 2. Compounds of formula I according to claim 1, wherein the two R, nonyl radicals, one R2 hydrogen, the other hydrogen or a group of the formula -S03R6, R3 is a group of the formula - (CH2CH20) m-R5, - (CHCH20) m-R5 or - (CH2CH2CH2CH20) m-R5, CH3 R4 is hydrogen or a group of the formula - (CH2CH20) n-R5, - (CH2CH2CH2CH20) n-R5 or - (CHCH-> 0) n-R5, preferably hydrogen, i CH3 one R5 is a group of the formula -S03R6, the other is hydrogen or a group of the formula -S03R6, all R6 is hydrogen, a sodium, potassium, ammonium ion or monoethanol ammonium, m is 0, 1, 2 or 3 and n is 0, 1 or 2, the sum m + n being 1, 2, 3 or 4, preferably 1. 2nd PATENT CLAIMS 1. Compounds of Formula I (I), OR. OR, wherein the two R, each an isooctyl, nonyl or dodecyl radical, the two R2 independently of one another are hydrogen or, if all R5 present are a group of the formula S03R6, also a group of the formula -S03R6, R3 is a group of the formula - (CH2CH20) m-Rs> - (C3H60) m-R5 or - (C4H80) m-R5, R4 is hydrogen or a group of the formula - (CH2CH20) n-R5, - (C3H60) n-R5 or - (C4H80) n-R5 an R5 is a group of the formula -S03R6, the possibly present second R5 hydrogen or a group of the formula -S03R6, all R6 are hydrogen, an alkali metal, an alkaline earth metal equivalent or a nitrogen base, m is 0, 1, 2 or 3 and n is 0, 1 or 2, the sum m + n in the molecule being at least 1, at most 4. 3. Compounds of formula I according to claim 1, wherein the two R | Nonyl residues, one R-> hydrogen, the other a group of the formula -SO3R6, " R3 is a group of the formula -CHCH2OR5 I. CH3 R4 is hydrogen, R5 is a group of the formula -S03R6 and both R6 are a group of the formula -®NH4 or -®NH3CH2CH2OH. 4. A process for the preparation of compounds of formula I, according to claim 1, characterized in that one mole of a compound of formula II wherein the two R, each an isooctyl, nonyl or dodecyl radical, R7 is a group of the formula - (CH2CH20) m-H, - (C3H60) m-H or - (C4H80) ra-H 5 R8 is a group of the formula - (CH2CH20) n-H, - (C3H60) n-H or - (C4H80) n-H, m is 0, 1, 2 or 3 and n is 0, 1 or 2, the sum m + n in the molecule being at least 1 and at most 4, with 1.5 to 2.5 mol of sulfur trioxide, sulfuric acid, amino-10 sulfonic acid or Chlorosulfonic acid.