DE1793740C3 - Quaternary ammonium compounds - Google Patents

Description

CH ₂ -C ₁₁ H ₅

C ₁₁ H ₅ -CH ₂

whereinX is an alkyl radical having 1 to 6 carbon atoms, Z is any anion, a few of which speed corresponds to the charge of the cation, B for a

or

—CHi group

-CH ₂ -N-CH ₂ -GrUpPe

A stands in which X has the above meaning and A is a hydrogen atom or a Benz) group.

The invention relates to water-soluble, quaternary ammonium compounds of the general formula

C ₁₁ H ₅ -CH ₂

X CH ₂ -C ₁₁ H ₅

N-CH, - (B) -CH ₂ -N

C ₁₁ H ₅ -CH ₂

where X is an alkyl radical with 1 to 6 carbon atoms and Z is any anion, whose valence corresponds to the charge of the cation, B for a

—CH, group

CH ₂ -C ₁₁ H ₅

-CH ₂ -N-CH ₂ -GrUpPe
A.

in which X has the above meaning and A is a hydrogen atom or a benzyl group.

The quaternary ammonium compounds according to the invention preferably have a molecular weight between 464 and about 40,000.

The compounds according to the invention have a good affinity for the fiber material and influence it The basic dyes are absorbed in a favorable manner. In contrast to known means, they produce in aqueous solutions have significantly lower amounts of disruptive foam. They have an effect in dye baths slower absorption of the basic dyes on the fiber material and are used to regulate the The absorption rate of basic dyes when dyeing polyacrylonitrile fibers or threads is excellent suitable. Compared to commercial preparations of similar composition (one of these was labeled as »Chemical characteristics« indicated: »solution of a quaternary ammonium salt«, while the other Dimethyl-benzyl-lauryl-ammonium chloride), with which comparative tests were carried out, resulted the ammonium compounds according to the invention have an important role in their use as retarding agents More regular application of the dye to the substrate during the entire dyeing period.

As already stated, it should also be noted that that the ammonium compounds according to the invention foam significantly less than the known commercially available retarding agents, which is an essential factor, especially in the case of continuous dyeing processes Represents advantage.

The ammonium compounds according to the invention can be in the form of pure compounds or as technical mixtures are used.

As a peralkylating agent for the preparation of the quaternary ammonium compounds according to the invention are for example alkyl halides and alkyl sulfates, which have alkyl radicals with 1 to 6 carbon atoms, suitable, for example n-hexyl iodide, n-butyl bromide, Methyl bromide, ethyl iodide, diethyl sulfate and especially dimethyl sulfate.

The ammonium compounds according to the invention are liquids of high viscosity at room temperature or tough, sticky pastes or solid crystalline substances. They are in alcohol-water mixtures, such as. B.

IO

fcopropanol-water mixture, or in water among those usual for dyeing with basic dyes Conditions soluble.

The following examples serve to provide further explanation of the present invention.

In these examples, parts are by weight, percentages are by weight and temperatures in degrees Celsius _f ind specified.

example 1

To a warmed at 8O ⁰ C solution of 74 parts (1 mole) of trimethylene diamine in 125 parts of water 506 parts of referencing with stirring (4 mol) of benzyl chloride tugetropft. The internal temperature of Reaktionsgemiiches should not rise above 100 ^0C.

After the dropwise addition, the mixture is stirred for a further 90 minutes at 90 to 95 ° C. and then 533 parts of a 30% strength sodium hydroxide solution (4 Mo ¹ NaOH) are added.

The water-insoluble amine separates out and is separated off. It is obtained in crystalline form with a melting point of 40 to 41 ^° C. (not corrected) by recrystallization from ethanol. 434 parts (1 mol) of the amine thus obtained are dissolved in 525 parts of benzene and heated to the boiling point of benzene. 252 parts (2 mol) of dimethyl sulfate are added with stirring and kept at the reflux temperature of the benzene for 4 to 5 hours. The resulting quaternary compound is insoluble in benzene and separates out as a viscous liquid. The supernatant benzene is a '_> decanted, the reaction product from benzene held by vacuum distillation removed (about 20 Torr and 70 to 8O ⁰ C). The result is a brown, very viscous mass.

The resulting product (ammonium compound no. 1) is soluble in water-isopropanol (1: 1). It owns an excellent retention capacity for basic dyes when dyeing polyacrylonitrile fibers.

Example 2

103 parts (1 mole) of diethylenetriamine is dissolved in 250 parts of water and heated to 80 to 90 ⁰ C. 569 parts (4.5 mol) of benzyl chloride are added dropwise to this solution. The temperature of the reaction mixture should not exceed 100 ⁰ C. After stirring for 90 minutes at 90 to 100 ^° C., 600 parts of a 30% strength sodium hydroxide solution (4.5 mol of NaOH) are added and the mixture is stirred for a further 15 minutes.

The reaction product, which is insoluble in water, is separated off and in a vacuum of about 15 torr at 100.degree dried.

The reaction product is a brown viscous liquid

508 parts (1 mol) of the amine thus obtained are heated to 60 to 65.degree. With stirring, 290 parts of dimethyl sulfate are added dropwise in about 30 to 40 minutes. The temperature rises when it is added and should not exceed 100 ° C. About 15 minutes after the dropwise addition, the reaction product becomes pasty-thick. There are 66 parts of isopropanol was added and stirred for 2 hours at 85 to 9O ⁰ C. Then a further 66 parts of isopropanol are stirred in and cooled to room temperature with stirring.

The quaternized product (ammonium compound no. 3) is dissolved in isopropanol / water; it has good retarding properties. The quaternization with dimethyl sulfate can also be carried out in an inert solvent such as benzene, in an amount of about 500 to 1000 parts per mole of the amine to be quaternized
Wind-up curves

Pre-shrunk polyacrylonitrile yarn is used as the substrate for the draw-on dyeing; pre-shrinking is done by treating the polyacrylonitrile yarn for 10 minutes, near the Boiling temperature, with an aqueous solution containing 1.0 g / l of p-octylphenyldecaethylene glycol and 0.5 g / l of formic acid contains, then it is rinsed with hot water and dried

Parts of pre-shrunk polyacrylonitrile yarn in the form of strands are in 5000 parts of a Dye liquor given the following composition:

1.0 part of a dye preparation that 20% consists of the dye of the formula

O NHCH,

ι

O NH-CH ₃ CH ₂ -CH ₂ -NiCH.,).,

and consists of 80% Glauber's salt.

2.0 parts acetic acid

2.0 parts sodium acetate

10.5 parts of calcined sodium sulfate

(before adding the retarding agent, the

pH value 4.2) and χ parts retarding agent.

^{The liquor temperature is brought to the boiling temperature of 90 °} C. in 15 minutes, after which the dyeing is carried out at the boil for 60 minutes.

Samples of the dyebath are taken at defined time intervals and their dye content is then taken colorimirisch determined.

The samples were taken at the following intervals:

at 95 ° C

at the start of cooking

10 minutes after the start of cooking

20 minutes after the start of cooking

30 minutes after the start of cooking

60 minutes after the start of cooking.

The colorimetric determination was carried out at 610 nm against water. The ones in the curves on the ordinate axis The specified percentages of the absorbed dye were taken from a calibration curve prepared beforehand taken.

The retardants were compared in 2 concentrations: X = 0.75 (Table 1) and, Y = 1.0 (Table 2).
In the tables means

as a percentage of the dye used, which is based on the

laser is wound,
t staining time in minutes

Retarding agent I: product according to example B of the parent patent 16 43 526 (column 4, lines 45 ff.) In the form of a solution containing 19% active substance and a total of 43% dry matter, retarding agent II: dimethyl-benzyl-lauryl-ammonium chloride
Retarding agent III: Commercially available quaternary

5 ^ 6

Ammonium salt with 2 quaternary N atoms and 2 on top of this the total volume (foam + liquid)

higher molecular weight (fat) residues (Cu to C22). read immediately.

The drawing-up curves during the dyeing of the polyacrylonitrile - a duplicate determination was made at room temperature

Textile material with said basic dye temperature and carried out at 70 ° C,

in the presence of the retarding agent I, 0.8 g / l of acetic acid run over the 5

entire staining range almost linear, i.e. the Na-Acnat 0.8g / l [solutions

The bath is exhausted and the dye is absorbed by a retarding agent 0.5 g / l J

evenly over the entire dyeing time (more straightforward

Course of the pull-up curve in the two graphic spaces - 70 "C

Representations). 10 temperature

The bath exhaustion or dye absorption at

Dyeing in the presence of the tested known retarding components 160 ml 177 ml

Products are not linear, i. i.e., in a certain slow-release agent II 200 ml 191 ml

The dye is absorbed quickly in the temperature range. The Redardiermittel III 209 ml 248 ml

Pull-up curve when dyeing in the presence of the well-known 15

Finds out in comparison to a coloring curve from the comparison of the foaming behavior of the products

without retarding agent, only a shift after tested retarding agent is clearly evident that the

a higher temperature range (S-shaped retarding agents to be used according to the invention 1

curve in a diagram in which the amount of dye foams significantly less than the compared

is applied in the dye bath against the dyeing time). 20 well-known products, for example in the case of continuous Dyeing process (e.g. in a jigger) of special

Foam behavior ^{advantage is} -

The rest, under the general formula of

100 ml each of the following solutions were covered by the claims of the present application

250 ml shaking cylinder shaken vigorously 40 times and 25 compounds show a comparable effect.

For this purpose 2 sheets of drawings

Claims (1)

ι - * ² Claim: Water-soluble, quaternary ammonium compounds of the general formula C ₁₁ H ₅ CH ₂ X CH ₂ -C ₁₁ H ₅ N-CH, - (B) -CH ₂ -N