DE2206267A1 - QUATERAL AMMONIUM COMPOUNDS - Google Patents

Description

wherein Ar is a phenyl radical which is replaced by methyl or chlorine

R. an alkylene chain with 2 to k carbon atoms, which can be substituted by methyl or hydroxyl kaiaa,

R "is an alkyl radical with 1 to h carbon atoms or a benzyl radical,

R ", R. an alkyl radical with 1 to 4 carbon atoms, X chlorine or methyl sulfate

mean and in what

R and R. together with the nitrogen atom have a nitrogen-interrupted polyalkylene ring 4-7 methylene groups, which also have can be interrupted by oxygen, or

R ", R- and R. together with the nitrogen atom _{can mean a heteroaromatic residue 6-Riu; g 9} which can also be substituted by methyl.

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- 2 - Ref. 2935

If R ₂ , R- and R are alkyl radicals, those compounds are preferred in which at least R ₂ , but better still R ₂ and R- are methyl.

Polyalkylene rings of the type mentioned are e.g. pyrrolidine, Piperidine, hexamethyleneimine and morpholine.

Heteroaromatic rings of the type mentioned are, for example, pyridine, 2-methylpyridine, 4-methylpyridine, 2,4-dimethylpyridine.

The compounds according to the invention can thereby be prepared be that a compound of the general formula II with a tertiary amine of the general Formula III implements:

Ar-OR ₁ -X + N

II

.R,

R,

III

Ar-OR ₁ -N

-R.

or that a compound of the general formula II is reacted with a secondary amine IV to give the compound V. and then quaternized with compound VI:

-0-R ₁ -X + HN

-HX

II

IV

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Ref. 2935

Ar-OR ₁ -N ^ ^J + R ₂ X V VI

Ar-OR ₁ -N-

* 2

Suitable secondary amines of the general formula IV are

for example:

Dimethylamine diethylamine di-n-propylamine Di-iso-propylamine, methyl-ethyl-amine, methyl-tuty1-amine Di-n-butylamine Dl-iso-dutylamine Morpholine Pyrrolidine Piperidine Hexame thy1enimin

As Quateraierungsmittel of the general formula VI can

e.g. used:

Methyl chloride ethyl chloride propyl chloride butyl chloride Dimethyl sulfate benzyl chloride

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Suitable tertiary amines of the general formula III are for example: trimethylamine triethylamine tripropylamine tributylamine dimethyl-ethyl-amine Methyl diethyl amine methyl dibutyl amine Dimethyl-benzyl-amine Dimethyl tewtyl amine Pyridine

2-, 3- or 4-methyl-pyridine 2,4-dimethylpyridine

The reaction between the compounds of the general formula II and III is normally carried out by heating the starting components to temperatures of 80 to 150 ^° C. preferably 100-130 ° C. The reaction is complete when the reaction product dissolves completely in water. The reaction can also be carried out in a suitable solvent, such as, for example, methyl ethyl ketone,

In the reaction between the compounds of general formulas II and IV, the released is used to bind HX either another mole of the secondary amine of the general formula IV or one mole of one

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other base, such as NaOH, is required. The implementation will made in a suitable solvent or in excess amine. The connection V is then subsequently, e.g. with methyl chloride or dimethyl sulfate, quaternized. The quaternization can also be carried out in a suitable solvent, e.g. can also be carried out in aqueous solution.

The compounds of the general formula I according to the invention are normally hygroscopic, poor crystallizing salts.

The exit ban fertilizers of the general formulas III, IV, VI are known. The output connections of the general formula II are known in many cases. For example, they can be produced by the following methods will.

a) By implementing a Na phenolate of the general Formula VII with a dichloro compound of the general formula VIII:

ArONa + Cl-R ₁ -Cl ^ Ar-OR ₁ -Cl

-NaCl

VII VIII IX

b) If R _{1 stands} for an ethylene chain which can also be substituted by methyl, it is possible to convert a phenol of the general formula X with a compound which contains the epoxy group XI to form the compound XII:

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Ii Il

ArOH + -C C- ^ Ar-6 -C -C -OH

X XI XII

The compound XII is then made to react with a compound HX:

Ii I I

ATtO-CC-OH + HX \ Ar-OCCX

¹¹ -H ₂ O ^Ϊ!

XII XIII

Suitable compounds with the epoxy group XI are, for example, ethylene oxide and

Propylene oxide.

;>) Another generally applicable possibility is to a phenolate of the general formula VII with a chlorohydroxy compound of the general formula XIV to convert to an ether alcohol of the general formula XV and to esterify this with HX afterwards:

ArONa + Cl-R ₁ -OH ^ Ar-OR ₁ -OH

-NaCl VII XIV XV

Ar-OR ₄ -OH * HX ^ Ar-OR ₁ -X

¹ HO

XV II

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d) In the event that R. is a propylene chain substituted by hydroxyl, the starting compounds are obtained in one stage by converting the phenol of the general formula VII with epichlorohydrin (formula XVI)

ArOH + CH ₂ - CH-CH ₂ -Cl

OH VIl XVl

Of course, the compounds of the general formulas XII and XV, which have an alcoholic OH group, also with thionyl chloride, phosphorus chlorides and other known processes in the corresponding Chlorine compounds are transferred

The compounds according to the invention are normally obtained in very pure form and in high yield. In They are very soluble in water.

The compounds of general formula I according to the invention can be used as temporary retarders in dyeing be used.

Acid modified fiber materials made of polyacrylonitrile can be known also in rich and deep shades color very easily with basic dyes. Unfortunately, the cation-active dyes are so dragging quickly on that usually an irregular

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Coloring is obtained · To obtain an even coloring obtained, the use of leveling aids, so-called retarders, specially developed for the polyacrylonitrile fibers is required. For example, for the level Coloring of polyacrylonitrile structures a process known (DAS 1 125 286), in which a quaternary alkoxy-alkyl-ammonium compound is used as a retarder, which has more than 8 carbon atoms in at least one hydrocarbon radical. Such retarders with long However, hydrophobic hydrocarbon residues have the disadvantage that, in the event of accidental overdosing, they stubbornly remove the polyacrylonitrile fiber to be dyed reserve and then make it practically impossible to achieve the planned depth of color or nuance. This inevitably results in losses due to the unused dye remaining in the bath. Retardant with such Properties are called permanent retarders.

It has been found that the relatively low molecular weight compounds according to the invention are excellent as temporary ones Retarders are suitable. They lead to level dyeings without reserving the fiber and practically without any basic dye to be retained in the dye bath. In addition, they even show a pronounced migration-promoting effect.

Thus, basic dyes and leveling aids can be used on structures made of polyacrylonitrile

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- 9 - Ref. 2935

then level them in a particularly simple and risk-free way Colorations are produced when a compound of the general formula I according to the invention is used as the leveling aid is used. In the context of the usual dyeing time wirö a practically complete exhaustion of the Dye ™ Solution achieved even if the leveling aid is accidentally overdosed «Because of the good migration freezes The effects of the compounds according to the invention can also be uneven Dyeings by treating the dyed material in blinds Dyebath leveled out with a compound according to the invention will.

The compounds according to the invention are useful as leveling auxiliaries in all colorations of basic dyes on fibers or textiles of any kind made from acrylonitrile-containing polymers effective. The fiber material can be polyacrylonitrile or © in polyacrylonitrile mixed polymer.

Basic dyes include dyes of the di- and triaryl methane series, the indolyl and diindolylaryl methane series, Oxazine, thiazine, diazine, indulin and cyanine dyes, as well as the basic azo and azamethine dyes to understand.

A mixture of two or more compounds according to the invention can also be used as a leveling aid. The compound or the mixture of the compounds is related to the dyebath in an amount of 0.1 to 5%

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* - ίο -

Ref. 2935

based on the weight of the material to be colored. To level out dyeings that are already uneven? : ■ '^ t one is generally somewhat larger © quantities *

example 1

79 g pyridine (1 mol) and 156 ,. » ; Fiiaooxyethyl chloride (1 mole) will lead to 2 0 ZiaiA ^ n heated to 120-125 ° C. The soft paste srsfcar; On cooling to a hard, light-colored crystal structure * Macrystallized on to mathylethyl ketone, colorless a _f hygroscopic crystals of N ^ -Phesoxyeth: J) · p ^ ridiriiuia-ciilorid of the formula

■ J

Eq

M.p. 114-118 ° C.

Analogously, fci

Cl /

o-CH ₀ -CF ₀ -F "

l ¹ ^ fp

Cl ^ö m.p. 14-142 ° C

cn. ,, φ

CH,

Cl

CH ^ / Vo-CH ₀ -CH ₀ .

CH,

Cl

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- li -

Ref. 2935

Example 2

In a liter tantalum autoclave, 80 g of pyridine (approx. 1 mol), 400 ml of Methyläthylketoii and 18? g of 3-chloro-2-hydroxy-l-phenoxypropane (1 mol; prepared from phenol and epichlorohydrin according to B. '41 _f p. 2730) heated to 120-125 ° for 15 hours with stirring Kristallisat albgesaugt ₉ washed with acetone and dried for 3 days in a vacuum generator over sulfuric acid. 134 g of H- {3-phenoxy-2-hydroxypropyl) pyridinium chloride of the formula are obtained

-CH ₂ -N ⁷ \

in the form of colorless crystals of melting point 133-136 ° (= 51 $ d.Th »),

Analysis (C ₁₈ H ₁₆ ClNO ₂ ): Ber, Cl = 13.4%; N = $ 5.3; O = $ 12.0

Found = $ 13.5; = 5

Example 3

185 g of 4-phenoxybutyl chloride (1 mol; color oil of boiling point 128-130 ° / 12 mm) and 80 g of pyridine were heated to 120-125 ° until the melt was clearly soluble in water. This was the case after about 15 hours. The melt of N- (4-phenoxy-butyl) pyridinium chloride of the formula

(P

(/ Vo-CH ₂ -CH ₂ -CH ₂ -CH ₂ -:

Cl

*) Ber.dtsch.Chem.Ges.

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Ref. 2935

was then cooled down to about 80 ° C. and at this temperature with the same amount of water (265 ml) diluted to a 50% solution. In this form, the product is ideally suited for use as a retarder.

The following was produced in an analogous manner:

CH

0-CH ₂ -CH ₂ -N- CH ₂

CH.

Cl

Example 4

10 g of polyacrylonitrile yarn are placed in a laboratory dyeing device in a liquor ratio of 1:40 in a bath heated to 98 ° C introduced, which is 0.075 g per liter of the commercial dye

CH

Cl

0.225 ml of glacial acetic acid and 0.45 g of N- (2-phenoxyethyl) pyridinium chloride (Example 1) contains. The dyeing is carried out for 90 minutes at 98 ° C. and a perfect, level red-violet color is obtained Coloring. The other compounds of Examples 1, 2 and 3 behave similarly under otherwise identical conditions, but without adding a compound according to the invention, one obtains a unusable, blotchy coloring.

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N (2-phenoxyethyl) pyridinium chloride does not show either Disadvantage of a blockage of the fiber, e.g. from a retarder of the formula

ei ^σ χνΐΐ:

C, JB _n --0-CH _n - N - CH,

'12 "25 2

CH ₃

is caused. This can be shown by placing 10 g of polyacrylonitrile yarn on each laboratory dyeing device one hour at 98 ° C with 0.9 g / liter of N- (2-phenoxyethyl) pyridinium chloride or of compound XVII and 0.225 ml of glacial acetic acid. Then the baths 0.225 g of each of the above dye were added and the dyeing was carried out at 98 ° C. for one hour. The one with N- (2-phenoxyethyl) pyridinium chloride A pretreated strand gives the same depth of color as a non-pretreated strand Strand. In contrast, the strand pretreated with compound XVII only gives an extremely small amount Staining, suggesting a blocking of the dye monkeys Make the fiber is based.

Example 5

205 g of N- (2-phenoxyethyl) piperidine (1 mol; colorless oil with a boiling point of 145-150 / 10 mm), 128 g of dimethyl sulfate were added over the course of an hour at 80-85 ° C then stirred for another 10 hours at the same temperature. The melt of N-methyl-N- (2-phenoxyethyl) -

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piperidinium methosulfate

CII ₂ -CII ₂

'O

which crystallized very slowly, became after cooling adjusted to a 50% solution with the same amount of water. The Eetarder effectiveness of this product corresponds quite exactly to that of N- (2-phenoxy-ethyl) -pyridinium chloride according to example 1.

In an analogous manner, 207 S were also N- (2-phenoxy-ethyl) -morpholine (colored oil with a boiling point of 160 ~ 163 ° / l2 mm) with Dimethyl sulfate reacted and thereby F «-Metbyl-N- (2-phenoxyethyl) -morpholiiiiuu-methoEii.lfat

-CH ₂ -CH ₂ - Nf Ö CH,

^lr x

obtain.

Also in the same way, 249 g of N- {2-phenoxy ethyl) -N, N-di-n-butylamine (colorless oil with boiling point 103 ° / 0.1 mm) reacted with dimethyl sulfate and thereby N-methylene-N- (2-phenoxy-ethyl) -N, N-di-n-butyl-ammonium-methosu 1 fat

-CHp-CE ₉ -N

obtain"

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These compounds are also in their retarding effect similar to the compound according to example 1.

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Claims (3)

Ref. 2935 claims 1. Quaternary ammonium compound of the general formula ^l 2 Ar-OR ₁ -N. -R, R, R_, R. wherein Ar is a phenyl radical which is replaced by methyl or chlorine can be substituted, R, an alkylene chain with 2 to h carbon atoms, which can be substituted by methyl or hydroxyl, Ro is an alkyl radical with 1 to 4 carbon atoms or a benzyl radical, an alkyl radical with 1 to h carbon atoms,
X chlorine or methyl sulfate means and in what R and R. together with the nitrogen atom form a polyalkylene ring interrupted by nitrogen with 4-7 methylene groups, which can also be interrupted by oxygen can or R ₂ , R_ and R. together with the nitrogen atom form a heteroaromatic 6-ring, which can also be substituted by methyl, can mean « 309833/1 - 17 - Ref. 2935 2. Process for producing level colorations on structures made of polyacrylonitrile using basic dyes and leveling aid, characterized in that a compound according to Claim 1 is used. 3. Method for leveling uneven dyeings more basic Dyes on structures made of polyacrylonitrile, characterized in that the material to be dyed is in a bath is treated with a compound according to claim 1. 309833/1164