DE1543529A1 - Polyquaternary ammonium compound and process for their preparation - Google Patents

Description

(D 51 070 IVb / l2qu)
DePaul Chemical Company Inc.

Mannheim, August 28, 1968

"v .. DePaul Chemical Company Inc. 44-27; Purvis Street Long Island City, New York / U.S.A.

Polyquaternary ammonium compound and process for their preparation

The present invention is a polyquaternary Ammonium compound with 8 to 20 nitrogen atoms of the formula

Polyquaternary ammonium compound with 8 Ms 20 nitrogen atoms of the formula

in which R identical or different alkyl radicals with 1 Ms 6 carbon atoms,

A and B is an alkylene, arylene or a Chalco- gene interrupted alkylene radical

X = 4 Ms 17,

Z is an anion residue

represents or

(A) an alkyl radical with 1 Ms 6 carbon atoms or

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(B) the formula
_R Z.

R -NB (if-A) _v

R R

denotes in which A, B, R and Z have the meanings given above and at least one R radical has the formula B and Y is 0-3.

The invention also relates to a method of manufacture this polyquaternary ammonium compound, which is characterized by dadureη is that η moles of an amine having at least 2 primary nitrogen atoms with n-1 moles of a dihalide are sufficient long converts to four times the condensation to a polyamine as many nitrogen atoms as the above amine has to carry out and then quadrupled the polyamine obtained.

It has been found that a special class of nitrogenous Condensation products and especially a special one Class of polyquaternary ammonium compounds, as agents for treating textile materials to be dyed or dyed, in particular as a means for fixing dyes on cellulosic materials, can be used, making excellent Properties of the dyed textiles, in particular a significantly improved washfastness, was brought about. At the same time it was found that these compounds do not affect the lightfastness of the colorations or the other Properties of textile materials, such as the Tensile strength.

Use of Compounds of the Present Invention

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improves the water resistance of dyeings, in particular on cellulosic materials.

The polyquaternary ammonium compounds of the present .Invention are generally characterized as high molecular weight Compounds containing 8 to 20 nitrogen atoms, at least 3 of which are quaternary nitrogen atoms and which represent remaining tertiary nitrogen atoms.

The polyquaternary ammonium compounds are generally prepared by the action of a polyamine having at least 2 primary nitrogen atoms on a dihalide such as an alkylene dihalide or an arylene dihalide. The polyamines with 2 primary nitrogen atoms react with the difunctional aliphatic or aromatic dihalides, whereby a polymer with a branched chain is obtained. The amount of starting materials is selected so that n-1 idols of the difunctional dihalide are applied to η moles of the polyamine.

The reaction is generally continued at medium temperatures under reflux conditions until the Reaction is complete. During the reaction, the acid formed is neutralized, whereby the Shifting the equilibrium in the direction of the formation of the desired condensation product is facilitated. After this the theoretical amount of acid formed in the reaction mixture and thereby confirming the completion of the reaction, the reaction product became room temperature cooled and then the reaction product obtained in the usual manner with any suitable quaternizing agent quaternized. After the quaternization

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reaction, the product obtained is the desired polyquaternary Ammonium compound of the present. Invention. The polyquaternary dye fixing agent of the invention has the following general formula i

Z Z "'

- (A — n) _y BNR (I)

in which R is an alkyl radical having 1 to 6 carbon atoms, A and B are alkylene, cycloalkylene, arylene or alkylene radicals or cycloalkylene radicals which are interrupted by 0, S, Se, Te or Po,

R, an alkyl radical with 1 to 6 carbon atoms or a radical dor formula

RN B - N A-) ^ ¹¹ '

a "" "Lr

and at least one radical R has the formula (II). R, R ₁ , A, B, Y and Z have the meaning given above or as follows:

X = 4 to 17

Y = 0 to 3

Z is any suitable anion, for example chloride, bromide, iodide, sulfate, phosphate, acetate, formate, chloroacetate, Nitrate, oxalate, benzoate.

The R radicals that can preferably be used are methyl or ethyl radicals and it is particularly advantageous if all R radicals

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Are methyl radicals. The preferred anions are halides, Sulfates and nitrates. The preferred A and B radicals are alkylene radicals having 1 to 6 carbon atoms, in particular Alkylene radicals with 2 to 4 carbon atoms.

As indicated above, these are the starting materials for manufacture the polyquaternary ammonium compounds of the present invention Invention of a polyamine and a dihalide.

The polyamines which can be used are those which contain two primary amine groups and in which additional amino groups are present, preferably secondary amino groups *. Examples of such connections are ¹ :

Athy lend iamin,

Diethylenetriamine,

Triethylenetetramine,

Tetraethylene pentamine,

Pentaethylene hexamine,

Propylenediamine,

Butylenediamine,

Amy lend iamin,

Hexylenediamine (1,6-diaminehexane), Dipropylenetriamine,

iDripropylente tramin,

Pentapropylonhexamine,

1,4-diaminocyelohexane,

β , / S'-diamino-Clj ^ -diethylcyclohexane.

The following are the formulas of some of these compounds specified:

(1) H ₂ NCH ₂ CH ₂ NHOH ₂ GH ₂ OH ₂ NHuH ₂ GH ₂ IiH ₂

(2) H ₂ NCH ₂ CH ₂ GH ₂ NHUH ₂ GH ₂ NHCH ₂ CH ₂ CH ₂ Nh ₂

(3) H ₂ NCH ₂ CH ₂ GH ₂ CH ₂ MCH ₂ Gh ₂ NHCH ₂ CH ₂ NH ₂

(4) H ₂ NCH ₂ CH ₂ NHGH ₂ GH ₂ NHCH ₂ CH ₂ CH ₂ Ch ₂ NH ₂

(5) H ₂ NCH ₂ GH ₂ NHCH ₂ CH ₂ CH ₂ NHCH ₂ Ch ₂ CH ₂ NHCH ₂ CH ₂ NH ₂

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It should be noted that the compounds (1) to (5) differed Liche alkylene cord lengths between the amino groups

In general, the alkylene chains between the amino groups can vary between 1 to 6 carbon atoms and the ratio the secondary amino groups to the primary amino groups should not exceed 2.1.

The dihalides that can be used include those im Commercially available dihaloalkanes and cycloalkanes, as well as the dihaloalkanes interrupted by 0, S, Se, Te or Po, such as, for example;

Dichloromethane,

Dichloroethane (ethylene chloride),

Dichloropropane, "

Dichloropentane (pentamethylene dichloride),

Dichlorohexane,

as well as the equivalent corresponding dibromo and diiodine compounds;

/ 3, ß'-dichlorodiethy lather,.

Tetraethylene glycol dichloride,
Ethylene glycol di- / 3-chloroethyl ether,

y, y'-dichlorodipropyl ether, · '.

1,4-cyclohexylene dichloride,
p-xylylene dichloride,

as well as the corresponding dibromine and diiodine compounds. Waiterhin do not need the reactive dihalogen groups immediately be e.g. B.

l-öhlor-2-ßrornäthan,
l-chloro-3-bromopropane,
l-ghlor-4-iodobutane. ■

The sulfur analogs of the oxygen-containing ones given above, for example Dihalides are also included.

The following examples serve to illustrate the present

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Invention. All parts are parts by weight unless otherwise is specified,

Example 1:

In a three-neck, two-liter flask equipped with a stirrer, thermometer, dropping funnel, water-cooled condenser and an ice-cooled Dewar condenser attached to it, as well as with a heating mantle, 500 g of water and, with some stirring, 292 grams of triethylenetetramine were added slowly. Yvährend the addition, the temperature rose to about 50 to 6O ⁰ C, because the dissolution is slightly exothermic. iiach the addition, the temperature reaches 80 ⁰ G and then 292 grams of ethylene dibromide very slowly through the dropping funnel added. Due to the exothermic reaction, the reaction mixture begins to reflux. The addition of the A ^- tüyl en bromide is interrupted until the reflux ceases and then another small amount is added until the reflux starts again. This is continued until all of the ethylene dibromide has been added. All the while the addition the temperature between 95 ⁰ O and reflux temperature is maintained and if necessary, especially against sin the addition, heat is supplied to the necessary temperature range to maintain. To complete the addition of the ethylene dibromide, the reaction mixture is stirred at reflux for one hour and then approximately 50 grams of water and the slight excess of the dibromide are distilled off. (Approximately 10 grams of excess ethylene dibromide is present in the 292 grams employed and above the stoichiometric amount necessary to make the polyamine of this reaction.) The amounts of ethylene dibromide and triethylenetetramine used in this example are 4 moles and 10 grams of amine and 3 iiol dibrocid. After the v / ater and excess dibroaid have been removed

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was, - the mixture is cooled to 20 to 25 ⁰ C. A 56.2 solution of polyamine in water is obtained.

The polyamine so produced is then quaternized as described below. 98 grams of the polyamine solution prepared above are placed in a 500 ml three-necked stirred flask equipped with a stirrer, thermometer, dropping funnel, water-cooled condenser and ice-water bath. To this, 104 grams of dimethyl sulfate are added at a temperature of 20 to 25 ^{° C.} Because of the strongly exothermic reaction, the addition is carried out very slowly using a fresh water bath in order to keep the temperature within the specified limits. After about one third of the dimethyl sulfate had been added, the pH value below about 6 was stopped. When the pH reached about 6, small amounts of caustic soda were added to maintain a pH between 6 and 8. After all the dimethylsulfate had been added, the reaction product was stirred for 1 hour at 5O ⁰ C with the above mentioned pH was maintained exactly. The end product is a quaternized polyamide; analysis shows the presence of five quaternary nitrogen atoms and 11 tertiary nitrogen atoms. The sulfate analysis shows a decrease in the dimethyl sulfate equivalent in the polyamines having five primary nitrogen atoms, 8 secondary nitrogen atoms and 3 tertiary nitrogen atoms. Elemental analysis of the polyamine shows a nitrogen content of 19 »55 ° and a molecular weight of 114-8.

The end product is a mixture of isomeric polyquaternary ammonium compounds of the following general formula:

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OH ₃ SO ₄

CH, S0. ι 3 4,

but not in X 4 to 11 and R at least one methyl radical represent more than 8 methyl radicals and the remaining R radicals the formula

■ N

⁰ A "

■ Ν

° 2 ^K 4

own, in which Y varies from ü to 3. The excellent Washability properties of the one prepared in Example 1 Product were made by treating cotton dyes with the named product and comparison of the dyeings treated in this way demonstrated with similar untreated color products using a standard wash test.

Example 2:

Dye stains were made using the following Dyestuff «, which is contained in the dyestuff standards regulations AAITC (American Association of Textile Chemists and Colorists) manufactured:

1. blue 86, -

2. yellow 28

3. red 79

4. purple 47

5. blue 67

6. FASTUSOL (registered trademark of General Aniline

and Film Corporation) gray LG-L.

The product of Example 1 is used to make each coloration

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to treat it, and is namely 1.6 fo Peststoff of the products of the process, based auf.das weight of the colored Paser applied. The dyed and treated products are compared with dyed untreated products by treating them under the action of a mild detergent for 5 and a half hours in a standard commercial washing machine. For 3s it was observed that the untreated dyeings are considerably less luminous and have a much less deep paring than the treated dyes, which are practically unchanged from the original dyeings before the washing.

One of the major disadvantages of most commercially available Dye fixing agents reside in the fact that although they improve the washfastness of dyeings can - they seriously impair the lightfastness. The dyeings produced in this example are a Standard light fastness test in an "Atlas" color fastness tester subject. The colorations were a certain time of the test method, which can be found in the table below exposed:

Coloring exposure time in hours

AWAY

blue 86 5 Io

yellow 28 20 40

red 79 20 40

purple 47 20 40

blue 67 20 40

FASTUSOL gray LGL 10 20

The untreated dye made with blue 86 showed same light resistance after 5 and 10 hours of exposure.

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Three competing dye fixers showed up to 10 hours Exposure to a substantial drop in lightfastness which is much sharper than the treated colorations of the invention. The colorations produced with yellow 28 show no decay after 20 hours, while the same colorations made with Competitive dye fixers were treated after 10 hours Impact drop sharply. Even the untreated dyeings show no dropping after 20 hours of exposure. After 40 hours The untreated dyeings show only a slight fall off and the treated dyeings a little stronger falling off. The coloration produced with red 79 shows a slight decrease after 20 hours, while the Competitive products cause breakage after 10 hours. "After 40 hours, the treated dyeings show a little greater decrease in light resistance than the untreated dyeings. The coloration treated with violet 47 gives a similar one Result like the dye treated with red 79 compared to the untreated dyeings and competing products. With The coloration produced in blue 67 shows a noticeably greater decrease after 10 hours than the untreated colorations; the garbage is however, after 4 hours, it was significantly less than that of the untreated Colorations. Competitive products, i.e. those that have dye fixation Containing agents cause a sharp break that makes the dye practically worthless after 5 hours. With gray treated coloration shows practically no dropping after 20 hours and therefore an excellent lightfastness, the in this respect is the same as the untreated dyeings. Different dye fixing agents competing that are used for this type of dyeing, produce excellent results Yv'as fastness, but reduce the lightfastness with sharp break-in from two and a half to five hours. That The above shows the top properties of the dye-fixer

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of Example 1. It also shows that improved wash fastness obtained by a large number of direct dyes. At the same time, it is shown that the dye-fixing agents with the same variety of dyes perform well in terms of light resistance.

Example 3:

A sample of fabric (Mill Broadcloth) dyed with ¹¹ "GMAFIX" (registered trademark of General Aniline and Film Corporation) is treated separately with two percent and three percent, based on the weight of the fiber (solids basis), turquoise blue FGW. The dyeings were carried out using 14.17 g of dye per 4.5 liters of dye bath It was surprising and not to be expected that not only the treated, dyed fabric obtained in this way had an excellent wash fastness that was greater than that of the untreated dyed fabric is characterized, but the lightfastness is also much higher.The same properties and improvements were noted using a dye concentration of 170 g per 4.5 liter dye bath; each of the two dye concentrations described herein were also noted obtained using a concentration of 3 % solid of the product of the example.

Example 4:

The procedure of Example 1 is repeated except that methyl chloride is used to quaternize the polyamine and the reaction is carried out in a closed system to prevent evaporation of methyl chloride (i.e., the Reaction is carried out under pressure). The product obtained in this way is essentially the same as that of Example 1, with the

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assume that the'anion, the polyquaternary ammonium compound is a chloride ion instead of a methyl sulfate ion.

Example 5:

Example 1 is repeated with the exception that, instead of ethylene dibromide, the following alkylene halides are used in separate experiments and in amounts which are the same as in Example 1 (ie 3 mol plus 5 % excess):

A. Ethylene dichloride

B. propylene dichloride

0. Pen tame thy lend ichlor id-D. Hexamethylene dichloride.

The products of each example are created by the same chemical identification methods are characterized by the properties of the nitrogen atoms or the branching but differ from the product of Example 1 in molecular weight because a different alkylene chain was introduced into the polyamine.

Example 6;

The products of the previous example are used for post-treatment of dyed cottons similar to that used in Example 2 and the results are similar to those in that Example were obtained.

Example 7:

Example 1 and Example 5c were each repeated, with the exception that the following amines were used in equimolar amounts instead of triethylenetetramine:

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A. Ethylenediamine

B. diethylenetriamine. · '

O. Pentaethylene hexamine

D. Dipropylenetriamine ₍ '.

B. l ^ -diaminocyclohexane.

Example 8:

Examples 1, 7B and 12 were used using equimolar amounts of the following dihalides in place of ethylene dibromide or propylene dichloride:

A. Tetraethylene glycol dichloride

B. p-xylene dichloride

G. 1-chloro-3-bromopropane.

Example 9:

Examples 1, 5A and 5D are prepared using the following Connections repeated, with the exception that quaternization is effected:

A. methyl iodide

B. propenyl chloride.

Example 10;

The polyamine of the following formula is quaternized as described below

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• Polyamtn A

H »Η

HgN-CHg-GH ₂ -Ii-GH ₂ GHgNCH ₂ GHgR-H

CH

. 2

CHg TT TT

N-CHgCHg-N-CHgGHgN-CHgGH ₂ NHg

GHo

CHg

N-CHgGHg-N-CHgCHgN-OHgGHgNH ₂

CHg TT JT

OHg yy

N-CH ₂ CH ₂ N-CH ₂ GH ₂ NH ₂

CH ₉

CH ₉ ι * -

NH ₂

As in Example 1, the polyamine A is quaternized with dimethyl sulfate, producing a pentaquaternary ammonium product (i.e. 5 primary nitrogen atoms are quaternized) in which all of the eight secondary nitrogen atoms have been methylated, to make 8 N-methyl tertiary nitrogens or a total of 11 tertiary nitrogen atoms. The quaternized product of this Example gives essentially the same results as those obtained in Examples 2 and 3.

Example 11;

A polyamine of the following formula was made as in Example 1 described, quaternized:

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HgN-OHgOHgNHOHgCHg-N-CHgCH ₂ -N-CHgCHg-NH

CHq CHq CHq

CHq CHq CHq

NH ₂ NH ₂ NH ₂

Example 12:

A polyamine of the following formula was obtained as in Example 1 described, quaternized:

HgN-OH ₂ CHgCHgNHCHgCHgCHgN-CHgCHgCHgN-CHgCH ₂ CHgNH

CHq CHq CHq

I C. t C. , C.

CHq ■ CHq CHq

CHq CHq CHq

NHg NHg NHg

Example 13;

A polyamine of the following formula was obtained as in Example 1 described, quaternized:

HgN-CH ₂ CHgNH-OHgOHgOOHgCHg-N-CHgCHgOCHgCHgN-CHgCH ₂ OCHgCHg

CHq -

CHq

NHg

Example 14:

A polyamine of the following formula was quaternized as described in Example 1:

CHq
I C. NH CHq
I C. CHq
I <- NHg CHq
ι C. NHg

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HgN-CHgCHgCHgNHCHgCHgN-CHgCHg-N-CHgCHgKH

CHp CH ₀ OH ₉ ι ^c ι 2 OHp 0H ₀
ι * · CH ₉ GHg GH ₉ OHp
ι * · NHg NHg NHg

Example 15:

A polyamine of the following formula was made as in Example 1 described, quaternized:

H
HgN-CHgCHg-N-CHgCHg-N-CH ₂ GH ₂ N-CHgGHg

GHg GH ₂ NH

CH ₉ CH ₉ GH ₉

ι <- ι ^c ι £ ■

NH NH GH ₂

CH ₉ GH ₉ left-H

I ^ t ^ ι

CH ₂ GH ₂ OH ₂

NH ₉ NH CH ₀

CHg N - CHgCHgNHGHgCHgNHg

GH ₀ CH ₀ NH OH ₂ CH ₀ NH ₀ GH ₉
NH ₂

3example 16:

The product of Example 1 is subjected to molecular distillation and 15 separate fractions are obtained. Each fraction is chemically identical but structurally isomeric. The product of Example 15 and that of Example IU * are identical to two of the above-mentioned political groups. Nuclear Magnetic Resonance Analysis shows that each of the fractions is a highly branched chain polyamine having the following analysis:

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Product;

1. A linear chain with 6 nitrogen atoms, the three branched ones Contains chains, one of which is a chain containing 2 nitrogen atoms and two of which are a chain containing 4 nitrogen atoms.

2. Its linear chain containing 7 nitrogen atoms with 3 branched ones Chains as follows:

(a) a chain with two nitrogen atoms.

(b) a chain with three nitrogen atoms

(c) a chain with four nitrogen atoms

3. A linear chain containing 8 nitrogen atoms with 3 branched ones Chains of what

(a) a chain with 1 nitrogen atom

(b) a chain with 3 nitrogen atoms

(c) are a chain with 4 nitrogen atoms.

4. A linear chain containing 8 nitrogen atoms with 3 side chains, as follows:

(a) two chains with 2 nitrogen atoms

(b) a chain with 4 nitrogen atoms.

5. A linear chain containing 8 nitrogen atoms with 3 side chains, as follows:

(a) a chain with two nitrogen atoms

(b) two chains with three nitrogen atoms.

6. A linear chain with 9 nitrogen atoms and 3 ^s side chains, as follows:

(a) a chain with 1 nitrogen atom

(b) a chain with 2 nitrogen atoms

(c) a chain with 4 nitrogen atoms.

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7. Its linear chain containing 9 nitrogen atoms with 3 side chains as follows:

(a) a chain with 1 nitrogen atom

(b) two chains with 3 nitrogen atoms.

8. A linear chain with 9 nitrogen atoms and 3 side chains as follows:

(a) two chains with 2 nitrogen atoms

(b) a chain with 3 nitrogen atoms.

9. A linear chain with 10 nitrogen atoms and 3 side chains as follows:

(a) two chains with 1 nitrogen atom one chain with 4 nitrogen atoms.

10. A linear 3-sided chain containing 10 nitrogen atoms chains as follows:

(a) a chain with 1 nitrogen atom

(b) a chain with 2 nitrogen atoms

(c) a chain with 3 nitrogen atoms.

11. Its linear chain containing 10 nitrogen atoms with 3 sides chains »each containing 2 nitrogen atoms.

12. A linear chain containing 11 nitrogen atoms with 3 side chains as follows:

(a) two chains with 1 nitrogen atom

(b) a chain with 3 nitrogen atoms.

13. Its linear chain containing 11 nitrogen atoms with 3 side chains as follows:

(a) a chain with 1 nitrogen atom

(b) two chains with 2 nitrogen atoms.

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14. A linear chain containing 12 nitrogen atoms with three side chains as follows:

(a) two chains with 1 nitrogen atom

(b) a chain with 2 nitrogen atoms.

15. A linear chain containing 13 nitrogen atoms with a 1 side chain containing nitrogen atom.

Although specific reaction conditions for the preparation of the quaternary ammonium compounds of the present invention are disclosed in Having given Example 1, it will be understood that other varied conditions can be used to carry out the condensation reaction. Such variations complete the changes the temperature of the reaction time and the amount of water used in the reaction mixture.

Furthermore, although only certain special anions were mentioned in connection with the quaternary ammonium compound, other suitable anions described herein can also be used. In general, other compounds can be selected from such specifically exemplified, can be produced by numerous techniques. Of these, the transformation of the ammonium chloride compound is said to be to the corresponding silver base and neutralization with an acid, whereby the desired anion is obtained.

The polyquaternary ammonium compounds were considered top products the dye-fixing agents, in particular for fixing dyes on textile materials, are described. They can also be used on or with synthetic fibers and natural fibers other than cellulosic in nature. It was

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also found that the polyquaternary ammonium compounds of the present invention with dyes and in particular with water-soluble and water-sensitive dyes can be combined to form insoluble products or pigments. Such materials can be in the absence any substrates made and used as a pigment in conventional Way to be used.

3s has also been found to be a unique application the polyquaternary ammonium compound of the present invention resides in its use, dyes to the conventional ones to fix mono- and multilinear color films. The use of such dye-fixing agents described here result in fixing the color in the films by making them much more resistant to environmental influences and strikethrough or migration of the coloring material in a single layer or between two adjacent layers impede.

/ Claim:

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Claims (2)

(D 51 070 IVb / l2qu) DePaul Chemical Company Inc. 1543529 Mannheim, August 28, 1968 Patent to sayings ' Polyquaternary ammonium compound with 8 to 20 nitrogen atoms of the formula R ₁ in R identical or different alkyl radicals with 1 to 6 carbon atoms, A and B are an alkylene, arylene or alkylene radical interrupted by an oxy-gen X = 4 to 17, Z is an anion residue represents or (A) an alkyl radical having 1 to 6 carbon atoms or (B) the formula - .ff B (ff — A) _v means in which A, B, R and Z have the meanings given above and at least one R radical has the formula B and Y is 0-3. ÜlHöi lajjsin ν * "- 1% ι aä. * I 4r. Ι sw * ο u _co Kiwerungsee ·. V. 4,». '1967} BATH ORIGINAL - patent claims - 2.) Process for the preparation of a polyquaternary ammonium compound having 8 to 20 nitrogen atoms of the formula in R the same or different alkyl radicals with 1 to 6 Carbon atoms, A and B is an alkylene, arylene or alkylene interrupted by a chalcogen X « 4 to 17, Z represent an anion radical or R (A) an alkyl radical having 1 to 6 carbon atoms or (B) the formula means in which A, B, R and Z have the meaning given above have and at least one R radical has the formula B and Y is 0 to 3, characterized in that η moles an amine with at least 2 primary nitrogen atoms reacts with n-1 moles of a dihalide for a sufficiently long time, to carry out the condensation to a polyamine having four times as many nitrogen atoms as the above amine has and then quadrupled the polyamine obtained. 9 0 9 8 4 0/1531 _b aD