US3560142A

US3560142A - Use of quaternary ammonium compounds in the dyeing of polyacrylonitrile with basic dyestuffs

Info

Publication number: US3560142A
Application number: US689354A
Authority: US
Inventors: Robert Christian Keller; Hilmar Roedel
Original assignee: Sandoz AG
Current assignee: Sandoz AG
Priority date: 1966-12-28
Filing date: 1967-12-11
Publication date: 1971-02-02
Anticipated expiration: 1988-02-02
Also published as: ES348624A1; CH484319A; DE1643526A1; FR1551361A; BE708560A; GB1160938A; DE1793740A1; CH1862966A4; DE1793740B2

Abstract

BENZYLATED OR NAPHTHYLATED POLYALKYLENE POLYAMINES QUATERNIZED WITH DIMETHYL SULPHATE ARE USED AS ADJUVANTS IN DYE BATHS CONTAINING A BASIC DYESTUFF IN ORDER TO REGULATE THE UPTAKE OF THE DYE ON FIBROUS MATERIALS CONSISTING OF OR CONTAINING POLYACRILONITRILE FIBRES OR THREADS.

Description

United States Patent US. Cl. 8-172 9 Claims ABSTRACT OF THE DISCLOSURE Benzylated or naphthylated polyalkylene polyamines quaternized with dimethyl sulphate are used as adjuvants in dye baths containing a basic dyestulf in order to regulate the uptake of the dye on fibrous materials consisting of or containing polyacrilonitrile fibres or threads.

BACKGROUND OF THE INVENTION When dyeing materials consisting of or containing polyacrylonitrile fibres or threads with basic dyestuffs difficulties are experienced in producing satisfactory dyeings, unless an adjuvant is used in the dye bath. Various adjuvants for producing such satisfactory dyeings have been proposed hitherto but they all have one or more disadvantages, especially the production of undesirable foam in the dye bath.

It is an object of the present invention to provide improved dyeing auxiliaries for use in the dyeing of materials consisting of or containing polyacrylonitrile fibres or threads.

It is a further object of the present invention to enable said polyacrylonitrile material to be dyed satisfactory with basic dyestuffs while avoiding or minimizing undesirable foaming.

It is a further object of the present invention to provide a dyeing auxiliary which enables the production of level dyeings when dyeing said polyacrylonitrile material with basic dyestuffs.

SUMMARY OF THE INVENTION The present invention provides a process for dyeing materials consisting of or containing polyacrylonitrile fibres or threads, which process comprises dyeing such a material in a dye bath containing a basic dyestuff under conditions for dyeing said polyacrylonitrile material with a basic dyestulf, the dyeing being effected in the presence of a quaternary ammonium compound which comprises:

(a) a plurality of basic nitrogen atoms of which at least 2 are present as quaternary ammonium groups,

(b) at least 2 aralkyl radicals selected from phenylalkyl radicals and naphthylalkyl radicals, each of said aralkyl radicals being attached to a nitrogen atom,

(c) at least 2 alkyl radicals with 1 to 6 carbon atoms each attached to a nitrogen atom, and

(d) at least one aliphatic radical linking together two basic nitrogen atoms which aliphatic radical consists Patented Feb. 2, 1971 of an alkylene radical with 2 to 8 carbon atoms devoid of any hetero atoms or of a plurality of alkylene radicals each of from 2 to 8 carbon atoms separated from one another by a sulphur or oxygen atom,

as a dyeing adjuvant, i.e. in an amount sufficient to produce satisfactory dyeings. The number of basic nitrogen atoms at (a) is preferably 2 to 7, but may be much greater.

The quaternary ammonium compounds of the present invention have a good affinity for the fibrous polyacrylonitrile material and favourably influence the uptake of the basic dyestuffs; in contradistinction to known dyeing assistants for regulating dyestuff uptake in similar situations, they do not produce any undesirable foam in aqueous solutions. In dye baths they cause a slowing down in the uptake of basic dyestuffs by the fibrous material and are most suitable for regulating the uptake speed of basic dyestuffs in dyeing polyacrylonitrile fibres or threads. As regards bath ratio, dyestulf quantity and dyeing temperature, dyeing conditions normally used for dyeing polyacrylonitrile material with basic dyestuffs are oper ative. The dyeing may be effected with increasing temperature, at C. or under pressure, for example at 100-120" C., in a closed vessel.

Apart from the quaternary ammonium compounds of the invention, bath additives usual in dyeing with basic dyestuffs may be present, for example salts such as sodium sulphate, -chloride or -acetate or acids such as acetic acid, or also buffer solutions.

The quaternary ammonium compounds of the invention may be employed in the form of pure compounds or as technical mixtures. Likewise, they may be used alone or in combination with suitable surface active compounds, such as for example surface active addition products of ethylene oxide and fatty amines, fatty alcohols, or alkylphenols. The amounts of the quaternary ammonium compounds to be used must be adjusted according to the circumstances of dyeing in each case, for example according to the nature and amount of the basic dyestuffs and according to the charatcer of the state of the fibrous material to be dyed. For example it amounts to 0.022% of the weight of the goods and may be added to the dye bath before or during the dyeing. It is also possible to pretreat the fibrous material with the quaternary compounds. The fibrous material to be dyed may be present in any desired form, e.g. as loose fibres, as yarn or as fabric; the fibrous material may consist of pure polyacrylonitrile or of mixed polymerizates containing a substantial proportion of polyacrylonitrile, e.g. mixed polymerizates of acrylonitrile with vinyl alcohol, vinyl acetate, acrylicand methacrylic acide esters, acrylic acid amides or vinyl chloride. Furthermore, it may be composed of a single type of fibres or of mixtures of such.

Examples of dyestuffs suitable for use in the process of the invention are dyes of the diand triarylmethane series, the azine-, oxazine-, thiazineand thiazole series, xanthene dyestuffs, acridine dyestuffs, quoinoline dyestuffs, quinophthalone dyestuffs, cyanine-, methine-, azomethineand polymethine dyestuffs, basic azoand basic anthraquirione dyestuffs, nitroand naphthoquinoneimine dyestuffs as well as dyestuffs with cyclic imonium or external onium radical.

The quaternary ammonium compounds of the present invention may be obtained in such a way that 1 mol of a dior polyamine, for example of the general formula wherein:

m is or a whole number,

n is an integer and r is 3 or any higher integer, with the proviso that m+r must be equal to n+3,

is reacted with at least 2 mol of an aralkylation agent of the naphthylalkyland/ or phenylalkyl series, and the resulting N-aralkylated polyamine in the form of the free amine is quaternized in manner known per se with a peralkylating agent which is suitable for introducing an alkyl radical with from 1 to 6 carbon atoms inclusive.

Examples of amines of the above Formula I are:

(l) Alkylene diamines, for instance ethylene diamine, propylene diamine, hexylene diamine, diaminooctane, N-monomethylhexylene diamine, di (arninopropyl)- sulphide;

(2) dialkylene triamines (these are preferred amines I), for instance diethylene triamine which is especially suitable, dipropylene triamine, bis (aminopr0pyl)- methylamine, dihexylene triamine;

(3) polyalkylene polyamines, for instance triethylene tetramine, tetraethylene pentamine, pentaethylene hexamine and hexaethylene heptamine and polyamines which may be obtained by the reduction of the addition products of acrylonitrile to amines, e.g. tetra- (aminopropyl)-pentaethylene hexamine. Likewise, substitution products of these amines are suitable such as for example a tetraethylene pentamine in which a labile hydrogen atom has been replaced by a methyl, ethyl, B-cyanoethyL, hydroxyethylor mercaptoethyl radical; and also polyethylene polyamines of high degree of polymerization, e.g. polyethylene imine having a molecular weight of 30,000 to 40,000.

(4) amines which may be obtained by the addition of acrylonitrile to a polyol or another material containing active hydrogen and subsequent reduction of the nitrile groups, for instance 1,2,3-tri-(aminoproxy)- propane.

Aralkylation agents of the naphthylalkyland the phenylalkyl series are, for example, 1-(chloromethyl)-naphthalene, 2-(chloromethyl)-naphthalene, 1- or 2-(2'-bromoethyl)-naphthalene, 2-, 3- or 4-methylbenzyl chloride, 2-, 3- or 4-ethylbenzyl bromide, 2-, 3- or 4-isopropylbenzyl chloride, fi-chloroand ,B-bromoethyl benzene, styrene oxide, 2-, 3- or 4-phenoxybenzyl chloride, phenoxyethyl chloride and especially benzyl chloride.

Examples of peralkylating agents are alkyl halides and alkyl sulphates having alkyl radicals with from 1 to 6 carbon atoms, for instance n-hexyl iodide, n-butyl bromide, methyl bromide, ethyl iodide, diethyl sulphate and especially dimethyl sulphate.

At room temperaure the ammonium compounds of the invention are liquids of high viscosity or tough sticky pastes or solid crystalline materials. They are soluble in alcohol-Water mixtures, e.g. a mixture of isopropanol and water, or in water under conditions usual in dyeing with basic dyestuffs.

The production of some quaternary ammonium compounds which are especially suitable for the dyeing process in accordance with the invention is exemplified below; the reagents and also the procedure of Example 3 is especially suitable. In these examples, as well as in the examples showing specific dyeing procedures, parts are parts by weight, percentages are percentages by weight and temperatures are stated in degrees centigrade.

Example 1 506 parts (4 mol) of benzyl chloride are added drop- Wise, while stirring, to a solution, heated to 80, of 74 parts (1 mol) of trimethylene diamine in 125 parts of Water. During this addition the temperature inside the reaction mixture should not rise above 100.

After the dropwise addition, stirring is continued for a further 90 minutes at 9095 and 533 parts of a 30% sodium hydroxide solution (4 mol NaOH) are then added.

The resulting water insoluble amine separates out and is removed; after recrystallization from ethanol it is obtained in crystalline form with a melting point of 404l (uncorrected) 434 parts (1 mol) of this crystalline amine are dissolved in 525 parts of benzene and heated to the boiling point of the benzene. 252 parts (2 mol) of dimethyl sulphate are added while stirring and kept for 45 hours at the reflux temperature of benzene. The resulting quaternary ammonuium compound is insoluble in benzene and separates in the form of a tough liquid. The supernatant benzene is decanted and the reaction product is freed of occluded benzene by vacuum distillation (about 20 mm. of Hg and -80). A brown, very tough mass results. The resulting product (ammonium compound No. 1) is soluble in water-isopropanol (1:1). It has an excellent retention power for basic dyestufis on dyeing polyacrylonitrile fibres.

Example 2 When the trimethylene diamine in Example 1 is replaced with the corresponding quantity of octamethylene diamine dissolved in 250 parts of water and working is effected in the same way as in Example 1, after recrystallization from ethanol, there is obtained an amine melting at 79-80 (uncorrected) which gives a brown tough mass (ammonium compound No. 2) after quaternizing. This has the same properties as the ammonium compound No. 1.

Example 3 103 parts (1 mol) of diethylene triamine are dissolved in 250 parts of water and heated to 80-90". 569 parts (4.5 mol) of benzyl chloride are added dropwise to this solution. The temperature of this reaction mixture should not exceed 100. After stirring for minutes at 90-100, 600 parts of a 30% sodium hydroxide solution (4.5 mol NaOH) are added and stirring is continued for a further 15 minutes.

The resulting water insoluble reaction product is separated and dried in a vacuum at about 15 mm. of Hg at The reaction product is a brown tough liquid.

508 parts (1 mol) of this brown tough liquid amine are heated to 60-65". 290 parts of dimethyl sulphate are added dropwise during 30-40 minutes while stirring. The temperature rises on the dropwise addition and should not exceed 100. 15 minutes after the dropwise addition the reaction product becomes pasty thick. 66 parts of isopropanol are added and stirring for 2 hours at 85-90" is effected. Thereafter a further 66 parts of isopropanol are stirred in and cooling is effected to room temperature while stirring.

The resulting quaternized product (ammonium compound No. 3) is dissolved in isopropanol-water; it has good retarding properties. The quaternization with dimethyl sulphate can likewise be efiected in an inert solvent, for instance benzene, used in an amount of about 500 to 1,000 parts per mol of the amine to be quaternized.

Example 4 110 parts (0.87 mol) of benzyl chloride are added dropwise with a speed such that the temperature does not exceed l20130 to 45 parts (about 0.145 mol) of a technical amine mixture consisting of 75% of bis-(hexamethylene) triamine, and higher homologs,

as well as amines of lower molecular Weight, nitriles and lactams. After the addition of benzyl chloride, 100 parts of water are added and the resulting material boiled at reflux for an hour.

115 parts of a 30% sodium hydroxide solution are then added dropwise. The resulting water insoluble benzylated amine separates out in the form of a liquid phase and is removed.

60 parts of dimethyl sulphate are added to 100 parts of the benzylated amine and the resulting material is stirred for 1 hour at 80-90. A viscous brown mass (ammonium compound No. 4) results; this is soluble in a mixture of water and isopropanol (1:1) and has an excellent retention power for basic dyestuffs in the dyeing of polyacrylonitrile fibres.

The following table lists further examples of specific After 60 minutes of further stirring, the dioxan is decanted off and the remaining quaternary product (ammonium compound No. 12) is dissolved in water/isopropanol (1:1).

One suitable method of carrying out the process of the invention comprises using as the dyeing adjuvant a quaternary ammonium compound which is a reaction product of:

(i) 1 mol of a dialkylene triamine with 4 to 16 carbon atoms in the molecule,

(ii) 44 /z mol of an aralkylation agent selected from the phenylalkyl and naphthylalkyl series, and

(iii) 2 /23 mol of a quaternization agent selected from alkyl halides with up to 6 carbon atoms in the molecule and alkyl sulphates with up to 6 carbon atoms in the molecule.

The following examples illustrate the dyeing process of the invention.

Example I 100 parts of polyacrylonitrile yarn in the form of a tow (More Dyeable Orlon 42, from the firm of Du Pont) are dyed in 5,000 parts of a dyebath containing 0.7 part of the dyestuff of the formula 39 2H4-H C H103 ammonium compounds of the invention; these compounds 01110-8039 are produced by following the procedure of the example shown in the last column. 2H5

TABLE 1 Melting point No. of the of the Quaternization ammonium Mols of benzylated Mols of solvent Production compound and benzyl amine, dimethyl according to Example Name of starting material Mol chloride degrees sulphate Name Parts Example- 5 Ethylene diamine 4 2 Benzene 525 1 6 Tetra-methylene diamine 4 2 do 525 1 Hexamethylene diamine 4 1 8 Dipropylene triamine 5 3 9 Tetraethylene pentamine 7 3 10 Pentaethylene hexamine 8 3 11 Mixture of 2,2,4- and 2,4,4-trimethyl-hexamethyl- 2 3 ene diamine.

Example 12 3 parts of sodium acetate 2 parts of 40% acetic acid and To 95 parts by weight of a 22.5% aqueous solution of polyethylene imine with a molecular Weight of from 30,000 to 40,000 there are added dropwise 70 parts by weight of benzyl chloride at 90. The reaction is exothermic; the inside temperature of the reaction mixture should be between 100 and 110 C. After the addition of the benzyl chloride is complete, stirring is effected for a further 1% hours at 95 to 100. Subsequently distillation is effected of the excess benzyl chloride with water in a slight vacuum (about 100 mm. of Hg); water must be added as soon as the product becomes viscous.

A total of parts by weight of benzyl chloride are recovered to that 50 parts by weight of benzyl chloride had been used up.

After removal of the benzyl chloride 60 parts by weight of a aqueous sodium hydroxidesolution are added dropwise. The benzylated polyamine, which is insoluble in water, separates out and is removed as liquid phase.

The lower aqueous layer is rejected, but the upper one is dried in a vacuum (15 mm. of Hg) at 105. The dried residue is light brown and very viscous.

parts by weight of the benzylated polyamine are taken up in 250 mm. of dioxan. parts by weight of dimethyl sulphate are slowly added dropwise at 80; the inside temperature should not exceed 105. The reaction product becomes highly viscous but remains stirrable.

0.6 part of the ammonium compound No. 1.

The fibrous material is put into the dyebath at 40, heating to -98 is effected during 45 minutes and dye ing at this temperature is effected for 60 minutes. The addition of adjuvant (i.e. ammonium compound No. 1) has a retarding and levelling effect on the uptake of the dyestuff so that a very level, light and wet stable red brown dyeing is obtained, Whereas without the addition of ammonium compound N0. 1 the dyestuff is taken up very quickly and the resulting dyeing is not level.

It is possible to replace the 0.6 part of the ammonium compound No. 1 with 0.79 part of the ammonium compound No. 5 or 11, or 0.59 part of the ammonium compound Nos. 2, 6, 7, 8 or 9, 0.46 part of the ammonium compound No. 3, 0.33 part of the ammonium compound No. 10 or 0.4 part of the ammonium compound No. 12 with similar advantageous results.

When the ammonium compounds Nos. 1 to 11 are used in dyeing with the dyestuff Basic Red. 26 (Cl. Supplement 1963, page 162), there likewise result level, light and wet stable violet tinged red dyeings.

Example II Working is effected in accordance with the data of Example I with the addition of ammonium compound No. 3 and the dyestuffs listed in the following table are used instead of dyestulf (A).

TABLE 2 Amount of the C .I. Amount ammonium number of the compound of the (lyestufi No. 3 in Name of dyestutf dyestutf in parts parts Safranin B 50 240 O. 7 0. 2 Brillantacridinorange 46 070 0. 7 0. 2 Methylviolett 5 B 0.... 42 555 0. 5 0.15 Auramin O 41 000 0. 7 0. 4 Rhodamin B 45 170 0. 7 0. 4 Gcnacrylblau 6 G 42 025 0. 5 0. 4 Baslc Red. 26.." O. 7 0.8 Dyestufl (B). 0. 7 0.6 Dyestufi (C) 0. 7 0.6

The dyestuffs (B) and (C) correspond to the respective formulae yellow Example III 100 parts of polyacrylonitrile yarns of various origins (as listed in Table 3) are dyed in 5,000 parts of a dyebath containing 3 parts of sodium acetate, 2 parts of 40% acetic acid, 0.16 to 1.0 part of an ammonium compound A likewise level, light and wet stable dyeing results when the dyestuff Basic Red. 26 is used instead of the dyestufi (A).

Example V 100 parts of polyacrylonitrile yarn in the form of a tow (type: More Dyeable Orlon 42 of the firm Du Pont) are dyed in 5,000 parts of a dyebath containing 0.7 part of dyestulf (A),

3 parts of sodium acetate, 2 parts of 40% acetic acid and 0.5 part of ammonium compound No. 4.

Working is elfected in the manner described in Example IV and a level red brown light and Wet stable dyeing results.

Instead of dyestuff (A) it is possible to use, for example, the following dyestuffs:

0.5% of the dyestuff Genacrylblau 6 g. ((3.1. 42025), 0.7% of the dyestutf (B) or 0.7% of the dyestulf Basic Red. 26.

as well as 0.7 part of the dyestufi (A). (i) an amine selected from the group consisting of:

TABLE 3 Ammonium compound Polyacrylonitrile material (adjuvant) Amount Name Manufacturer No. in parts Crylor 20 Crylor SA (France) 3 0. l6 Icacryl 16.-. Soc. ACSA Appl. chim. (Italy) 3 0.40 Dralon HB Bayer Leverkusen (Germany). 3 0.30 Courtelle. Courtaulds Ltd. (Great Britai 3 0. Acrylan Chemstrand Corg. (U.S.A.) g 0.138 Euroacryl Soc. ANIO (Italy) 5 0.79 10 0. 79 Exlan r Japan Exlan Ind. Co. Ltd. (Japan) 8 Example IV 100 parts of polyacrylonitrile yarns in the form of a tow (More Dyeable Orlon 42) are dyed in 5,000 parts of a dyebath containing:

0.7 part of dyestuff (A),

3 parts of sodium acetate,

2 parts of 40% acetic acid,

0.395 part of ammonium compound No. 3, and

0.395 part of an addition product of 35 mol of ethylene oxide and 1 mol of castor oil.

The fibrous material is put into the bath at 40, heating to 9598 is effected during 45 minutes and dyeing at this temperature is carried out for minutes. The ad juvant addition has a retarding and levelling elfect on the uptake of the dyestutl so that a level, light and Wet stable dyeing results.

a=a dialkylene triamine with 4 to 16 carbon atoms in the molecule,

b an alkylene diamine with 2 to 8 carbon atoms in the molecule,

c=a polyalkylene polyamine or a derivative thereof selected from triethylene tetramine, tetraethylene pentamine, pentaethylene hexamine and hexaethylene heptamine, tetra (amino-propyl)- pentaethylene hexamine and polyethylene polyamines of high degree of polymerization, and of molecular weight of about 30,000 to 40,000;

d=1,2,3-tri-(aminopropoxy)-propane.

(ii) an aralkylation or phenylalkylation agent selected from the group consisting of l-(chloromethyl)- naphthalene, 2-(chloromethyl)-naphthalene, 1- or 2- (2-bromoethyl)-naphthalene, 2-, 3- or 4-me'thylbenzyl chloride, 2-, 3- or 4-ethylbenzyl bromide, 2-, 3- or 4- isopropylbenzyl chloride, ,B-chloroand fl-bromoethyl benzene ,styrene oxide, 2-, 3- or 4-phenoxybenzyl chloride, phenoxyethyl chloride and benzy chloride;

(iii) a quaternization agent selected from alkyl halides with up to 6 carbon atoms in the molecule and alkyl sulphates with up to 6 carbon atoms in the molecule.

2. A process according to claim 1, in which said quaternary ammonium compound is a reaction product of:

(i) an alkylene diamine with 2 to 8 carbon atoms in the molecule,

(ii) an aralkylation agent selected from the phenylalkyl and naphthylalkyl series, and

3. A process according to claim 1, in which said quaternary ammonium compound is a reaction product of:

(i) a polyalkylene polyamine or a derivative thereof selected from triethylene tetramine, tetraethylene pentamine, pentaethylene hexamine and hexaethylene heptamine, 1,2,3-tri-(aminopropoxy) propane and polyethylene polyamines of high degree of polymerization,

4. A process according to claim 1, in which said quaternary ammonium compound is a reaction product of:

(i) 1,2,3-tri-(aminopropoxy)-propane,

5. A process according to claim 1, in which the quaternary ammonium compound is a reaction product of:

(i) diethylene triamine,

(ii) benzyl chloride, and

(iii) dimethyl sulphate,

6. The process according to claim 5 wherein 103 parts of diethylene triamine dissolved in water is reacted with 56.9 parts benzyl chloride at to C.; the resultant product is then quaternized with dimethyl sulfate.

7. A process according to claim 1, in which said quaternary ammonium compound is a reaction product of:

(i) an alkylene diamine with 2 to 8 carbon atoms in the molecule,

8. A process according to claim 7, in which constituent (iii) is selected from n-hexyl iodide, n-butyl bromide, methyl bromide, ethyl iodide, diethyl sulphate and dimethyl sulphate.

9. A process according to claim 7, in which constituent (i) is a mixture of amines.

References Cited UNITED STATES PATENTS 2,083,181 6/1937 Zweifel et al. 8-84 2,891,835 6/1959 Matter et al. 8177X 2,967,755 1/1961 Keller 8-84 2,984,539 5/1961 Matter et al. 8177X GEORGE E, LESMES, Primary Examiner T. J. HERBERT, JR., Assistant Examiner us. 01. X.R, s--s4, 177

- UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION Patent No, 3) D d February 2,

Inventofls) Robert Christian Keller, et a1 It is certified that: error appears in the above-identified patent and that said Letters Patent are hereby corrected as shown below:

Column 10, line 6, "56.9" should read 569 Signed and sealed this 10th day of October 1 E- SEAL) Attest:

EDWARD M.FLETCHER,JR. 7 ROBERT GOT'I'SCHALK Attesting Officer Commissioner of Patents )RM PO-IOSO (10-69) a 0.! sovummn mums emu luo 0-10-04.