GB1601815A

GB1601815A - Quaternary ammonium compounds and their use as retarders in the dyeing of anionic polyacrylonitrile fibres with cationic dyes

Info

Publication number: GB1601815A
Application number: GB1529777A
Authority: GB
Original assignee: Yorkshire Chemicals Ltd
Current assignee: Yorkshire Chemicals Ltd
Priority date: 1978-03-28
Filing date: 1978-03-28
Publication date: 1981-11-04

Description

(54) QUATERNARY AMMONIUM COMPOUNDS AND THEIR USE AS RETARDERS IN THE DYEING OF ANIONIC POLYACRYLONITRILE FIBRES WITH CATIONIC DYES (71) We, YORKSHIRE CHEMICALS LIMITED, a British Company of Black Bull Street, Leeds LSl0 IHP, West Yorkshire, do hereby declare the invention, for which we pray that a patent may be granted to us, and the method by which it is to be performed, to be particularly described in and by the following statement: This invention relates to novel quaternary ammonium compounds, to processes for their manufacture, and to their use as retarding or restraining agents in the dyeing of anionic polyacrylonitrile fibres by cationic dyes, also known as basic dyes. In particular it relates to quaternary ammonium compounds in which more than one quaternary amino group is attached to a hydrocarbon radical at such points on the hydrocarbon radical that the quaternary ammonium groups are widely separated.

Quaternary ammonium compounds have been used for many years in the dyeing of polyacrylonitrile fibres with cationic dyes. Their role has been primarily one of controlling the rate of dyeing. It is probable that this is achieved by the preferential attachment of the quaternary ammonium compound at the active dyeing sites. This will reduce the rate at which the cationic dye is adsorbed since the quaternary ammonium compound will first have to be displaced by the dye.

The rate of dye adsorption can in this way be controlled.

Although a considerable measure of success has been obtained by use of the quaternary ammonium compounds available hitherto, certain disadvantages have been associated with many of them. Thus the quaternary ammonium compound, if if is effective as a retarder, often becomes very firmly attached to the fibre. This may make over-dyeing, for the purpose of correcting or modifying the shade, difficult or even impossible. It is also frequently the case that the quaternary ammonium compounds, used hitherto, have a deleterious effect upon the lightfastness of the dyes used. It is also the case, from time to time, that certain cationic dyes can be hydrolysed or decomposed quite readily in the presence of certain quaternary ammonium compounds.

We have found, surprisingly, that the compounds of the present invention whilst being excellent retarding or retraining agents in the dyeing of anionic polyacrylonitrile fibres with cationic dyes, still permit over-dyeing of the dyed material. Moreover, in general, they show very little influence on the lightfastness of the dye used. Why the quaternary ammonium compounds of the present invention should differ so much from similar quaternary ammonium compounds derived from monobasic aliphatic acids is not known at the present time.

According to the present invention, water-soluble quaternary ammonium compounds are provided of the following general formula:

in which R1 represents a hydrocarbon radical derived from a dibasic or polybasic aliphatic or cycloaliphatic acid such that at least 8 carbon atoms are present as a hydrocarbon chain between each 'carboxyl group.

R2 and R3 each individually represnts an alkyl group containing up to 5 carbon atoms, R4 represents an alkyl group containing up to 5 carbon atoms or -CH2Ar.

wherein Ar is a phenyl group or a chlorinated phenyl group e.g. 3.4 dichlorophenyl, R5 represents an alkylene group containing up to 4 carbon atoms, Q represents -0- or -NR6-, wherein R6 represents hydrogen or an alkyl group containing up to 5 carbon atoms, m represents the acid functionality of the parent polybasic acid from which R is derived and can be 2, 3 or 4, Xfl- represents an anion whch renders the compound soluble in water, preferably C-, SO4--, or MeSO4-, and n represents the valency of the anion, with the proviso that the groups:

need not be identical to one another.

As examples of the dibasic or polybasic carboxylic acids which may be used as the source of the hydrocarbon radical R1, may be quoted dibasic acids of the general formula (II)

where n is at least 8 for example dodecane -l,l dioic acid. Of particular value in the performance of this invention are certain modified unsaturated fatty acids of the type present in the so-called drying oils. One such acid can be made by reacting linoleic acid with acrylic acid to form a mixture of dibasic acids of the structures (III) and (IV), from which it will be seen that the carboxylic groups are separated by chains of at least 9 and 10 carbon atoms respectively.

Particularly suitable dibasic and polybasic acids are to be found in the widelv known class known as "dimer acids". These acids are products of the drying oil industry and are polymerisation products of the unsaturated drying oil acids such as linoleic and linolenic acid. The dibasic polymeric acid in which the degree of polymerisation is 2 is the major component of the commercially available "dimer acid", but also present are varying proportions, according to the process of manufacture, of higher polymers. The constitution of dimer acid itself is stated to be that shown in formula (V), wherein it will be seen that there is a chain of 16 carbon atoms between the carboxylic groups.

We have found dimer acids in particular, to be eminently suitable as a source of the hydrocarbon radical R1 in the execution of this invention.

The quaternary ammonium compounds of the invention are most conveniently prepared by heating aliphatic dibasic or polybasic acid with an amino alcohol of formula (VI) or with a diamine of the formula (VII) where R2, R3, Rs and R6 have the meanings given above.

If it is desirable to avoid any discoloration of the reaction product due to oxidation, it may be advisable to carry out this reaction in an inert atmosphere, for example under nitrogen.

Water is eliminated during the reaction and the temperature of the reaction mixture is adjusted to maintain a steady evolution thereof. This water is preferably condensed and collected in a receiver, and the extent of the reaction can be estimated by measuring the quantity of water collected. When the esterification or amide formation is substantially complete, the product is quaternised by heating with a quaternising agent such as benzyl chloride, methyl sulphate or 3,4dichlorobenzyl chloride. If desired, the esterification, or amide formation, may be carried out in the presence of a solvent capable of forming a constant boiling azeotropic mixture with water. A suitable solvent for this purpose is toluene. The quaternization may also be carried out in a solvent. The rate of quaternisation in general, is often dependent upon the solvent used. Polar solvents, e.g.

nitrobenzene, frequently accelerate the reaction, as compared with non-polar solvents such as hydrocarbons.

Although the preferred methods form the product of the invention directly from the dibasic or polybasic acid, alternatives exist. Thus the acid may be converted into the acid chloride which can then be used to react with compounds (VI) or (VII). Such methods are obvious modifications of the method just described.

According to the present invention there is also provided a method of dyeing anionic polyacrylonitrile fibres with cationic dyes characterised by the presence of one or more of the quaternary ammonium compounds of the present invention during dyeing.

The invention also includes the over-dyeing of fibres dyed in this way.

Anionic polyacrylonitrile fibres include fibres of acrylonitrile homopolymers and particularly acrylonitrile copolymers containing at least 50% and preferably from 80 to 98 ó by weight of acrylonitrile units, which polymers (with or without conventional comonomers such as acrylamide, acrylic esters, methacrylic esters, vinyl esters and vinyl chloride) contain comonomers having anionic group, for example olefinically unsaturated carboxylic acids such as acrylic acid, methacrylic acid or also olefinically unsaturated sulfonic acids. In some cases the content of carboxylic groups in the polyacrylonitrile formed by hydrolysis of a small portion of the nitrile groups is sufficient.

The quaternary ammonium compounds of the invention are very suitable for use as retarders in the dyeing of polyacrylonitrile fibres with cationic dyes. These retarders successfully compete with the cationic dyes for the anionic sites in the fibre, thus producing a slower and more even rate of strike of the dyes to give a more level dyeing. Conventional additions to the dyebath such as soldium sulphate, sodium acetate or acids such as formic or acetic, may be made in addition to the quaternary ammonium compounds to be used according to the invention.

The amount of the quaternary ammonium compounds of the invention to be used must be altered according to the amount of cationic dye being applied as well as the type of acrylic fibre to which the dye is being applied.

Amounts varying from 0.002 to 5070 and preferably 0.02 to 4% of the compounds of the invention may be used based on the weight of the fibres being dyed. The quaternary ammonium compound may either be applied to the fibres prior to dyeing with the cationic dyestuffs or may be applied at the same time as the dyestuffs.

The acrylic fibres may be dyed in any form, for example, loose fibres, yarn or cloth and in any of the different dyeing machines that are used for batch dyeing these forms of the acrylic fibres.

After dyeing anionic polyacrylonitrile fibres with cationic dyes in the presence of the more conventional quaternary ammonium compounds such as cetyl trimethyl ammonium bromide, it is found that further additions of cationic dye to the dyebath cannot be exhausted on to the fibres. The anionic sites in the polyacrylonitrile fibres are effectively, permanently blocked by the presence of the more conventional retarder. It has been found that when polyacrylonitrile fibres are dyed with cationic dyes in the presence of quaternary ammonium compounds of the invention, further additions in cationic dye to the dyebath may be made and the dye successfully exhausted on to the fibres. This process may be described as 'over dyeing' and is often carried out to change the shade of the fibres during dyeing, for example, to cover up any unlevelness that may have occurred due to mechanical problems with the dyeing machinery. The fibres may be 'over dyed' for example, to change a yellow to a black or navy. This process is further illustrated in Examples 6 and 7 below.

Some of the more conventional quaternary ammonium compounds which have been used as retarders in dyeing anionic polyacrylonitrile fibres, for example, cetyl trimethylammonium bromide, produce a deleterious effect on the lightfastness of dyeings produced in their presence with certain cationic dyes. It has been found that the compounds of the present invention do not, in general, have this effect.

The invention is illustrated, but not limited by, the following Examples.

Example 1 280 g commercial dimer acid (Hystrene 3680--Hystrene is a registered Trade Mark, ex Humko Products, Kraftco Corporation, Memphis, Tennessee, U.S.A.) are heated with stirring together with 90 g N,N-dimethylaminoethanol in a vessel equipped with a water trap and reflux condenser, under a mantle of nitrogen. The temperature of the mixture is gradually raised from 145"C to 2000C during which time approximately 18 ml water are eliminated and collected in the water trap. This process takes about 8 hours. The product of the reaction is then cooled to 600C and 126 g benzyl chloride is added dropwise with stirring during which time the temperature is allowed to rise to 1200C and the mixture is heated for a further 4 hours &commat; 1300C. Any residual benzyl chloride can be removed under vacuum. A yellow, viscous mass is obtained, which is soluble in water to give a faint cloudy solution, and totally soluble in a mixture of iso-propanol and water (3:5).

Example 2 The procedure described in Preparation 1 is repeated using 103 g N,Ndimethylaminopropylamine in place of N,N-dimethylaminoethanol. A yellow viscous liquid, completely soluble in water is obtained.

Example 3 5 g of Courtelle (Courtelle is a registered Trade Mark) yarn (an anionic polyacrylonitrile fibre manufactured by Courtaulds Ltd.) were entered into a dyebath containing 200 ml of water and 1 ml of a 10% solution of glacial acetic acid.

4 ml of 1% aqueous solution of C. I. Basic Red 59 was then added to the dyebath together with 5 ml of a 1% aqueous solution of the product of Example 1. The dyebath temperature was raised to 98"C at a rate of rise of temperature of 1 C per minute, and this temperature held for a further 90 minutes. After cooling slowly, the yarn was removed from the dyebath and washed in warm water. The yarn was found to be dyed very level to a bright ruby red shade. A similar dyeing carried out without the chemical of the invention being present was found to be very unlevel.

The unlevelness being attributed to the high rate of dyeing of the C. I. Basic Red 59 which had been successfully slowed down in the presence of the chemical of the invention.

The lightfastness of the dyed yarn when exposed to Xenon arc light was found to be equal to that when the yarn was dyed with C. I. Basic Red 59 in the absence of the chemical of this invention.

Example 4 100 kg of knitted Courtelle fabric was introduced into a winch dyeing machine which had been filled with 3,500 kg of water to which 1 kg of glacial acetic acid and 1 kg of sodium acetate crystals had been previously added in a dissolved state. 1.5 kg of C. I. Basic Blue 54 were dissolved in 50 kg of boiling water and this solution was slowly added to the dyebath. 750 g of a product made according to the method of Example 1 were then added to the dyebath and the temperature raised at 0.750C per minute to 98"C. This temperature was then maintained for 90 minutes. The dyebath was then dropped and the fabric washed with warm water. After drying, the bright blue fabric was found to be very level and free from dyeing faults. When this dyed fabric was compared to a similar fabric dyed in the absence of the levelling agent, which is the chemical of the invention, it was realised that the omission of the levelling agent gave an unlevel dyeing. The lightfastness of the fabric dyed in the presence of the levelling agent of the invention when exposed to Xenon Arc light was found to be no lower than when dyed in the absence of the levelling agent.

Example 5 100 kg of Courtelle yarn was introduced into a yarn package dyeing machine together with 2,500 kg of water containing 750 g of glacial acetic acid and 750 g of sodium acetate. 3.5 kg of a product made according to Example 2 were dissolved in the dyebath and the liquor kept circulating at 350C.

100 g of C. I. Basic Yellow 28 were dissolved in boiling water prior to adding to the dyebath. The temperature of the dyebath was raised at 1.50C/minute to 980C and kept at this temperature for 90 minutes. The yarn was then washed with warm water.

After drying, the bright yellow yarn was found to be free from unlevelness and in a very satisfactory condition.

Example 6 The dyeing was carried out as in Example 5 but after the Basic Yellow 28 had been given 90 minutes at 98"C, it was decided to turn the shade to a greenish blue.

1 kg of C. I. Basic Blue 54 was dissolved in boiling water and added to the dyebath at 50"C. The temperature was raised at 10minute to 980C and given a further 90 minutes at this temperature.

On cooling and washing off the yarn it was noticed that the deep greenish blue dyeing was very level and the C. I. Basic Blue 54 had exhausted well from the dyebath.

The lightfastness of the dyeing was found to be equal to that of a dyeing carried out in the absence of the chemical of the invention. In the latter case, the dyeing was very unlevel.

Example 7 The dyeing was carried out as in Example 6 but in place of the levelling agent of the invention, 3.5 kg of a quaternary compound produced by quaternising N,Ndimethylstearylamine with methyl chloride was introduced into the dyebath.

This produced a dyeing that was not only unlevel but the blue dye had given very poor exhaustion and the shade was a yellowish turquoise blue. This type of quaternary ammonium compound had permanently blocked the fibre sites so preventing the blue dye from exhausting. The quaternary ammonium compound used in this Example also reduced the lightfastness of the dyeing to such an extent that it was unacceptable.

WHAT WE CLAIM IS: I. A water-soluble quaternary ammonium compound of the following general formula:

**WARNING** end of DESC field may overlap start of CLMS **.

Claims

**WARNING** start of CLMS field may overlap end of DESC **. found to be dyed very level to a bright ruby red shade. A similar dyeing carried out without the chemical of the invention being present was found to be very unlevel. The unlevelness being attributed to the high rate of dyeing of the C. I. Basic Red 59 which had been successfully slowed down in the presence of the chemical of the invention. The lightfastness of the dyed yarn when exposed to Xenon arc light was found to be equal to that when the yarn was dyed with C. I. Basic Red 59 in the absence of the chemical of this invention. Example 4 100 kg of knitted Courtelle fabric was introduced into a winch dyeing machine which had been filled with 3,500 kg of water to which 1 kg of glacial acetic acid and 1 kg of sodium acetate crystals had been previously added in a dissolved state. 1.5 kg of C. I. Basic Blue 54 were dissolved in 50 kg of boiling water and this solution was slowly added to the dyebath. 750 g of a product made according to the method of Example 1 were then added to the dyebath and the temperature raised at 0.750C per minute to 98"C. This temperature was then maintained for 90 minutes. The dyebath was then dropped and the fabric washed with warm water. After drying, the bright blue fabric was found to be very level and free from dyeing faults. When this dyed fabric was compared to a similar fabric dyed in the absence of the levelling agent, which is the chemical of the invention, it was realised that the omission of the levelling agent gave an unlevel dyeing. The lightfastness of the fabric dyed in the presence of the levelling agent of the invention when exposed to Xenon Arc light was found to be no lower than when dyed in the absence of the levelling agent. Example 5 100 kg of Courtelle yarn was introduced into a yarn package dyeing machine together with 2,500 kg of water containing 750 g of glacial acetic acid and 750 g of sodium acetate. 3.5 kg of a product made according to Example 2 were dissolved in the dyebath and the liquor kept circulating at 350C. 100 g of C. I. Basic Yellow 28 were dissolved in boiling water prior to adding to the dyebath. The temperature of the dyebath was raised at 1.50C/minute to 980C and kept at this temperature for 90 minutes. The yarn was then washed with warm water. After drying, the bright yellow yarn was found to be free from unlevelness and in a very satisfactory condition. Example 6 The dyeing was carried out as in Example 5 but after the Basic Yellow 28 had been given 90 minutes at 98"C, it was decided to turn the shade to a greenish blue.

in which R1 represents a hydrocarbon radical derived from a dibasic or polybasic aliphatic or cycloaliphatic acid such that at least 8 carbon atoms are present as a hydrocarbon chain between each carboxyl group, R2 and R3 each individually represents an alkyl group containing up to 5 carbon atoms R4 represents an alkyl group containing up to 5 carbon atoms or -CH2Ar.

wherein Ar is a phenyl group or a chlorinated phenyl group, R5 represents an alkylene group containing up to 4 carbon atoms, Q represents -0- or -NR6-, wherein R6 represents hydrogen or an alkyl group containing up to 5 carbon atoms, m represents the acid functionality of the parent polybasic acid from which R is derived and can be 2, 3 or 4, X"- represents an anion which renders the compound soluble in water, and n represents the valency of the anion, with the proviso that the groups:

need not be identical to one another.

2. A compound as claimed in claim 1, in which the carboxylic acid, source of the hydrocarbon radical R1, is a dibasic acid of the general formula (II)

where n is at least 8.

3. A water-soluble quaternary ammonium compound substantially as hereinbefore described in any one of the foregoing Examples 1 to 6.

4. A method of preparing a quaternary ammonium compound as claimed in claim I which comprises heating the aliphatic dibasic or polybasic acid or acid chloride thereof with an amino alcohol of formula (VI) or with a diamine of the formula (VII)

wherein R2, R3, R5, and R6 have the meanings given in claim 1 and then heating the product with a quaternising agent.

5. A process as claimed in claim 4 in which the esterification or amide formation is carried out in an inert atmosphere.

6. A method of preparing a quaternary ammonium compound substantially as hereinbefore described in Example I or 2.

7. A method of dyeing anionic polyacrylonitrile fibres with cationic dyes in which one or more of the quaternary ammonium compounds as claimed in any one of claims I to 3, are present during dyeing.

8. A method as claimed in claim 7, in which from 0.002 to 5% of quaternary ammonium compounds as claimed in any one of claims I to 3, based on the weight of the fibres being dyed, is used.

9. A method as claimed in claim 8, in which from 0.02 to 4% of quaternary ammonium compound as claimed in any one of claims I to 3, based on the weight of fibres being dyed, is used.

10. A method as claimed in any one of claims 7 to 9, in which the quaternary ammonium compound is applied to the fibres with the dyestuff.

I 1. A method as claimed in claim 7, substantially as hereinbefore described in any one of the foregoing Examples 3 to 5.

12. A method of dyeing in which fibres dyed in accordance with the process of any one of claims 7 to 11 are over-dyed.

13. A process as claimed in claim 11, substantially as hereinbefore described in foregoing Example 6.

14. Acrylic fibres whenever dyed by a method as claimed in any one of claims 7 to 13.