CA1060890A - Process for the manufacture of anthraquinone dyestuff mixtures - Google Patents

Abstract

PROCESS FOR THE MANUFACTURE OF ANTHRAQUINONE DYESTUFF MIXTURES

Abstract of the Disclosure A process for the manufacture of anthraquinone dyestuff mixtures by brominating one mol of a diphenyl ether of the formula

Description

~60~9 - It has been found that valuable anthraquinone mixtures are obtained if one mol of a diphenyl ether of the formula ~ 0_O~
Rl or of a mixture of such compounds, wherein Rl denotes a hydrogen atom or a phenyl or phenoxy group, is brominated with a quantity of bromine between 1 and 2 mols, if Rl denotes a hydrogen atom, or is brominated with a quantity of bromine between 0.9 and 2 mols, if Rl denotes a phenyl or phenoxy group, and the resulting bromination product is reacted with a molar quantity, corresponding to the degree of bromination, of a monoaminoanthraquinone or a mixture of monoaminoanthraquinones of the ~ormula \1,~ \./ \ / ~
I 11 11 1 ~II) / ~-/ \0/ \-~ \

Xl Xl wherein one Xl denotes a hydrogen atom or a hydroxyl, alko~y, arylmercapto, arylamino, acylamino or benzthiazolylmercapto group, and the remaining Xl denote hydrogen atoms, and one Z denotes a hydrogen or chlorine atom and the others denote hydrogen atoms.
The diphenyl ethers which are used as the starting materials are known compounds.
me following may be mentioned as examples: 2- or 4-phenyldiphenyl ether and 2- or ~-phenoxydiphenyl ether.
l'he unsubstituted diphenyl ether is preferred.
Mixtures of the ethers mentioned can also be used with advantage.
The bromination is carried out in accordance with generally known methods using elementary bromine, preferably in an organic solvent, for example chlorobenzene, o-dichloro~
benzene, trichlorobenzene and, in particular, nitrobenzene, B - 2 - ~

1al6~90 in a temperature range from -10 to 150 C, preferably 20-60C, and optionally in the presence of a halogenation catalyst, such as iodine or an iron salt.
It is appropriate to use 5-15 parts of the solvent to 1 part of the diphenyl ether.
A mixture of monobrominated and dibrominated diphenyl ethers is formed in this bromination.
These diphenyl ethers are reacted with a molar quan-tity, corresponding to the degree of bromination, of a mono-aminoanthraquinone or a mixture of various monoaminoanthra-quinones.
In the above formula II, the alkoxy groups preferably denote methoxy groups and the aryl radicals preferably denote phenyl radicals which are optionally substituted by halogen atoms, alkyl or alkoxy groups containing 1-4 C
atoms, or trifluoromethyl groups, and the acylamino group denotes, for 1~6~89~
example, an alkanoylamino group having 2-6 C atoms, but preferably denotes a benzoylamino group which is optionally substituted by halogen atoms or alkyl or alkoxy groups con-taining 1-4 C atoms.
l-Amino-4-hydroxyanthraquinone 9 which leads to blue dyestuf~s, is particularly preferred.
- The following may be mentioned as further examples of aminoanthraquinones: l-aminoanthraquinone, l-amino-~-chloroanthraquinone, l-amino-6- or 7-chloroanthraquinone, 1-amino-4-methoxyanthraquinone, 1-amino-5-methoxyanthraquinone, l-amino-4-phenoxyanthraquinone, 1-amino-4-phenylmercapto-anthraquinone, l-amino-5-phenylmercaptoanthraquinone, 1-amino-8-phenylmercaptoanthraquinone, 1-amino-4-phenylamino-anthraquinone, l-amino-4-benzoylaminoanthraquinone, l-amino-4-(2',3'- or 4'-chlorobenzoylamino)-anthraquinone, l-amino-5-benzoylaminoanthraquinone, 1-amino-5-(2',~'- or 4'-chloro-benzoylamino)-anthraquinone, l-amino-8-benzoylaminoanthra-quinone, l-amino-4-benzthiazolylmercaptoan-thraquinone and 1-amino-5-benzthiazolylmercaptoanthraquinone.
The mixture of the brominated ethers is reacted, appropriately without isolating it from the reaction mixture, directly with -the aminoanthraquinone or aminoanthraquinone mixture. This stage o~ the process is appropriately carried out in the presence of acid-binding agents, such as alkali me~al carbonates or acetates, and catalysts, such as copper or copper compounds, at temperatures between 150 and 250.
In -the simplest case, that is to say when using 89~

single-substance aminoanthraquinones as the starting materials, the dyestuffs which can be obtained in accordance with the invention are preferably mixtures consisting to the extent of 10-90% of monocondensation produc-ts of the formulae AN0 1 ~ ~ (III) and/or .

~ 0 ~ (IV) and to the extent of 90 - 10% of dyestuffs of the formula . I \
~-~ (V) , \R~

wherein Rl has the meaning indicated above and the A
represent identical or different an-thraquinone radicals.
Mixtures of particular interes-t are those containing dyestuffs of the formulae (III), (IV) and (V) wherein A denotes ~ 060890 a radical of the formula z ~ ~ ~ 1 z (VI) Xl Xl ~

wherein Xl and Z have the meaning indicated above, and particularly those wherein A denotes the radical o~ the for-mula O .

(VII) OH

Particularly preferred mixtures are those consistingto the extent of lQ - 90% of the dyestuff of the formula . ~, (VIII) 0~
and to the extent of 90 - 10% of the dyestuff of the formula 1(~6~ 390 HN ~ ~ ~ - NH

~ ~ ~ (IX) - O OH ~lo If mixtures of ethers and/or aminoanthraquinones are used as the starting materials, the number of the components present in the mixtures is, of course 7 multiplied.
The mixtures obtained in accordance with the inven-tion are preferentially suitable for the bulk dyeing of thermoplastics, for example polystyrene and copolymers thereof, polyolefines, polycarbonates and polyamides 9 but particularly linear polyesters~
Linear polyesters which should be mentioned par-ticularly are those which are obtained by the polycondensa-tion of terephthalic acid or esters thereof with glycols of the formula HO-(CH2)n-OH wherein n denotes the number 2 - 10, or with 1,4-di(hydroxymethyl)-cyclohexane, or by the poly-condensa-tion of glycol ethers of hydroxybenzoic acids, for example p-(~-hydroxyethoxy)-benzoic acid. The term linear polyesters also encompasses copolyesters which are obtained by the partial replacement of the terephthalic acid by another dicarboxylic acid and/or by the partial replacement of the glycol by another diol. However, the polyethylene terephthalates are of particular interest.
The linear polyesters to be dyed are appropriately ~` . .
, ~06~39~
intimately mixed, in the form of powders, chips or granules, with the dyestuff. This can be effected, for example, by sprinkling the finely divided, dry dyestuff powder onto the polyester particles or by treating the polyester particles with a solution or dispersion of the dyestuff in an organic solvent and subsequently removing the solvent.
Finally, the substance used for dyeing can also be directly added to the molten polymer or can also be added before or during the polycondensation of the polyethylene terephthalate.
The ratio of dyestuff to polyester can vary within wide limits, depending on the depth of colour desired. In general, the use o~ 0.01 - 3 parts of dyestuff to 100 parts of polyester is recommended.
The polye~ster particles treated in this way are melted in the extruder in accordance with known processes anda~e extru~èd to give ; articles, particularly films or fibres, or cast to give sheets.
Articles which are evenly and intensively dyed and have good fastness to light are obtained. The dyed fibres which can be obtained in accordance with the process are distinguished, in addition, by outstanding fastness to wet and dry cleaning.
A particular advantage of the dyestuffsto be used in accordance with the invention consists in the fact that they dissolve in the polyester melt and, surprisingly, stand up -to high -temperatures of up to 300C, without decomposition, so 3L06~390 that significantly clearer dyeings are obtained than when pigments are used. DOS 2,343,127 describes the manufacture of single-substance dyestuffs of the formula (IX). Com-pared with these, the mixtures which can be obtained in accordance with the invention are dis-tinguished by better solubility in polymers and 3 par-ticularly, by better fastness to rubbing after thermofixing.
In the Examples which follow, unless otherwise recorded, the parts denote parts by weight and the percentages denote percentages by weight.
Example 1 A solution of 28.8 parts of bromine in 50 parts of nitrobenzene is run, whilst stirring, over the course of an hour,into a solution of 17 parts of diphenyl ether in 150 parts of nitrobenzene, after adding 0.01 par-t of iodine.
The reaction mixture is stirred for a further hour at room temperature. 36 parts of anhydrous sodium acetate, 43 parts of l-amino-4~hydroxyanthraquinone~ 1 part of copper-I
chloride and 1 part of copper powder are then added and the mixture is stirred for 28 hours at 200 - 210C, whilst dis-tilling off the acetic acid formed. After cooling to 70C, 1,000 parts of alcohol are added, the mixture is allowed to cool completely and the product which has separated out is removed and washed with alcohol and then wi-th hot water.
The moist dyestuff is stirred in 1,000 parts of 5% strength hydrochloric acid and 0.5 part of sodium nitrite is added in portions. The mix-ture is then warmed to 80C, stirred for 30 ~L06089~

minutes and fil-tered while hot and the produc-~ is thoroughly washed with hot water. After drying at 80C in vacuo, 55 parts of a blue dyestuff are obtained, which dyes polyester in bulk, by the melt spinning process, in fast, blue shades.
The dyeings are also distinguished, in deep shades, both by good resistance to marking-o:Ef against other fabrics during thermofixing and by good fastness to rubbing of the dyed material after thermofixing.
Similar dyestuffs are obtained, analogously to the instructions of Example 1, if a diphenyl ether derivative listed in the table which follows is treated with bromine in the molar ratio indicated and is then condensed with l-amino~
4-hydroxyanthraquinone in the same ratio or using a quantity of the latter which is not more than 10% below the equivalent amount.

, _...... ~ . . _._ Example Diphenyl ether derivative Molar bromin~ Shade in . ation ratio polyester .... ___ ... .. .~ ___

2 diphenyl ether 1 : 1.5 blue

3 I~ ., 1 : 1.6

4 ll ll 1 : 1.7 hydroquinonediphenyl ether 0.9 : 1 n 6 . " " 1 : 1.4 7 ~ " 1 : 1 ll 82-phenyldiphenyl ether 0.9 : 1 n 911 11 1 1 ll 10ll ll 1 : 1.2 , , ._~ _ _~

Green dyestuffs are obtained i~ bromination mixtures of diphenyl ether according to the preceding Examples are condensed with corresponding molar quanti-ties of l-amino-4-anilinoanthraquinone instead of l-amino-4-hydroxyanthraquin-one.

17 parts of diphenyl ether are treated, in nitro-benzene, with 19.2 parts of bromine in a manner corresponding to Example 1, and, after adding 20 parts of sodium acetate, 0.5 part of copper-I chloride and 0.5 par-t of copper powder, are condensed for 12 hours at 200-210C with 4.1 parts of l-amino-4-benzoylaminoanthraquinone. After ~orking up in accordance with Example 1, a blue dyestuff is obtained, which dyes polyester, by the melt spinning process, in clear, fast, blue shades.
Example 12 17 parts of diphenyl ether are treated in nitro-benzene with 27.2 parts of bromine, in accordance with Example 1, and, after adding 25 parts of anhydrous sodium acetate, 0.5 part of copper-I chloride and 0.5 part of copper powder, are condensed for 22 hours at 200-210C wi-th a mixture of 28.7 parts of 1-amino-4-hydroxyanthraquinone and 13.7 parts of l-amino-4-benzoylaminoanthraquinone, and the mix-ture is worked up in accordance with Example 1. This gi~es 52 parts of a dyestuff which dyes polyester by the melt spinning pro-cess in blue shades.

..

3L06~39() Example 13 A mix-ture of 3.4 parts of diphenyl ether and 21.2 parts of hydroquinonediphenyl e-ther in 150 parts of nitro-benzene is brominated, in accordance with -the ins-tructions of Example 1, using a solution of 19.2 parts of bromine in 50 parts of nitrobenzene, and is then condensed analogously with 29 par-ts of 1-amino-4-hydroxyanthraquinone. After further working up in accordance with Example 1, a dyestuff mixture is obtained, which dyes polyester by the melt spinning pro-cess in fast blue shades.
14 (Dyeing Example) Granules of undelustred polyethylene terephthalate, suitable for fibre manufacture, are shaken in a closable vessel on a shaking machine for 15 minutes with 1% of the dyestuff mixture obtained in accordance with Example 1.
The evenly dyed granule particles are spun, on a melt spinning apparatus (285C + 3C, residence time in the spinning machine approx. 5 minutes)j into filaments which are stretched on a stretch-and-twist installa-tion and wound on a spool. By virtue of the solubility of the dyestuffs in polyethylene terephthalate, vivid blue dyeings are obtained.
The dyed material can be treated and tested as follows:

=
A sample of the dyed ma-terial is -treated for 30 seconds at 210C in a precision ironing press and is additionally post-fixed for 30 minutes a-t 135Co 1~601~9~

b) ~
Dry, undyed co-tton or polyethylene terephthalate fabric is passed to and ~ro 10 times in a Crockmeter, using a pressure o~ 900 g for 10 seconds over a sample, 10 cm long, of the dyed and thermofixed material. The marking-off of the undyed material is assessed.

` A sample of the dyed material is treated in a precision ironing press for 30 seconds a-t 210C with an undyed comparison fabric (polyamide or polyester).
The dyestuff mixture obtained in accordance with Example 1 is superior to the dyestuff obtained in accordance with Example 147 of DOS 29343,127, in respect of fastness to rubbing after thermofixing.

--- 13 ~

Claims (9)

THE EMBODIMENTS OF THE INVENTION IN WHICH AN EXCLUSIVE
PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:

1, Process for the manufacture of anthraquinone dyestuff mixtures, where-in one mol of a diphenyl ether of the formula or of a mixture of such compounds, wherein R1 denotes a hydrogen atom or a phenyl or phenoxy group, is brominated with a quantity of bromine between 1 and 2 mols, if R1 denotes a hydrogen atom, or is brominated with a quantity of bromine between 0.9 and 2 mols, if R1 denotes a phenyl or phenoxy group, and the resulting bromination product is reacted with a molar quantity, corres-ponding to the degree of bromination of a monoaminoanthraquinone or a mixture of monoaminoanthraquinones of the formula wherein one X1 denotes a hydrogen atom or a hydroxyl, alkoxy, arylmercapto, arylamino, benzthiazolylmercapto or acylamino group, and the remaining X1 de-note hydrogen atoms, and one Z denotes a hydrogen or chlorine atom and the others denote hydrogen atoms.

2. Process according to claim 1 wherein a diphenyl ether in which R
denotes hydrogen is brominated using 1.4 to 1.9 mole of bromine.

3. Process according to claim 1, wherein a diphenyl ether in which R
denotes phenyl or phenoxy is brominated using 0.9 to 1.5 mols of bromine.

4. Process according to claim 1 wherein 1-amino-4-hydroxyanthraquinone is used as the aminoanthraquinone.

5. Process according to claim 1, wherein the reaction is carried out in nitrobenzene.

6. Mixtures obtained according to the process of claim 1 consisting to the extent of 10 - 90% of dyestuffs of the formula and/or and to the extent of 90 - 10% of dyestuffs of the formula wherein R1 has the meaning indicated in claim 1 and the A's represent identi-cal or different anthraquinone radicals of the formula wherein one X1 denotes a hydrogen atom or a hydroxyl, alkoxy, arylmercapto, arylamino, benzthiazolylmercapto or acylamino group, and the remaining X1 denote hydrogen atoms, and one Z denotes a hydrogen or chlorine atom, and the others denote hydrogen atoms.

7, Mixtures of anthraquinone dyestuffs according to claim 6, wherein A denotes a radical of the formula

8. Mixtures of anthraquinone dyestuffs according to claim 6 or 7, con-sisting to the extent of 10 - 90% of a dyestuff of the formula and to the extent of 90 - 10% of a dyestuff of the formula

9, Mixtures of anthraquinone dyestuffs according to claim 6, consisting to the extent of 70 - 90% of a dyestuff of the formula and to the extent of 30 - 10% of a dyestuff of the formula