CS206829B1 - Mixed green dyes containing iron complexes derived from nitrosonaphtolsulpho-acides or their salts and method of their manufacture - Google Patents

Description

(54) Mixed green dyes containing iron complexes derived from nitrosonaflolsulfoacids or their salts and process for their preparation

BACKGROUND OF THE INVENTION The present invention relates to mixed green starches containing iron nitrosonaphtholsulfo acid complexes or salts thereof, and to a process for their preparation.

Of the green nitrosonaphthol complexes of iron, the coloring of the dye has been limited until now »

Cl Pigment Green 8 (Pigment Grin B), which is a Pe-complex derived from 1-ritroso-2-naphthol,

Cl Acid Green 1 (Grine PLX, Naphthol Green B), a Pe-complex derived from 1-nitroso-2-naphthol-6-sulfoacid and GI Acid Green 4 (Naphthol Green G), a Pe-complex derived from 2 These dyes were used in the dyeing of animal textile fibers and synthetic materials of the polyamide type C1 Pigment Green 8 were used in the production of wallpaper.

Existing methods for preparing these green nitrosonaphthalic iron complexes are based on the reaction between naphthol or the corresponding naphtholsulfoacids and nitrites followed by the action of some of the ferrous salts. Therefore, the main problem of production was the economics of preparation of pure raw materials.

For example, 2-naphthol-6-sulfoacid, required for Cl Acid Green 1, is obtained by sulfonating 2-naphthol. subsequent reaction in an excess of acid sírové.Je known that low-temperature, long-term sulphonation by treatment with 2-naphthol * 95-97% ^of HgSO ^ ^ * ^SLC mixture of 2-naphthol-6- and -8-sulfoisomerů in a ratio of about 1 »first Sulfonation of 2-naphthol using 95-100% 83 * -4 at 95-100 ° C, besides 2-naphthol-6-sulfoacid as the main product, also contains a minor proportion of 2-naphthol-8-sulfoisomer in the reaction mixture and 10% 2-naphthol-3,6- and 1,3-, 6,8-disulfo acids. Separation of individual isomers or separation of accompanying disulfonic acids is tedious and laborious, the production equipment required is large, the production is burdened with a considerable amount of waste and the process thus becomes relatively expensive.

The present invention protects mixed green dyes containing iron complexes derived from nitrosonaphthol-sulfoacids or their salts of formula I

NO

wherein the substituents -NO and -OH are bonded to adjacent carbons of the core and Me denotes H, Na, K, ~ 2 'ΝΗ ⁺ and n 1 to 3, wherein for mixtures where the main component is a monosulfonated dye, the disulfonated dye content is 2 up to 45 mol% and trisulfonated dye 0 to 20 mol% and in mixtures with disulfonated dye as the main constituent, the content of trisulfonated dye is 5 to 30 mol% and the content of monosulfonated dye 0 to 40 mol% and the preparation thereof to a mixture of naphtholsulfonated acids or their salts of the general formula

wherein Me and n are as defined above with nitrosating agents and iron (II) salts.

The mixed dyes obtained consist of components which do not show any significant differences in spectral behavior and thus exhibit a single component. From the measured spectra of aqueous dye solutions derived, for example, from 1-nitroso-2-naphthol-6-sulfoacid with an acsorption maximum of 720 mm, 2- nitroso-1-naphthol-4-sulfoacids with an absorption maximum of 710 mm and 1-nitroso-2-naphthol-3,6-disulfoacids with an absorption maximum of 718 mm and absorption band ranges (for all three dyes from 550 mm to 950 nm), these constitutively different dyes can be considered to be identical in behavior, with the course of the absorption curves not changing over the entire pH range of 4.2 to 10.8. These manifestations predetermine mixed green dyes of nitrosonaphthol type for wide application in new non-traditional areas, for example when using solar energy for water heating, or they can serve as additives to organic polymers used in packaging, where their presence achieves destruction of discarded packages in daylight. dyes can also serve as components of heat and light filters in areas where sunlight can be exerted, such as to control algae growth in water reservoirs.

For the preparation of mixed green dyes, according to the present invention, crude naphtholsulfo acids or their salts containing isomers or di and trisulfoderivatives can be used as products of subsequent reactions, which makes it possible to produce green dyes in an incomparably more economical way than conventional one-component greens; This eliminates the need for intensive, demanding and costly cleaning and accompanying by-products, not only that they are not - in the new production process - defective, but that they are largely involved in the formation of active dye components and thus increase the yield.

According to the present invention, it is even possible to easily and advantageously process reaction mixtures from the production of naphtholsulfonic acids, for example from the sulfonation of 2-naphthol, where most sulfoproducts and residual sulfuric acid from sulfonation are used as the acid component in the subsequent nitrates with nitrites.

Waste from the production of naphtholsulfonic acids can also be treated by the described process, where often the low content of products and their relatively high solubility in waste leaches no longer lead to rational isolation or the mother liquors after separation of the main product contain isomers; in these cases, the new dyes do not have to be isolated, but are used directly as reaction mixtures (after adjustments such as pH adjustment and the like) if necessary, as effective components for solar water heating water tanks or as additive to fuel tanks. can be used, for example, in the manufacture of 2-naphthol-6-sulfoacids;

(Schaffer's acid), where a significant amount of 2-naphthol-3,6-disulfonic acid or salts (i.e., R-acids or R-salts) is present in the waste. However, mixtures can also be processed according to the invention wastes containing, for example, 1-naphthol- and 2-naphthol-sulfoacids.When the mineral acid is converted into ammonium, potassium, and magnesium salts in the treatment of mixtures of naphtholsulfonic acids with sulfuric acid, these may be used as fatty fertilizers when applying green dyes in breeding tanks.

Mixed green dyes of the general formula Γ can also be prepared according to U.S. Pat. No. 2,383,762 or U.S. Pat. No. 859,344 by mixing salts of naphtholsulfonic acids II - in an aqueous medium with a nitrosating agent and one of the ferrous salts, for example, iron vitriol.

Example 1

900 g of a paste containing 625 g of 2-naphthol-6-sulfonic acid sodium salt (i.e. 1.0 mol) and 73.7 g of 2-naphthol-3,6-disulfonic acid disodium salt (i.e. 0.30 mol) is stirred in 3 l of water, 8 g of caustic soda are added to the solution, 606 ml of an aqueous sodium nitrite solution containing 139.5 g of NaNOg is added and the solution is cooled to 0 to 2 ° C by adding 1,400 g of ice.

In addition, a cold dilute sulfuric acid solution is prepared by adding 160 g of 62% sulfuric acid to 0.5 l of water and 1 kg of ice, adjusting the volume to approximately 2 l with a defect or ice of about 0 ° C. This cooled, dilute sulfuric acid with a steady stream. shows to the bottom of a cold solution of the naphtholsulfo acid nitrite salt with slow stirring over 8 hours. The pH of the reaction mixture was then adjusted to pH 5-6 (about 4 ml consumption) by addition of formic acid and stirred for 10 hours.

Then a solution prepared from 198 g of green vitriol and 0.5 l of water is added over 10 minutes. The mixture is stirred for 5 hours and used as such for dyeing, for example, water in solar water heaters or breeding tanks and the like.

9 l of a solution are obtained in which dyes are present in a coloristic strength corresponding to 710 g of the naphthol green B type.

Example 2

From the mother liquor waste after isolation of the dipotassium salt of 2-naphthol-6,8-disulfonic acid (the so-called G-salt), the volume containing 2.1 moles of 2-naphthol-sulfo derivatives (predominantly 2-naphthol-3,6) is measured. -disulfoacid or its salt (so-called R-salts) is made up to a volume of 31 with water and nitration and metallocomprexation are also carried out by the addition of green vitriol as described in Example 1. A solution of about 9 liters of green dyes is obtained. colorist strength equivalent to 690 g of Naphthol Green B.

Example 3

A mixture of the sodium salt of 2-naphthol-6-sulfoacid with the disodium salt of 2-naphthol-3,6-disulfonic acid, the same composition as in Example 1, was treated in the same manner as in Example 1 except that 141.5 g of crystalline iron (II) chloride (PeClg. 4 HgO). Dye yield and shade are identical to Example 1.

Example 4

A dye was prepared from the waste liquors after isolation of the dipotassium salt of 2-naphthol-6,8-disulfonic acid as in Example 2 except that 175 g of crystalline ferric acetate (CH CHCOO) was used instead of green vitriol to form a color complex.

H ₂ O) with practically the same result as in Example 2.

Claims (4)

SUBJECT OF THE INVENTION 1. Mixed green pigments comprising iron complexes derived from nitrosonaphtholsulfoacids or their salts of the general formula I wherein the substituents -NO and -OH are bonded to adjacent carbons of the nucleus and Me denotes H, Na, K, gS, g® NH4 and n = 1 to 3, wherein for mixtures wherein the main component is a monosulfonated dye, the disulfonated dye content is 2 to 45 mol% and the trisulfonated dye is 0 to 20 mol% and in the mixtures with the disulfonated dye as the main component the trisulfonated dye content is 5 to 30 mol% and % monosulfonated dye 0 to 40 mol%; 2. A process for the preparation of the mixed green dyes as defined in item 1, characterized in that the mixture of naphtholsulfonated acids or their salts of the formula II wherein Me and n are as defined above is treated with nitrosating agents and iron (II) salts. 3. A process for the preparation of mixed green dyes as defined in claim 1, characterized in that the nitrosating agents and iron (II) salts are reacted. mixtures of the naphtholsulfonic acids of the formula II as obtained by sulfonating the naphthols. 4. A process for the preparation of mixed green dyes as defined in claim 1, characterized in that the nitrosating agents and iron (II) salts are treated with wastes in the production of naphtholsulfoderivatives such as 2-naphthol-6-sulfoacid and 2-naphthol-6,8-disulfoacid or its salts. .