KR0143777B1 - Compositions of Materials Based on Diketopyrrolopyrrole - Google Patents

Abstract

The present invention,

a) at least one diketopyrrolopyrrole of the general formula (I) and

b) a composition of matter containing 0.5 to 10% by weight (based on diketopyrrolopyrrole a) of a mixture of three or more different symmetrical and asymmetric diketopyrrolopyrroles of the general formula (I). :

Where

R₁, R₂, R₃ and R₄ are independently of each other H, Cl, Br, CH ₃ , OCH ₃ , C ₆ H ₅ or CN,

However the mixture b) at least one of the radicals R₁, R₂, R₃ or R₄ in the formula -SO ₃ X Contains groups of (X See paragraph 1 for this meaning).

Compositions of this type of material are particularly suitable for dyeing high molecular weight organic materials and are characterized by good flowability and high saturation of the dyeings dyed therewith.

Description

[Name of invention]

Compositions of Materials Based on Diketopyrrolopyrrole

Detailed description of the invention

The present invention relates to a novel composition of materials containing diketopyrrolopyrrole and small amounts of a mixture of at least three diketopyrrolopyrroles partially sulfonated.

Diketopyrrolopyrroles are known compounds which are described, for example, in US Pat. Nos. 4,415,685 and 4,585,878 as pigments for coloring organic polymers. It can be seen in US Pat. No. 4,791,204, for example, that pigment properties and fluidity can be improved by mixing small amounts of sulfonated, carboxylated, phosphonated or N-imidomethylated diketopyrrolopyrrole with diketopyrrolopyrrole. However, the properties of these mixtures are noteworthy but do not always meet the high technical demands of today. As well as their manufacture is difficult and therefore expensive in terms of energy.

Recently, when a small amount of a mixture of at least partially sulfonated three or more different symmetrical and asymmetrical diketopyrrolopyrroles is mixed with diketopyrrolopyrrole, the pigment properties of diketopyrrolopyrrole, in particular fluidity and specific color properties (e.g., It has been found that saturation can be improved to a considerable extent. Compared to the crude sulfonated diketopyrrolopyrroles described in US Pat. No. 4,791,204, which requires four steps to prepare, the sulfonated diketopyrrolopyrrole mixtures used in the present invention can be prepared in two stages and consequently Significant energy can be saved, thus less environmental damage.

Therefore, the present invention

a) at least one diketopyrrolopyrrole of the general formula (I) and

b) a composition of matter containing 0.5 to 10% by weight (based on diketopyrrolopyrrole a) of a mixture of three or more different symmetrical and asymmetric diketopyrrolopyrroles of the general formula (I). :

Where

in a)

R₁, R₂, R₃ and R₄ are independently of each other H, Cl, Br, CH ₃ , OCH ₃ , C ₆ H ₅ or CN,

in b),

R₁, R₂, R₃ and R₄ are independently of each other H, Cl, Br, CH ₃ , OCH ₃ , C ₆ H ₅ or general formula -SO ₃ X Is the flag of,

X H Or general formula Or N (R ₅ ) is a group of (R ₆ ) (R ₇ ) (R ₈ ),

Is an n-valent metal cation,

n is 1 to 3,

R ₅ , R ₆ , R ₇ and R ₈ are independently of each other hydrogen, C ₁ -C ₁₈ alkyl, C ₅ -C ₆ cycloalkyl or phenyl unsubstituted or substituted by C ₁ -C ₁₈ alkyl, or R ₇ and R ₈ together with the N atom form a pinolidine, imidazolidine, piperidine, piperazine or morpholine radical, or R ₆ , R ₇ and R ₈ together with the N atom are pyrrole, pyridine, picoline , Pyrazine, quinoline or isoquinoline radicals,

However, in the mixture a radical R₁, R₂, R₃, R₄ or at least one of the general formula -SO ₃ X It is the flag of.

In the composition of matter according to the invention, the diketopyrrolopyrroles of general formula (I) are preferably to both component a) and component b), wherein R ₂ and R 'are hydrogen and R' and R₃ are independently of each other 4-Cl, Diketopyrrolopyrrole which is 4-Br, 4-CH ₃ , 4-OCH ₃ , 4-C ₆ H ₅ , 3-CN or in particular hydrogen and 4-Cl.

Diketopyrrolopy is mixed with sulfonated diketopyrrolopy mixture b) in diketopyrrolopy a) in an amount of 1.5 to 7% by weight relative to a).

X Is preferably H , Or especially general formula It is the flag of.

X General formula If attributable to Examples of alkali metal, alkaline earth metal, aluminum or transition metal cations such as Na , K , Mg ² , Ca ² , Sr , Ba ² , Mn ² , Cu ² , Ni ² , Cd ² , Co ³ , Al ³ And Cr ³ But preferably an alkali or alkaline earth metal cation (n is 1 or 2), in particular Ca ² to be.

If the possible substituents are C ₁ -C ₁₈ alkyl, examples of these are methyl, ethyl, n-propyl, isopropyl, n-bufil, secondary-butyl, tert-butyl, n-pentyl, tert-pentyl, Hexyl, heptyl, octyl, decyl, dodecyl, tetradecyl, hexadecyl, heptadecyl or octadecyl.

When R ₅ , R ₆ , R ₇ and R ₈ are C ₅ -C ₆ cycloalkyl, examples are cyclopentyl, or in particular cyclohexyl.

As panyl substituted by C ₁ -C ₁₈ alkyl, R ₅ , R ₆ , R ₇ and R ₈ are preferably phenyl substituted by C ₁₂ -C ₁₈ alkyl.

N As examples of (R ₅ ) (R ₆ ) (R ₇ ) (R ₈ ), the following may be mentioned. : N H ₄ , N H ₃ CH ₃ , N H ₂ (CH ₃ ) ₂ , N H ₃ C ₂ H ₅ , N H ₂ (C ₂ H ₅ ) ₂ , N H ₃ C ₃ H ₇ -iso, N H ₃ -n-octadecyl, N H ₃ -cyclohexyl, N H _2- (cyclohexyl), N H ₂ (CH ₃ ) (C ₆ H ₅ ), N H ₃ C ₆ H ₅ , N H ₃ -p-octadecylphenyl, N (CH ₃ ) ₄ and N (CH ₃ ) ₃ -n-hexadecyl.

As mentioned above, diketopyrrolopyrrole of the general formula (I) is a known compound.

The sulfonated diketopyrrolopyrrole mixtures b) are novel and have R₁, R₂, R₃, R₄ and X It is another subject of the present invention for purposes of definition and purposes.

A mixture of two different nitriles of the following general formulas (III) and (IV) in the presence of a strong base; [(III): The molar ratio of (IV) is from 9: 1, to 1: 9, preferably from 3: 1 to 1 : 3, especially 1: 1] After reacting 2 moles with 1 mole of succinic acid diesters of the following general formula (II), the resulting mixture is reacted by known methods by fuming sulfuric acid, concentrated sulfuric acid, liquid sulfur trioxide, or chlorosulfonation. These are prepared by phonation (this is the subject of the present invention):

In which R is lower alkyl,

R₁, R₂, R₃ and R₄ are independently of each other H, Cl, Br, CH ₃ , OCH ₃ , or C ₆ H ₅ , and at least one of the radicals R₁, R₂, R₃ and R₄ must be hydrogen.

Corresponding metal or amine salt derivatives by reacting the product thus obtained in two steps with a metal salt (e.g. acetate, carbonane, chloride, nitrate or sulphate) suitable for the present invention, or amine or amine salt, if necessary Switch to

Examples of R as lower alkyl are methyl, ethyl and especially isopropyl, tert-butyl and tert-amyl.

Succinic acid esters of formula (II) and nitriles of formulas (III) and (IV) are compounds which must be known and can be prepared by known methods.

It is appropriate to react the nitrile with succinic acid diesters in an organic solvent. Examples of suitable solvents are primary, secondary or tertiary C ₁ -C ₁₀ alcohols such as methylol, ethylol, n-propanol, isopropanol, n-butanol, secondary-butanol, tert-butanol, n- Pentanol, 2-methyl-2-butanol, 2-methyl-2-pentanol, 3-methyl-3-pentanol, 2-methyl-2-hexanol, 3-ethyl-3-pentanol or 2,4 , 4-trimethyl-2-pentanol), glycols such as ethylene glycol or diethylene glycol, and ethers such as tetrahydroburan or dioxane, or glycol ethers such as ethylene glycol methyl ether, ethylene glycol ethyl Ethers, diethylene glycol monomethyl ether or diethylene glycol monoethyl ether), and bipolar aprotic solvents such as acetonitrile, benzonitrile, dimethylformamide, N, N-dimethylacetamide, nitrobenzene or N- Methylpyrrolidone), aliphatic or aromatic hydrocarbons [e.g. benzene or benzene substituted by alkyl, alkoxy or halogen (e.g. There are pyridine, picoline, quinoline) ene, xylene, anisole or chlorobenzene), or an aromatic N- heterocyclic compound (eg. In addition, a mixture of nitriles to be reacted can be used as a solvent when the liquid is at a temperature at which the reaction proceeds. The solvents mentioned can also be used as mixtures. It is appropriate to use 5 to 20 parts by weight of solvent per 1 part by weight of reactant. Alcohols, in particular secondary or tertiary alcohols, are preferably used as the solvent. Preferred tert-alcohols are tert-butanol and tert-amyl alcohol.

The reaction is carried out in the presence of a strong base. Examples of suitable strong bases include alkali metal hydroxides such as sodium hydroxide, potassium hydroxide or lithium hydroxide; Or alkali metal hydroxides such as calcium hydroxide or magnesium hydroxide; Or alkali metal amides such as lithium amide or sodium amide; Or alkali metal hydrides such as lithium hydride or sodium hydride; Or sodium methylate, sodium ethylate, sodium n-propylate, sodium isopropylate, sodium n-butylate, sodium secondary-butylate, sodium tert-butylate, sodium 2-methyl-2-butylate, Sodium 2-methyl-2-pentylate, sodium 3-methyl-3-pentylate or sodium, 3-methyl-3-pentylate, potassium methylate, potassium ethylate, potassium n-propylate, potassium isopropylate , Potassium n-butylate, potassium secondary-butylate, potassium tert-butylate, potassium 2-methyl-2-butylate, potassium 2-methyl-2-pentylate, potassium 3-methyl-3-pentylate Or potassium 3-ethyl-3-pentylate, or lithium methylate, lithium ethylate, lithium n-propylate, lithium isopropylate, lithium n-butylate, lithium secondary-butylate, lithium tert-butylate , Lithium 2-methyl-2-butylate, lithium 2-methyl-2-pentylate, lithium Alkaline earth metal or alkali metal alcoholates derived from primary, secondary, or tertiary aliphatic C ₁ -C ₁₀ alcohols, such as 3-methyl-3-pentylate or lithium 3-ethyl-3-pentylate; Or alkaline earth metals or alkali metal or alkali metal phenates or o-alkyl-substituted phenates such as sodium-o-cresolate or potassium o-cresolate. However, it is also possible to use mixtures of the bases mentioned.

The strong base used is preferably an alkali metal alcoholate wherein the alkali metal is sodium or potassium and the alcoholate is derived from secondary or tertiary alcohols. Examples of particularly preferred strong bases are sodium isopropylate sodium secondary-butylate, sodium tert-butylane and sodium tert-amylate or potassium isopropylate, potassium secondary-butylate, potassium tert-butylate And potassium tert-amylate.

The strong base can be used in particular in an amount of 0.1 to 4 moles, preferably 1.9 to 2.2 moles, relative to the reacting succinic acid diester. Depending on the reactants and processes, the use of even smaller amounts of base, for example when recycling, has an advantageous effect on yield. On the other hand, using an excess of base has a desirable effect on yield. Typically, however, a stoichiometric amount of base is sufficient.

A phase transfer catalyst can be used with the strong base mentioned. This is particularly advantageous when the solubility of the water base in the special solvent is low. A phase transfer catalyst may be used in an amount of 0.001 to 50 mol%, preferably 0.01 to 0.3 mol%, relative to the reacting succinic acid diester. Suitable phase transfer catalysts for this purpose are the conventional phase transfer catalysts described in the literature, such as, for example, CHEMTECH, February 1980, page 111, Table 1, ie quaternary salts, cyclic polyethers, ring-opening chains. Oxides of phosphorus or sulfur with polyethers, N-alkylphosphoramides or methylene bridges.

It is suitable to react at 60-140 degreeC, Preferably it is 80-120 degreeC.

In order to react the nitrile and the succinic acid diester, in principle, all the components are brought to a low temperature, and the mixture is heated to the reaction temperature, or the individual components may be added to the other components in any order within the range of the reaction temperature.

In a preferred embodiment having a particularly preferred effect on yield, the nitrile mixture is first taken with the base and then the succinic acid diester is added within the reaction temperature.

In the case of alcoholates derived from lower alcohols such as methylol, ethylol, n-propanol, isopropanol or tert-butanol, the lower alcohol produced during the reaction must be continuously removed from the reaction medium in order to obtain high yields.

When using alcohol as a solvent and alcohol lane as a base, it may be advantageous to select alcohols and alcoholates having the same alkyl moiety. Likewise, succinic acid diesters may be advantageous if they contain such alkyl groups.

Acids, C ₁ -C ₄ alcohols such as methylol or ethylol can be used to hydrolyze the condensation product, but preferably water can be used. Examples of suitable acids are aliphatic or aromatic carboxylic acids or sulfonic acids, for example formic acid, acetic acid, propionic acid, oxalic acid, benzoic acid or benzenesulfonic acid. Suitable acids are also mineral acids such as hydrogen chloride, aqueous solutions thereof, carbonic acid or dilute sulfuric acid and phosphoric acid.

The diketopyrrolopyrrole mixture precipitates upon hydrolysis and can be isolated by filtration.

In sulfonation, the concentration of the sulfonating agent used and the selected reaction conditions are closely related to the number of sulfonic acid groups introduced into the diketopyrrolopyrrole mixture.

The composition of the material according to the invention is obtained by mixing directly in the desired proportions the individual components a) and b) in the pasting medium or in an additional mixing process in water or sulfuric acid. Subsequent treatment of the composition of the material according to the invention (such as containing sodium salts) with an appropriate metal salt, such as Ca (SO ₄ ), can be metathesized, if necessary, to produce the desired metal salt.

The composition of matter according to the invention can be used as a pigment for coloring high molecular weight organic materials.

Examples of high molecular weight organic materials which can be colored or dyed individually or as a mixture by the composition of the material according to the invention include cellulose ethers and esters such as ethylcellulose, nitrocellulose cellulose acetate or cellulose butyrate; Aminoplasts, especially arearea / formaldehyde and melamine / formaldehyde resins, alkyd resins, phenoplasts, polycarbonates, polyolepins, polystyrenes, polyvinyl chlorides, polyamides, polyurethanes, polyesters, fluorine Polymers such as polyfluoroethylene, polytrifluorochloroethylene or tetrafluoroethylene / hexafluoroflopropylene copolymers, and natural or synthetic resins such as rubber, casein, silicone and silicone resins (such as polymeric resins or Condensation resin).

The high molecular weight organic compounds mentioned may be present as homogeneous mixtures in the form of plastic compositions or melts or in the form of spinning solutions, lacquers, paints or printing inks. Depending on the end use, it is advantageous to use the composition of the material according to the invention as a toner or in the form of a formulation. The compositions of matter according to the invention can be used in amounts of 0.01 to 30% by weight, preferably 0.1 to 10% by weight, relative to the high molecular weight organic material to be dyed.

These substrates can be dyed with compositions of this type of material by mixing the composition of materials according to the invention into a high molecular weight organic material, if appropriate, in the form of a masterbatch using a roll mill, mixing device or grinding device. By known methods such as calendering, compression-molding, extrusion, stretch-coating, casting or injection molding, the dyed material is brought into the desired final form. It is desirable to incorporate a plasticizer into the high molecular weight compound prior to molding to produce a soft molded product or to reduce its brittleness. Phosphoric acid, phthalic acid or sebacdan can be used as the plasticizer. The plasticizer can be incorporated into the polymer before or after incorporation of the composition of matter according to the invention. Fillers or coloring components (such as white natural or black pigments) as well as compositions of the material according to the invention can be added to the high molecular weight organic material in order to produce different shades.

In dye paints and printing inks, the composition of the high molecular weight organic material and the material according to the invention together with additives such as fillers, other pigments, desiccants or plasticizers, if necessary, are made into fine dispersions or solutions in organic solvents or solvent mixtures. The process that follows may be to disperse or dissolve the individual components alone or together with several and then combine the components together.

Dyed articles obtained by the compositions of matter according to the invention characterized by good flowability, such as plastics, fibers, paints or prints, have good dispersibility; High color intensity; It is distinguished by its overall good properties such as good color fastness and good gloss to excess dyeing, migration, heat, light and weathering.

However, the sulfonated diketopyrrolopyrrole mixtures used as component b) in the compositions of matter according to the invention can be used as pigments in the dyeing of the above-mentioned discerning organic materials. It may be used for this purpose as a crude product or after appropriate conditioning / post-treatment, for example as already described in the compositions of matter according to the invention. The present invention is explained in detail by the following examples.

Example 1

a) 120 ml of tert-amyl alcohol (anhydrous) are first introduced into a sulfonated flask under nitrogen. With gentle stirring, 6.9 g sodium and 0.1 g sodium salt of bis-2-ethylhexylsulfosuccinate are added and the mixture is heated to 95-102 ° C. Hold overnight at 95 ° C. under vigorous stirring under molten sodium nitrogen. The resulting solution is cooled to 85 ° C. and a mixture of 14.04 g of 4-chlorobenzonitrile and 10.3 g of benzonitrile is added. 20.3 g of diisopropyl succinate are added over 2 hours at 95 ° C. The reaction mixture was oiled at 95 ° C. for 5 hours to terminate the reaction and then cooled to room temperature. The resulting mixture is poured into 300 ml of cold water and the mixture is heated at reflux for 1 h and then steam distilled. The resulting mixture is filtered at 60 ° C. and the product is washed with 1000 ml of water and dried in a vacuum oven at 80 ° C. Yield: 23.6 g of red powder containing a compound of the following general formula:

Analysis (%): found: C = 64.93; H = 3.45; N = 8.38; Cl = 13.72.

b) 160 g of 25% fuming sulfuric acid and 160 g of sulfuric acid monohydrate are first put into a sulfonated flask. 20 g of the mixture obtained in Example 1a) are introduced at 2-5 ° C. over 30 minutes. The mixture is stirred at room temperature for 20 hours and the resulting solution is poured into 1000 g of ice and 280 ml of water. The resulting suspension is stirred for 15 minutes, heated to 75 ° C. and then 120 g of NaCl is added. The mixture is stirred at 75 ° C. for 1 hour to terminate the reaction. The suspension is filtered at room temperature and the material on the filter paper is washed with 5% NaCl solution until the filtrate can be colorless and the material on filtration is dried in a vacuum drying chamber. 29.0 g of reddish purple powder are obtained.

c) 964 g of wet 1,4-diketo-3,6-di- (4-chlorophenyl) -pyrrolo- [3,4-c] -pyrrole (solid content 36.3%) are placed in a sulfonated flask. The volume is made up to 8 liters with deionized water. After stirring for 1 hour at room temperature, a solution of 8.1 g of the product prepared in Example 1b) in 900 ml of water (60 ° C.) is added and the mixture is stirred at room temperature for 2 hours. 100 g of CaCl ₂ dissolved in about 500 ml of water is added and the mixture is heated to 75 ° C., stirred at 75 ° C. for 1 hour, and filtered at room temperature. The material on the filter paper is washed thoroughly with water and dried in a vacuum drying chamber at 80 ° C. This gives 352 g of a red powder having turbid color and flow characteristics.

[Examples 2 to 6]

Except for using 1,4-diketo-3,6-di- (4-chlorophenyl) -pyrrolo- [3,4-c] -pyrrole as the wet filter cake with the pigments listed in the table below. The same process as in Example 1c) is performed. Obtained pigment powders with excellent flow and color properties.

(Example Number)

Example 7

The process is as described in Example 1c) except that trimethylhexateylammonium bromide is used instead of CaCl ₂ . A red pigment is obtained having excellent flow and color properties.

Example 8

The process is as described in Example 5 except that trimethylhexateylammonium bromide was used instead of CaCl ₂ . A red pigment is obtained which has excellent flow and color properties.

Example 9

The process is as described in Example 6 except that trimethylhexateylammonium bromide was used instead of CaCl ₂ . Orange pigments are obtained which have excellent flow and color properties.

Example 10

The process is as described in Example 1a) except that a corresponding amount of 4-phenylbenzonitrile is used instead of 4-chlorobenzonitrile. The resulting red pigment powder is further processed in a similar manner as in Examples 1b) and 1c). A red pigment is obtained having excellent flow and color properties.

Example 11

The process is as described in Example 1a) except that a corresponding amount of 4-methylbenzonitrile is used instead of 4-chlorobenzonitrile. The resulting red pigment powder is further processed in a similar manner as in Examples 1b) and 1c). A red pigment is obtained having excellent flow and color properties.

Example 12

Use in alkyd / melamine stove paints

460 g of steatite sphere of 8mm diameter, in xylene Alkyd resin 58.7 g in 60% solution of Alkydal F 310 (BAYER AG) in xylene 58.7 g Alkyd Resin in 60% solution of Alkydal F 32 (BAYER AG), in 1% solution in xylene Silikonol A 2.0g (BAYER AG), n-butanol 4.0g, Dowanol 4.0g, xylene 15g, dispersant A mixture of an alkyd lacquer consisting of 5.6 g of Disperbyk D-160 (BYK-Chemie) and 28.0 g of the pigment mixture prepared according to Example 1 is dispersed for 72 hours in a glass bottle on a roller stand (with a turning lid). Xylene After addition of 24.0 g of melamine component in the form of a 90% solution of Cymel 327 (Cyanamid), the mixture is further dispersed on the roller stand for 1 hour. The steatite sphere is then removed. The dyed lacquer paste thus obtained was It is applied to a Milar transparent film and then baked at 130 ° C. for 30 minutes (50 μm of paint film thickness) to obtain a red dye having excellent color and flow characteristics.

Claims (11)

a) a mixture of at least three diketopyrrolopyrroles of the general formula (I) and b) at least three different symmetrical and asymmetric diketopyrrolopyrroles of the general formula (I) based on a) diketopyrrolopyrrole 0.5 Compositions of matter containing from 10% by weight; In the above formula, In a), R₁, R₂, R₃ and R₄ are independently of each other H, Cl, Br, CH ₃ , OCH ₃ , C ₆ H ₅ or CN, and in b), R₁, R₂, R₃ and R₄ are independent of each other H, Cl, Br, CH ₃ , OCH ₃ , C ₆ H ₅ or general formula -SO ₃ X Is the flag of X H Or general formula Or N (R ₅ ) is a group of (R ₆ ) (R ₇ ) (R ₈ ), Is an n-valent metal cation, n is 1 to 3, and R ₅ , R ₆ , R ₇ and R ₈ are independently of each other hydrogen, C ₁ -C ₁₈ alkyl, C ₅ -C ₆ cycloalkyl or unsubstituted or C Phenyl substituted by _1- C ₁₈ alkyl, or R ₇ and R ₈ together with the N atom form a pinolidine, imidazolidine, piperidine, piperazine or morpholine radical or R ₆ , R ₇ And R ₈ together with the N atom form a pyrrole, pyridine, picoline, quinoline or isoquinoline radical, provided that at least one of the radicals R₁, R₂, R₃, or R₄ in this mixture is of the formula -SO ₃ X It is the flag of. The diketopyrrolopyrroles of the general formula (I) according to claim 1, wherein in both a) and b) R ₂ and R₄ are hydrogen and R₁ and R₃ are independently of each other hydrogen, 4-Cl, 4-Br, 4- A composition of matter which is diketopyrrolopyrrole which is CH ₃ , 4-OCH ₃ , 4-C ₆ H ₅ or 3-CN. The diketopyrrolopyrrole of claim 1, wherein the diketopyrrolopyrrole of formula (I) is diketopyrrolopyrrole in which both R2 and R₄ are hydrogen and R₁ and R3 are independently hydrogen, 4-Cl in both a) and b). Composition. The composition of matter according to claim 1, wherein the sulfonated diketopyrrolopyrrole mixture b) is mixed with diketopyrrolopyrrole a) in an amount of 1.5 to 7% by weight relative to diketopyrrolopyrrole a). The compound of claim 1 wherein X H Or general formula Is the flag of, A composition of matter wherein the alkali metal, alkaline earth metal, aluminum or transition metal cation. The compound of claim 1 wherein X General formula Is the flag of, Is an alkali metal or alkaline earth metal, a cation and n is 1 or 2. The compound of claim 1 wherein X A composition of matter wherein the calcium cation is. Mixtures of three or more different symmetric and asymmetric diketopyrrolopyrroles of the general formula (I) Wherein R₁, R₂, R₃ and R₄ are independently of each other H, Cl, Br, CH ₃ , OCH ₃ , C ₆ H ₅ or general formula -SO ₃ X Is the flag of X H Or general formula Or N (R ₅ ) is a group of (R ₆ ) (R ₇ ) (R ₈ ), Is an n-valent metal cation, n is 1 to 3, and R ₅ , R ₆ , R ₇ and R ₈ are independently of each other hydrogen, C ₁ -C ₁₈ alkyl, C ₅ -C ₆ cycloalkyl or unsubstituted or C Phenyl substituted by _1- C ₁₈ alkyl, or R ₇ and R ₈ together with the N atom form a pinolidine, imidazolidine, piperidine, piperazine or morpholine radical or R ₆ , R ₇ And R ₈ together with the N atom form a pyrrole, pyridine, picoline, quinoline or isoquinoline radical, provided that at least one of the radicals R₁, R₂, R₃, or R₄ in this mixture is of the formula -SO ₃ X It is the flag of. A mixture of two different nitriles of the general formulas (III) and (IV) in the presence of a strong base; [mole ratio of (III): (IV) is from 9: 1 to 1: 9] The reaction mixture was reacted with 1 mole of succinic acid diester, and the resulting mixture was sulfonated in a known manner by fuming sulfuric acid, concentrated sulfuric acid, liquid sulfur trioxide, or chlorosulfonation to give different symmetrical and asymmetrical dekets of the general formula (I) Method for preparing a mixture of three or more topyrrolopyrroles: Wherein R₁, R₂, R₃ and R₄ are independently of each other H, Cl, Br, CH ₃ , OCH ₃ , C ₆ H ₅ or general formula -SO ₃ X Is the flag of, X H Or general formula Or N (R ₅ ) is a group of (R ₆ ) (R ₇ ) (R ₈ ), Is an n-valent metal cation, n is 1 to 3, and R ₅ , R ₆ , R ₇ and R ₈ are independently of each other hydrogen, C ₁ -C ₁₈ alkyl, C ₅ -C ₆ cycloalkyl or unsubstituted or C Phenyl substituted by _1- C ₁₈ alkyl, or R ₇ and R ₈ together with the N atom form a pinolidine, imidazolidine, piperidine, piperazine or morpholine radical or R ₆ , R ₇ And R ₈ together with the N atom form a pyrrole, pyridine, picoline, pyrazine, quinoline or isoquinoline radical, provided that at least one of the radicals R₁, R ₂ , R₃, or R₄ in this mixture is of the formula -SO ₃ X In formulas (II), (III) and (IV), R is lower alkyl and R ', R2, R₃ and R' are independently of each other H, Cl, Br, CH ₃ , OCH ₃ , or C ₆ H ₅ and at least one of the radicals R₁, R₂, R₃ and R₄ must be hydrogen. A high molecular weight organic material containing the composition of matter according to claim 1. A high molecular weight organic material containing the mixture according to claim 8.