JP2931087B2 - Novel composition based on diketopyrrolopyrrole - Google Patents

Description

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

Diketopyrrolopyrrole is a known compound and is described, for example, in US Pat. Nos. 4,415,685 and 4,858,578 as pigments for coloring organic polymers.
From U.S. Pat. No. 4,791,204, it is also possible to improve pigment properties by incorporating a small amount of diketopyrrolopyrrole, for example, sulfonated, carboxylated, sulfonated or N-imidomethylated diketopyrrolopyrrole. It is also known that flow (rheological) properties can be improved. The properties of such mixtures are certainly noteworthy, but do not always meet the demands of the state of the art. In addition, the production of such mixtures is cumbersome and has high energy costs.

Thus, here, according to the invention, the pigmentary properties of the diketopyrrolopyrrole, in particular its rheological properties as well as certain chromatic properties, such as, in particular, the chroma, are at least partially sulfonated at least partially. It has been found that the incorporation of three different symmetric and asymmetric diketopyrrolopyrroles into the diketopyrrolopyrrole can be greatly improved. The most similar sulfonated diketopyrrolopyrrole known from U.S. Pat.No. 4,791,204 requires four steps in its preparation, by comparison, the sulfonated diketopyrrolopyrrole mixture used in the present invention is It can be manufactured in only two steps. Thus, considerable energy savings are possible, and thus the impact on the environment is reduced.

That is, the present invention provides a composition containing the following components.

(A) at least one diketopyrrolopyro of the following formula:
Rule(Where R₁, R_Two, R_Three, R_FourAre independently of each other H, Cl, Br, CH_Three, O
CH_Three, C₆H_FiveOr CN) and (b) 0.2 with respect to the diketopyrrolopyrrole (a).
5 to 10% by weight of at least three different symmetries
Of diketopyrrolopyrroles of the formula I in the form and in the asymmetric form
[Where R in formula I is₁, R_Two, R_Three, R_FourAre independent of each other
H, Cl, Br, CH_Three, OCH_Three, C₆H_FiveOr the formula -SO_Three X of
A group of the formula: Is H Or formula Mⁿ/ n
Group, or formula N (R_Five) (R₆) (R₇) (R₈) Means
Yes, where MⁿIs an n-valent metal cation, n is a number of 1, 2 or 3, R_Five, R₆, R₇, R₈Are each independently hydrogen, C₁−
C_18-Alkyl, C_Five−C_6-Cycloalkyl, substituted
Not or C₁−C_18-Fe substituted by alkyl
Stands for nil or R₇And R₈And they are combined
A pyrrolidine group, an imidazolidine group,
Forms piperidine, piperazine or morpholine
Do or R₆, R₇, R₈Is the N source to which they are attached
Prol, pyridine, picoline, pyra
Gin, quinoline or isoquinoline
But the radical R in the mixture₁, R_Two, R_Three, R_FourAt least
One is the formula -SO_Three X Is).

In the composition according to the invention, the diketopyrrolopyrrole of the formula I, both component (a) and component (b), is preferably such that R ₂ and R ₄ are hydrogen and R ₁ and R ₃ are independent of each other. a hydrogen, 4-Cl, 4-Br , 4-CH 3, 4-OCH 3, 4-C
₆ H _5, 3-CN, in particular diketopyrrolopyrrole to mean hydrogen and 4-Cl.

Also, a sulfonated diketopyrrolopyrrole mixture (b)
Is preferably 1. to diketopyrrolopyrrole (a).
It is incorporated into diketopyrrolopyrrole (a) in an amount of 5 to 7% by weight.

 X Is preferably H Or particularly preferably of the formula M
ⁿ/ n group.

 X Is the formula Mⁿ/ nⁿAs an example
Are alkali metal ions, alkaline earth metal ions,
Minium ions or transition metal cations are considered.
For example, Na , K , Mg², Ca², Sr², B
a², Mn², Cu², Ni², Cd², Co³, Al
³And Cr³It is. Particularly preferred are alkalis
Metal ion or alkaline earth metal ion (n = 1 or
Is 2) and Ca²Is most preferred.

Examples of the substituents C ₁ -C _18-alkyl present is optionally methyl, ethyl, n-propyl, isopropyl, n-
Butyl, sec-butyl, tert-butyl, n-pentyl, t
ert-pentyl, hexyl, heptyl, octyl, decyl, dodecyl, tetradecyl, hexadecyl, heptadecyl or octadecyl.

Examples of _{R 5, R 6, R 7} , meaning of R ₈ to C ₅ -C _6- cycloalkyl is cyclopentyl or preferably cyclohexyl.

R ₅ as phenyl substituted with C ₁ -C ₁₈ -alkyl,
R ₆ , R ₇ , R ₈ are preferably phenyl substituted by C ₁₂ -C ₁₈ -alkyl.

 N (R_Five) (R₆) (R₇) (R₈An example of) is
: N H_Four, N H_ThreeCH_Three, N H_Two(CH_Three)₂, N H_ThreeC_TwoH_Five,
N H_Two(C_TwoH_Five)₂, N H_ThreeC_ThreeH₇-Iso, N H_Three-N-o
Kutadecyl, N H_Three-Cyclohexyl, N H_Two-(Shiku
Rohexyl)₂, N H_Two(CH_Three) (C₆H_Five), N H_ThreeC
₆H_Five, N H_Three-P-octadecylphenyl, N (CH_Three)
₄, And N (CH_Three)₃-N-hexadecyl.

As already mentioned above, the diketopyrrolopyrroles of the formula I are known compounds.

 Mixture (b) of sulfonated diketopyrrolopyrrole is new
And R₁, R_Two, R_Three, R_FourAnd X About
Another object of the present invention, together with its preferred examples,
is there.

The process for producing this novel mixture (b) is also included in the subject of the present invention, and its production is carried out, for example, as follows. That is, in the presence of a strong base, (wherein, R represents a lower alkyl) wherein _{ROOC-CH 2 -CH 2 -COOR (} II) with 1 mole of succinic acid diester of the formula (Wherein R ₁ , R ₂ , R ₃ , and R ₄ are each independently H, Cl, Br,
CH ₃ , OCH ₃ or C ₆ H ₅ , but at least one of R ₁ , R ₂ , R ₃ , R ₄ must be hydrogen)
Reacting two different nitriles with 2 mol of a mixture, the molar ratio of III: IV being 9: 1 to 1: 9, preferably 3: 1 to 1: 3, particularly preferably 1: 1 and The mixture obtained is then sulfonated in a manner known per se using fuming sulfuric acid, sulfuric acid, liquid sulfur trioxide or chlorosulfonic acid. The product obtained in these two steps can, if desired, be reacted with a suitable metal salt according to the invention, such as an acetate, carbonate, chloride, nitrate or sulfate, to give the corresponding metal salt derivative, or an amine or an amine. It can be converted to an amine salt derivative by reacting with a salt.

Examples of lower alkyl represented by R are methyl, ethyl, especially isopropyl, tert-butyl, tert-amyl and the like.

The succinic diesters of formula II, and the nitriles of formulas III and IV are known compounds and can be prepared by known methods.

The reaction between the succinic diester and the nitrile is suitably carried out in an organic solvent. Examples of suitable solvents are given below.

Primary, secondary or tertiary alcohols having 1 to 10 carbon atoms, such as methanol, ethanol, n-propanol, isopropanol, n-butanol, sec-
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, 2,4,
Glycols such as ethylene glycol or diethylene glycol; ethers such as tetrahydrofuran or dioxane; glycol ethers such as ethylene glycol methyl ether, ethylene glycol ethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, etc. Dipolar aprotic solvents such as acetonitrile, benzonitrile, dimethylformamide, N, N-dimethylacetamide, nitrobenzene, N-methylpyrrolidone and the like; aliphatic or aromatic hydrocarbons such as benzene, or substituted by alkyl, alkoxy or halogen Benzene, such as toluene, xylene, anisole or chlorobenzene; Aromatic N-heterocyclic compounds such as pyridine, picoline, quinoline and the like.

Furthermore, the nitrile mixture to be reacted can also be used simultaneously as a solvent, provided that it is liquid within the temperature range in which the reaction takes place. The solvents exemplified above can be used as a mixture. Suitably 5 to 20 parts by weight of solvent are used per part by weight of reactants. Alcohols, especially secondary or tertiary alcohols, are preferably used as solvents. Particularly preferred tertiary alcohols are tert-butanol and tert-amyl alcohol.

The reaction is performed in the presence of a strong base. Examples of suitable strong bases are alkali metal hydroxides such as sodium hydroxide, potassium hydroxide and lithium hydroxide, alkaline earth metal hydroxides such as calcium hydroxide and magnesium hydroxide, or lithium amide and sodium amide. Such as alkali metal amide or lithium hydride,
Alkali metal hydrides such as sodium hydride, and also alkali metal or alkaline earth metal alcoholates, especially derived from primary, secondary or tertiary aliphatic alcohols having 1 to 10 carbon atoms, for example,
These are the alcoholates exemplified below. Sodium methylate, ethylate, n-propylate, isopropylate, n-butyrate, sec-butyrate, tert-butyrate, 2-methyl-2-butyrate, 2-methyl-2
-Pentylate, 3-methyl-3-pentylate, 3-
Ethyl-3-pentylate; potassium methylate, ethylate, n-propylate, isopropylate, n-butyrate, sec-butyrate, tert-butyrate, 2-methyl-2-butyrate, 2-methyl-2-pentylate, 3-methyl -3-
Pentylate, 3-ethyl-3-pentylate; lithium methylate, ethylate, n-propylate, isopropylate, n-butyrate, sec-butyrate, tert-butylate, 2-methyl-2-butyrate, 2-methyl-2-pentylate , 3-methyl-3-
Pentylates, 3-ethyl-3-pentylates; also alkaline earth metal or alkaline earth metal phenates or o-alkyl-substituted phenates, such as sodium o-cresolate or potassium o-cresolate.

 Mixtures of the aforementioned bases can also be used.

The strong base preferably used is an alkali metal alcoholate, wherein the alkali metal is especially sodium or potassium, and the alcohol is particularly preferably a secondary or tertiary alcohol. Thus, particularly preferred examples of strong bases are sodium isopropylate, sodium sec-butylate, sodium tert-butylate,
Sodium tert-amylate or potassium isopropylate, potassium sec-butylate, potassium tert-
Butyrate, potassium tert-amylate and the like.

The strong base can be used in an amount of 0.1 to 4 moles, preferably 1.9 to 2.2 moles, based on the reactant succinic diester. Depending on the nature of the reactants and the manner in which the reaction is carried out, for example in the case of recycle, a lower amount of base has a distinctly advantageous effect on the yield. On the other hand, in some cases, the use of excess base has a favorable effect on yield. However, in principle, stoichiometric amounts are sufficient.

The strong bases described above can be used together with a phase transfer catalyst. This is particularly advantageous when the solubility of certain bases in certain solvents is low. The phase transfer catalyst is
It can be used in an amount of 0.001 to 50 mol%, preferably 0.01 to 0.3 mol%, based on the reactant succinic diester. Suitable phase transfer catalysts for this purpose are the customary phase transfer catalysts described in the literature, such as Hemtech (“CH
EMTECH "), February 1980, page 111, Table 1 on page 111. That is, quaternary salts of phosphorus or sulfur with methylene bridges, cyclic polyethers, ring-opened poly. Ether, N-alkylphosphoramide or oxide.

The reaction is suitably carried out at a temperature between 60 and 140 ° C, preferably between 80 and 120 ° C.

In order to react the succinic diester with the nitrile, the following embodiments are in principle possible. That is, all components are initially charged at a relatively low temperature, and the mixture is heated to a range of reaction temperatures. Or,
The individual components are added sequentially in the desired order within the reaction temperature range.

A particularly preferred embodiment for obtaining good yields is to first combine the nitrile mixture with the base and feed it to the succinic diester within the reaction temperature range.

Particularly when alcoholates derived from lower alcohols such as methanol, ethanol, n-propanol, isopropanol, tert-butanol are used,
In order to achieve high yields, it will be necessary to continuously remove the lower alcohol formed during the reaction from the reaction catalyst.

If alcohols are used as solvents and alcoholates are used as bases, it is advantageous to choose alcohols and alcoholates having the same alkyl moiety. Furthermore, it would be even more advantageous if the succinic diester also contained the same alkyl group.

To hydrolyze the condensation products, acids or alcohols having 1 to 4 carbon atoms, such as methanol or ethanol, can be used. However, water is preferably used. Examples of suitable acids are aliphatic or aromatic carboxylic or sulfonic acids, for example formic acid, acetic acid, propionic acid, oxalic acid, benzoic acid or benzenesulfonic acid. Mineral acids can also be used, for example, hydrochloric acid,
The aqueous solution, carbonic acid or diluted sulfuric acid or phosphoric acid is suitable.

The diketopyrrolopyrrole mixture precipitates during the course of the hydrolysis and can be isolated by filtration.

The concentration of the sulfonating agent used in the sulfonation as well as the reaction conditions are chosen in close relation to the number of sulfonic acid groups to be introduced into the diketopyrrolopyrrole mixture.

The compositions according to the invention are mixed by mixing the components (a) and (b) in the desired proportions directly in the pasting medium or alternatively by an additional mixing step in water or sulfuric acid. Can be obtained by: If desired, the preparation of the composition can be followed by a metathesis to obtain the desired metal salt. This can be a composition according to the invention (for example one containing a sodium salt).
With an appropriate metal salt [eg, Ca (SO ₄ )].

The composition of the present invention can be used as a pigment for coloring a high molecular weight organic material.

Examples of high molecular weight organic materials that can be dyed or colored with the composition of the present invention are: cellulose ethers and esters such as ethyl cellulose, nitrocellulose, cellulose acetate, cellulose butyrate, natural or synthetic resins, For example, polymerized or condensed resins such as aminoplasts, especially urea / formaldehyde resins and melamine / formaldehyde resins, alkyd resins, phenolplasts, polycarbonates, polyolefins, polystyrene, polyvinyl chloride, polyamides, polyurethanes, polyesters, fluoropolymers such as polyfluoro Ethylene, polytrifluorochloroethylene or tetrafluoroethylene / hexafluoropropylene copolymers, as well as rubber, casein, silicone and silicone Such as a resin. These can be alone or in mixtures.

The polymer compounds exemplified above may be a single compound or a mixture in the form of a plastic composition or a melt, or in the form of a spinning solution, lacquer, paint, or printing ink. For some applications, it may be advantageous to use the dye in the form of a toner or formulation. The composition according to the invention is used in an amount of 0.01 to 30% by weight, preferably 0.1 to 10% by weight, based on the high molecular weight organic material to be colored.

The coloring of the high-molecular-weight organic material with the composition according to the invention is carried out, for example, by incorporating the composition, in the form of a masterbatch, optionally with the substrate, using a roll mill, a mixing device or a milling device. You. The colored material is then processed to the desired final shape in a manner known per se, such as calendering, compression molding, extrusion, spray coating, casting, injection molding and the like. It is often desirable to incorporate a plasticizer into the matrix polymer prior to processing to produce a soft molded article or to reduce the brittleness of the molded article. Suitable plasticizers are, for example, esters of phosphoric acid, phthalic acid or sebacic acid. The addition of the plasticizer can be performed before or after blending the composition into the polymer. In addition to the composition of the present invention, fillers or other coloring material components such as white pigments, colored pigments or black pigments can be added to the high-molecular-weight organic material in any amount in order to obtain various colors.

When coloring paints and printing inks, the high-molecular-weight organic material and the composition of the present invention are optionally added, for example, fillers,
Finely dispersed or dissolved in a common organic solvent or solvent mixture together with other pigments, desiccants or plasticizers to form a finely dispersed product or solution. The individual components may be dispersed or dissolved separately or several at once and all components may be combined later.

The colorants obtained using the compositions according to the invention with good rheological properties, for example in the form of plastics, fibers, paints or prints, have excellent overall properties, such as good dispersibility, high color strength, Furthermore, it is characterized by its recoatability, excellent fastness to migration, heat, light and weather and its good gloss.

The sulfonated diketopyrrolopyrrole mixture used as the component (b) in the composition of the present invention can itself be used as a pigment for coloring a high-molecular organic material as described above. For this purpose, the mixture can be used in the form of a crude product, or after having been subjected to suitable conditioning or work-up as described above for the composition according to the invention. .

 Hereinafter, the present invention will be further described with reference to examples.

Example 1 (a) First, 120 ml of t-amyl alcohol (anhydrous) is placed in a sulfonation flask under a nitrogen atmosphere. To this, 6.9 g of sodium and 0.1 g of sodium salt of bis-2-ethylhexyl sulfosuccinate were slowly stirred.
Is added. The mixture is heated to 95-102 ° C and held at 95 ° C under a nitrogen atmosphere overnight with vigorous stirring of the molten sodium. 85 ° C
And cooled to 14.04 g of 4-chlorobenzonitrile
Of benzonitrile and 10.3 g of benzonitrile are added. After this, 20.3 g of diisopropyl succinate was added at 95 ° C.
For 2 hours. The reaction mixture is kept at 95 ° C. for another 5 hours to complete the reaction. Then cool to room temperature and pour over 300 ml of cold water. The mixture is heated at reflux for 1 hour and then subjected to steam distillation. The resulting mixture was filtered at 60 ° C. and the product was washed with 1000 ml of water,
Dry in a vacuum oven at 80 ° C.

This gives 23.6 g of a red powder. It contains substantially three compounds of the formula:

Analysis (%) Measurement: C = 64.93; H = 3.45; N = 8.38; Cl = 13.72. (B) First, 160 g of 25% fuming sulfuric acid and 160 g of sulfuric acid-hydrate are put into a sulfonation flask. To this, 20 g of the mixture obtained in Example 1 (a) are introduced at 2 to 5 ° C. over 30 minutes. The mixture is stirred at room temperature for 20 hours and the resulting solution is poured onto a mixture of 1000 g of ice and 280 ml of water. The resulting suspension was stirred for 15 minutes, heated to 75 ° C, and then NaCl
Add 120 g. The mixture is stirred at 75 ° C. for 1 hour to complete the reaction. Afterwards the suspension is filtered to room temperature and the filter residue is washed with a 5% NaCl solution until the filtrate is colorless. The filtration residue is dried in a vacuum drying chamber to obtain a magenta powder 2.
Obtain 9.0g.

Analysis (%) C = 40.7; H = 2.3; N = 5.1; S = 4.8; Cl = 17.9. Cl ion = 9.6; H ₂ O = 2.4. (C) First, wet (solid content 36.3%) 1,4 -Diketo-3,6-di-
964 g of (4-chlorophenyl) -pyrrolo- [3,4-c] -pyrrole are charged to a sulfonation flask. Make up to volume 8 with deionized water. After stirring for 1 hour at room temperature, a solution of 8.1 g of the product prepared in Example 1 (b) in 900 ml of water (60 ° C.) is added. The mixture is stirred at room temperature for 2 hours.
Thereafter, 100 g of CaCl ₂ dissolved in about 500 ml of water are added, the mixture is heated to 75 ° C., stirred at 75 ° C. for 1 hour and filtered at room temperature. The filter residue is thoroughly washed with water and dried at 80 ° C. in a vacuum drying cabinet. This gives 352 g of a red powder having excellent chromatic and rheological properties.

Example 2-6 1,4-diketo-3,6-di- (4-
Example 1 using the pigments listed below instead of (chlorophenyl) -pyrrolo- [3,4-c] -pyrrole
The operation was performed as described in (c). A pigment powder having the same excellent chromatic and rheological properties was obtained.

Example 7 The operation was carried out as described in Example 1 (c) above, using trimethylhexadecyl ammonium bromide instead of CaCl ₂ . A red pigment having excellent chromatic and rheological properties was obtained.

Procedure was carried out as described in Example 5 using trimethyl hexadecyl ammonium bromide in place of Example 8 CaCl _2. A red pigment having excellent chromatic and rheological properties was obtained.

Procedure was carried out as described in Example 5 using trimethyl hexadecyl ammonium bromide in place of Example 9 CaCl _2. An orange pigment having excellent chromatic and rheological properties was obtained.

Example 10 The procedure was as described in Example 1 (a) above, using an equivalent amount of 4-phenylbenzonitrile instead of 4-chlorobenzonitrile. The obtained red pigment was further processed in the same manner as in Examples 1 (b) and (c). A red pigment having excellent rheological and chromatic properties was obtained.

Example 11 The procedure was as described in Example 1 (a) above, using an equivalent amount of 4-methylbenzonitrile instead of 4-chlorobenzonitrile. The obtained red pigment was further processed in the same manner as in Examples 1 (b) and (c). A red pigment having excellent rheological and chromatic properties was obtained.

Example 12 Example for use in alkyd / melamine baking paint 460 g of steatite beads 8 mm in diameter, alkyd lacquer of the following composition and pigment mixture prepared according to Example 1
28.0 g was loaded into a glass bottle with a screw cap and dispersed on a roller stand for 72 hours.

Alkyd lacquer composition: 60% xylene solution of alkyd resin Alkydal F310 [BAYER] 58.7g 60% of alkyd resin alkydal F32 (Bayer)
Xylene solution 58.7 g Silicone ale (Silikonoel) A1% xylene solution (Bayer) 2.0 g n-butanol 4.0 g Dowanol 4.0 xylene 15 g Dispersant Disperbyk D-160 [BK Chemical Co., Ltd. BKY-Chemie) 5.6 g After adding 24.0 g of a 90% xylene solution of melamine component Cymel 327 (Cyanamid), the mixture was dispersed on a roller stand for another hour. Thereafter, steatite beads were removed. The resulting colored paint paste is then applied to Mylar (Mila
r) applied to a transparent film and baked at 130 ° C. for 30 minutes (coat thickness 50 μm). A red paint having excellent chromatic and rheological properties was obtained.

──────────────────────────────────────────────────続 き Continuation of the front page (56) References JP-A-62-295966 (JP, A) JP-A-62-149759 (JP, A) JP-A-61-120861 (JP, A) JP-A-3-3 210375 (JP, A) U.S. Pat. No. 4,791,204 (US, A) (58) Fields investigated (Int. Cl. ⁶ , DB name) C09B 67/22 C09B 67/20 C07D 487/04 C08K 5/3412-5/357

Claims (5)

(57) [Claims] (A) at least one diketo of the following formula:
Pyrrolopyrrole(Where R₁, R_Two, R_Three, R_FourAre independently of each other H, Cl, Br, CH_Three, OCH
_Three, C₆H_FiveOr CN) and (b) 0.5 to said diketopyrrolopyrrole (a).
Up to 10% by weight of at least three different symmetric shapes
Of diketopyrrolopyrroles of the formula I in unsymmetrical form
[Wherein R in formula I₁, R_Two, R_Three, R_FourAre independent of each other
H, Cl, Br, CH_Three, OCH_Three, C₆H_FiveOr the formula -SO_Three X of
A group of the formula: Is H Or formula Mⁿ/ n
Group, or formula N (R_Five) (R₆) (R₇) (R₈) Means
Yes, where MⁿIs an n-valent metal cation, n is a number of 1, 2 or 3, R_Five, R₆, R₇, R₈Are each independently hydrogen, C₁−C
₁₈-Alkyl, C_Five−C₆-Cycloalkyl, substituted
Not or C₁−C₁₈-Phenyl substituted by alkyl
Stands for phenyl or R₇And R₈And they combine
Pyrrolidine group, imidazolidine with N atom
Group, piperidine group, piperazine group or morpholine group
Form or R₆, R₇, R₈Are they combined
Together with the N atom, a propyl group, a pyridine group, a picoline group,
Means pyrazine, quinoline or isoquinoline
The radical R in the mixture₁, R_Two, R_Three, R_FourAt least one of
Is the formula -SO_Three X Is a composition comprising: 2. At least three different types of symmetric shapes and
Of diketopyrrolopyrrole of the formula I below and in asymmetric form
Stuff (Where R₁, R_Two, R_Three, R_FourAre independently of each other H, Cl, Br, CH_Three, OCH
_Three, C₆H_FiveOr the formula -SO_Three X Wherein X represents a group
Is H Or formula Mⁿ/ n group or the formula N (R_Five)
(R₆) (R₇) (R₈), Where MⁿIs an n-valent metal cation, n is a number of 1, 2 or 3, R_Five, R₆, R₇, R₈Are each independently hydrogen, C₁−C
₁₈-Alkyl, C_Five−C₆-Cycloalkyl, substituted
Not or C₁−C₁₈-Phenyl substituted by alkyl
Stands for phenyl or R₇And R₈And they combine
Pyrrolidine group, imidazolidine with N atom
Group, piperidine group, piperazine group or morpholine group
Form or R₆, R₇, R₈Are they combined
Together with the N atom, a pyrrole group, a pyridine group, a picoline group,
Means pyrazine, quinoline or isoquinoline
But the radical R in the mixture₁, R_Two, R_Three, R_FourAt least
One is the formula -SO_Three X Is). 3. At least three different types of symmetric shapes and
Of diketopyrrolopyrrole of the formula I below and in asymmetric form
Stuff (Where R₁, R_Two, R_Three, R_FourAre independently of each other H, Cl, Br, CH_Three, OCH
_Three, C₆H_FiveOr the formula -SO_Three X Wherein X represents a group
Is H , H Or formula Mⁿ/ n group or the formula N
(R_Five) (R₆) (R₇) (R₈), Where MⁿIs an n-valent metal cation, n is a number of 1, 2 or 3, R_Five, R₆, R₇, R₈Are each independently hydrogen, C₁−C
₁₈-Alkyl, C_Five−C₆-Cycloalkyl, substituted
Not or C₁−C₁₈-Phenyl substituted by alkyl
Stands for phenyl or R₇And R₈And they combine
Pyrrolidine group, imidazolidine with N atom
Group, piperidine group, piperazine group or morpholine group
Form or R₆, R₇, R₈Are they combined
Together with the N atom, a pyrrole group, a pyridine group, a picoline group,
Means pyrazine, quinoline or isoquinoline
But the radical R in the mixture₁, R_Two, R_Three, R_FourAt least
One is the formula -SO_Three X In the manufacturing method,
Formula ROOC-CH_Two−CH_Two-COOR (II) (wherein R represents lower alkyl)
One mole of the stell, in the presence of a strong base,(Where R₁, R_Two, R_Three, R_FourAre independently of each other H, Cl, Br, CH_Three, OCH
_ThreeOr C₆H_FiveMeans, but R₁, R_Two, R_Three, R_FourFew
At least one means hydrogen) with a molar ratio of III: IV of 9: 1
2 moles of a mixture of two different nitriles that is from 1: 9
And the resulting mixture is then known per se
Depending on the method, fuming sulfuric acid, concentrated sulfuric acid, liquid sulfur trioxide, or
Specializes in sulfonation using chlorosulfonic acid.
How to sign. 4. A polymer organic material containing the composition according to claim 1. 5. A high molecular weight organic material containing the mixture according to claim 2.