DE19636032A1 - Bridged perinone, quino-phthalone or perinone-quino-phthalone compound - Google Patents

Abstract

Bridged perinone, quinophthalone and perinone-quinophthalone compounds of formula (I) and their tautomers are new: Ar1, Ar2 = group completing optionally substituted carbocyclic aromatics; B = optionally substituted alkylene, oxygen (-O-), an ester group of the formula -C(=O)-O- or -C(=O)-O-(CH2)r-O-C(=O)-, attached to an aromatic carbon (C) atom at each end; r = 1-4; X1, X2 = groups of formula (IIA) and (IIB); with the group of the formula -C(O)-O- or -C(N-)- adjacent to the C=C double bond; Y = optionally substituted benzene or naphthalene ring; Z = optionally substituted ortho-phenylene, ortho-naphthylene, peri-(1,8)-naphthylene or arylene of > 2 condensed benzene rings bridged in the ortho-position or the position corresponding to the peri-position in naphthalene; Ra = hydrogen or hydroxyl; Rb = H or halogen, especially fluorine, bromine or chlorine. Also claimed are plastics coloured with compound(s) (I).

Description

The invention relates to bridged perinones, processes for their preparation and their use for the mass coloring of plastics.

It is known to use perinone dyes, for example from FR-A-1075.110 or US-A-5,466,805 are known for use in bulk coloring plastics.

Such compounds are characterized by good temperature stability and high light fastness, but their fastness to sublimation is still better worth reading. In the dyeing process, i.e. H. in the injection molding machines, it happens at temperatures above 240 ° C it is not uncommon for an undesirable Sublimation of the dye, which contaminates the work tool, which is due agile cleaning measures required.

The object of the present invention was therefore to improve perinone dyes to provide the sublimation fastness.

Compounds of the general formula (I) have been found

wherein
A₁ and A₂ independently of one another are optionally substituted ortho-phenylene, ortho-naphthylene, peri- (1,8) -naphthyiene or arylene from more than two fused benzene rings, the aryl radicals having more than two fused benzene rings in ortho - or are bridged according to a peri slope in the naphthalene,
Ar₁ and Ar₂ independently of one another are radicals for completing optionally substituted carbocyclic aromatics and
B represents an optionally substituted alkylene group, each of which is bonded to an aromatic carbon atom of the two radicals Ar₁ and Ar₂.

The peri position actually corresponds to the 1,8 position in naphthalene. This However, importance is given both in the literature and in the sense of the present Registration also extended to Arylene, which more than two with each other have fused benzene rings.

Examples of possible substituents for arylenes A₁, A₂ and carbocyclic aromas Ar₁ and Ar₂ are:
C₁-C₆-alkyl, halogen, nitro, aryl, aryloxysulfonyl, hydroxy, C₁-C₆-alkoxy, aryloxy, optionally substituted by alkyl or acyl amino, optionally substituted by alkyl or aryl aminosulfonyl or a fused cycloaliphatic or heterocyclic ring.

Preferred substituents are:
Chlorine, bromine, nitro, methoxy, NH₂, benzyloxy, hydroxy, -SO₂O (C₆H₅), -SO₂N (CH₃) ₂, -SO₂NHCH₃, methyl, ethyl, n-propyl, iso-propyl, n-, sec-, tert. -Butyl, NHCOCH₃, -N (C₂H₅) ₂ or optionally substituted phenyl.

As a possible substituent of the alkylene group B, which is straight-chain or branched can be, for example, CF₃ to be mentioned.

Ar₁ and Ar₂ is particularly preferably a radical to complete a gene optionally substituted benzene or naphthalene ring, especially one ge optionally substituted benzene ring.

Particularly preferred radicals A₁ and A₂ correspond independently of one another an optionally substituted peri- (1,8) -naphthylene.

Compounds of the formula (I) are particularly preferred, those of the formula (II) correspond

wherein
n and m independently of one another represent a number from 0 to 4,
R₁ and R₂ are each independently the same or different and can assume the meaning of the substituents mentioned for the radicals A₁, A₂, Ar₁ and Ar₂, in particular halogen and C₁-C₆-alkyl,
o and p independently of one another represent a number from 0 to 2, in particular 0 or 1,
R₃ and R₄ are each independently the same or different and can assume the meaning of the substituents mentioned for the radicals A₁, A₂, Ar₁ and Ar₂, in particular halogen, NO₂, -NH-acyl or -NH-alkyl and
B has the meaning given above.

The preferred meaning of B is an optionally substituted one C₁-C₅ alkylene group. In particular, the following should be mentioned:

B very particularly preferably represents -CH₂-, -CH (CF₃) -, -C (CF₃) ₂- or -C (CH₃) ₂-.  

Compounds of the formula (I) are very particularly preferred
wherein
A₁ = A₂ and
Ar₁ = Ar₂ mean.

Compounds of the formula (II)
wherein
n = m,
R₁ = R₂,
o = p and
R₃ = R₄ mean
being in particular
n, m, o and p stand for 0.

The optionally substituted alkylene group in the meaning of B is on the respective aromatics Ar₁ or Ar₂ preferably in the para position to a carb oxyl group bound.

Compounds of the formula (III) are particularly preferred

wherein
n, m, R₁, R₂ and B have the meanings given above.

The compounds according to the invention are notable for excellent Fastness to sublimation in the mass dyeing of plastics. They also own very good light fastness, good thermal stability and a particularly high color Strength. A comparison in the color strength compared to the non-doubled Perinon shows a more than additive increase, recognizing a synergistic effect leaves.

A particular advantage with the symmetrical perinones of formula (I), ie where A₁ = A₂ and Ar₁ = Ar₂ means, compared to not over the bridge member B. doubled perinones is that with almost identical shade of verdop peltem to the undoubted system the color strength when using the same amount is generally significantly higher in the perinones according to the invention.

The perinones of formula (I) according to the invention have different meanings lines for A₁ and A₂ and / or for Ar₁ and Ar₂, it may be advantageous to possibly resulting mixtures of symmetrical resulting from production and unsymmetrical perinones of formula (I) for the intended use to lead.

The invention further relates to a method for producing the fiction, ge moderate compounds of formula (I), which is characterized in that Tetracarboxylic acids or their anhydrides of the formula (IV)

wherein
Ar₁, Ar₂ and B have the meanings given above,
condensed with diamines of the formula (V) and / or (VI),

where the sum of the diamines V and VI used is two molar equivalents, based on the tetracarboxylic acid IV, and A₁ and A₂ corresponds to the above To have meaning.

The condensation can be directly by melting together equimolar men gene of the components of formulas (IV) and (V) or (VI) at one temperature from 120 ° C to 250 ° C, preferably at 120 to 180 ° C, or more advantageously in a solvent at a temperature of 120 ° C to 220 ° C, preferably at 120 to 180 ° C, optionally under pressure, with a distillative removal of the water of reaction can take place.

Suitable solvents are, for example: chlorobenzene, o-dichlorobenzene, tri chlorobenzene, xylene, dimethylformamide, N-methylpyrrolidone, glacial acetic acid, propion acid, phenol, cresols, phenoxyethanol, glycols and their mono- and dialkyl ether, alcohols, e.g. B. methanol, ethanol, i-propanol, water and aqueous solution medium such as B. dilute sulfuric acid u. a.

If necessary, the reaction can be carried out with the addition of an acidic catalyst.

Suitable catalysts are, for example: zinc chloride, p-toluenesulfonic acid, hydrochloric acid, sulfuric acid, organic acids and others
The tetracarboxylic acid of the formula (IV) is particularly preferably used in the form of its anhydride.

Compounds of the formula (IV) are preferably used, those of the formula (VII) or their anhydrides

wherein
R₃, R₄, B, o and p have the meanings given above.

Compounds of the formula (IV) which are very particularly preferably used are: correspond to formula (VIII) or their anhydrides

in which
B represents -CH₂-, -CH (CF₃) -, -C (CF₃) ₂- or -C (CH₃) ₂-.

The diamines of the formula (V) or (VI) are known or can be exemplified wise produce analogous known diamines.

Preferred aromatic diamines of the formula (V) or (VI) are:
o-phenylenediamine, chloro-o-phenylenediamine, dichloro-o-phenylenediamine, methyl-o-phenylenediamine, ethyl-o-phenylenediamine, methoxy-o-phenylenediamine, acetamino-o-phenylenediamine, phenyl-o-phenylenediamine, naphthylene-o diamines, also 1,8-naphthylenediamine, chloro-1,8-naphthylenediamine, dichloro-1,8-naphthylenediamine, methyl-1,8-naphthylenediamine, dimethyl-1,8-naphthylenediamine, methoxy-1,8-naphthylenediamine , Ethoxy-1,8-naphthylenediamine, acetamino-1,8-naphthylenediamine and 1,8-diaminoacetnaphthylene.

In a further preferred process variant, an optionally substi tuiert peri-naphthylenediamine as a compound of formula (V) or (VI) sets, especially 1,8-naphthylenediamine.  

The invention further relates to compounds of formula IV or their anhydrides, wherein Ar₁ and Ar₂ have the meaning given above and
B is a radical of the formula

means.

Preferred compounds of formula IV according to the invention correspond to Preferred forms already specified above, d. H. of the formula VII or VIII with the corresponding substituent meanings, where B is that for the inventive Compounds of formula IV has the scope of meaning given.

The invention further relates to a process for the preparation of the compounds of the formula IV, which is characterized in that dichlorides of the formula IX

Cl-B-Cl (IX)

with dimethyl compounds of the formula X and / or XI

implemented under Triedel-Crafts conditions, the amount of Ver Bonds X and XI together have at least 2 mole equivalents per mole of ver makes bond IX, and the reaction product obtained is then oxidized becomes. Ar₁, Ar₂, and B have the broadest meaning given above.  

A preferred compound of formula X or XI is o-xylene. As an oxi dating agent is preferably to be mentioned nitric acid.

Some compounds of formula (IV) are partly from JP-A-60 166 325, DE-A-2.337.63 1, Chem. Heterocycl. Comp. 30, 1994, pp. 31-34 and US-A-3,332,964.

Dyes of the formula (I), which are optionally substituted by the group of Carrying alkyl or arylaminosulfonyl radicals can be found, for example, in the ent speaking dyes of formula (I) in which a substituent is a chlorine sulfonyl radical means represent with alkyl or arylamines.

Dyes according to the invention in which a substituent is an aryloxysulfonyl radical, can also by reacting the corresponding chlorosulfonyl dyes Phenols or naphthols in the presence of a base, e.g. B. pyridine, triethylamine, Alkali or alkaline earth carbonates, hydroxides or oxides can be obtained.

Dyes of the formula (I) in which substituents for alkyloxy or acyloxy stand, can additionally by alkylation or acylation of the Invention appropriate dyes that carry a hydroxy group, are shown.

Those dyes of the formula (I) with an optionally acylated or alkylated Amino groups can also be reduced by reduction with conventional reducing agents, e.g. B. iron, zinc, sodium sulfide, hydrogen and. a. the corresponding connection gene in which the corresponding substituent represents a nitro group, and optionally subsequent acylation or alkylation can be obtained. Of the Acylation step can also be carried out in the course of the reduction by adding a Acylating agent take place.

The reaction mixture is preferably worked up by dilution with alcohols such as methanol, ethanol, propanol or butanol. Aromatic too Diluents such as chlorobenzene or toluene can be used. The The method according to the invention provides the compounds according to the invention preferably in yields of 90-95% of theory.

The dyes according to the invention are outstandingly suitable for dyeing Plastics in bulk.  

Mass coloring is understood to mean, in particular, processes in which the dye is incorporated into the molten plastic mass, e.g. More colorful Using an extruder or where the dye is already the starting compo Nenten for the production of the plastic, for. B. monomers before polymerization, is added.

Particularly preferred plastics are thermoplastics, for example vinyl poly mers, polyesters and polyamides.

Suitable vinyl polymers are polystyrene, styrene-acrylonitrile copolymers, styrene Butadiene copolymers, styrene-butadiene-acrylonitrile terpolymers, polymethacrylate, Polyvinyl chloride and a.

Other suitable polyesters are: polyethylene terephthalates, polycarbonates and Cellulose esters.

Polystyrene, styrene copolymers, polycarbonates and polymeth are preferred acrylate. Polystyrene is particularly preferred.

The high-molecular compounds mentioned can be used individually or in mixtures, exist as plastic masses or melts.

The dyes of the invention are used in finely divided form brought, wherein dispersants can be used but do not have to.

If the dyes (I) are used after the polymerization, they are also used the plastic granulate mixed dry or ground and this mixture e.g. B. plasticized and homogenized on mixing rollers or in screws. Man can also add the dyes to the molten mass and this distribute homogeneously by stirring. The material so pre-colored is then like usual z. B. by spinning to bristles, threads etc. or by extrusion or further processed into molded parts by injection molding.

Since the dyes of the formula (I) compared to polymerization catalysts, in particular special peroxides are resistant, it is also possible to dye the mono Add raw materials for the plastics and then in the presence to polymerize polymerization catalysts. To do this, the dyes  preferably dissolved in the monomeric components or intimately ver with them mixes.

The dyes of the formula (I) are preferably used for dyeing the above Polymers in amounts of 0.0001 to 1 wt .-%, in particular 0.01 to 0.5 wt .-%, based on the amount of polymer used.

By adding pigments insoluble in the polymers, such as. B. titanium dioxide, corresponding valuable muted stains can be obtained.

Titanium dioxide can be present in an amount of 0.01 to 10% by weight, preferably 0.1 to 5 wt .-%, based on the amount of polymer, are used.

Mixtures of different can also be used in the process according to the invention Dyes of the formula (I) and / or mixtures of dyes of the formula (I) with other dyes and / or inorganic or organic pigments be set.

The invention is explained, but not limited to the following examples, in which the parts are given by weight. Percentages by weight mean (% by weight).

Examples example 1

16.8 g of 4,4'-isopropylidene-di phthalic acid dianhydride and 19.0 g of 1,8-naphthylenediamine were added to 150 ml of o-dichlorobenzene with stirring. In the presence of a nitrogen atmosphere, the mixture was heated to 130 ° C. and this temperature was held for 8 hours. The mixture was then heated to 150 ° C. for a further 3 h, then cooled to 80 ° C., and 150 ml of methanol were added to the reaction mixture. After a further 2 h at 65-70 ° C., the mixture was cooled to room temperature, stirred for 1 h at room temperature and the dye was filtered off. The dye was then washed with 100 ml of methanol and then washed with 250 ml of hot water and dried in vacuo at 60 ° C.
Yield: 27.9 g = 96% of theory.

The dye has the structural formula

Instead of o-dichlorobenzene, other solvents such as e.g. B. o-xylene, Phenol, diphenyl ether or ditolyl ether used. The yellowish orange color fabric colors plastics such as polystyrene, polycarbonate, polyester, polyamide or Copolymers of acrylonitrile, butadiene and styrene in the mass in sublimation real, lightfast and temperature stable dyeings.

According to thermogravimetric analysis, only one was found at 400 ° C Dye sublimation loss of 5%. In the unbridged dye of the formula

on the other hand, the dye loss by sublimation was the same under the same conditions 9%.

Example 2

150 ml of phenol were mixed with stirring at a temperature of about 80 ° C in a nitrogen atmosphere with 15.4 g of 4,4'-methylenediphthalic acid dianhydride and 16.0 g of 1,8-naphthylenediamine. The reaction mixture was heated to 130 ° C. and held at this temperature for 8 hours. The mixture was then cooled to 80 ° C., 250 ml of methanol were added and the mixture was stirred at 60-65 ° C. for 2 h. The reaction mixture was cooled to room temperature and stirred for 1 h. The resulting dye was filtered off, washed with 100 ml of methanol and 250 ml of hot water and dried in vacuo at 60 ° C.
Yield: 27 g = 93% of theory.

The dye has the formula

The dye colored plastics such as polystyrene, polycarbonate, copolymers made of polyacrylonitrile, butadiene and styrene in the mass in yellow-orange shades. The Colorings are sublimation-fast and have high light fastness and high temperature temperature stability. Thermogravimetric analysis of the dye showed at 400 ° C a weight loss by sublimation which is clearly below that of the non ver bridged connection, as already mentioned in Example 1, was.  

Example 3

200 ml of o-dichlorobenzene were passed over with nitrogen, with 15.4 g of 4,4 ′ - [2,2,2-trifluoro-1- (trifluoromethyl) ethylidene] diphthalic acid dihydride and 16.0 g of naphthalenediamine 1.8 offset. The mixture was heated to 130 ° C. and kept at this temperature for 8 hours. The mixture was then cooled to 80 ° C. and 250 ml of methanol were added to the reaction mixture. The mixture was stirred at 60-65 ° C for 2 h and then cooled to room temperature. The dye precipitate was filtered off and washed with 100 ml of methanol. Then it was washed with 250 ml of hot water and dried in vacuo at 60 ° C.
Yield: 19.2 g = 94% of theory.

The dye has the structural formula

and dyes polystyrene in bulk, copolymers of acrylonitrile, butadiene and styrene, polycarbonate and polyester in yellow-orange shades with very good Fastness properties such as light fastness, migration fastness, thermal stability as well Sublimation fastness.

A thermogravimetric analysis of this dye at 400 ° C was one Substantially lower loss of substance due to sublimation can be observed than with the non-bridged dye mentioned in Example 1.

Claims (14)

1. Compounds of formula (I) wherein
A₁ and A₂ independently of one another optionally substituted ortho-phenylene, ortho-naphthylene, peri- (1,8) -naphthylene or arylene from more than two fused benzene rings, the aryl radicals having more than two fused benzo rings in ortho - or are bridged according to a peri position in the naphthalene,
Ar₁ and Ar₂ independently of one another radicals to complete optionally substituted carbocyclic aromatics and
B represents an optionally substituted alkylene group, each of which is bound to an aromatic carbon atom of the two radicals Ar 1 and Ar 2. 2. Compounds according to claim 1, characterized in that Ar₁ and Ar₂ radicals to complete an optionally substituted Are benzene or naphthalene ring. 3. Compounds according to claim 1, characterized in that A₁ and A₂ independently substituted, optionally substituted peri- (1,8) -naphthyls correspond. 4. Compounds according to claim 1, which correspond to the formula (II) wherein
n and m independently of one another represent a number from 0 to 4,
R₁ and R₂ are each independently the same or different and C₁-C₆-alkyl, halogen, nitro, aryl, aryloxysulfonyl, hydroxy, C₁-C₆-alkoxy, aryloxy, optionally substituted by alkyl or acyl amino, optionally substituted by alkyl or aryl ized aminosulfonyl or a fused-on cycloaliphatic or heterocyclic ring,
o and p independently of one another represent a number from 0 to 2, in particular 0 or 1,
R₃ and R₄ are each independently the same or different and C₁-C₆-alkyl, halogen, nitro, aryl, aryloxysulfonyl, hydroxy, C₁-C₆-alkoxy, aryloxy, optionally substituted by alkyl or acyl-substituted amino, optionally by alkyl or aryl ized aminosulfonyl or a fused-on cycloaliphatic or heterocyclic ring, and
B has the meaning given above. 5. Compounds according to claim 1, characterized in that B is a ge optionally substituted C₁-C₅ alkylene group. 6. Compounds according to claim 1, characterized in that B -CH₂-, -CH₂-CH₂-, -CH₂CH₂CH₂-, -CH₂CH₂CH₂CH₂-, means. 7. Compounds according to claim 1, wherein
A₁ = A₂ and
Ar₁ = Ar₂ mean. 8. Compounds according to claim 4, which correspond to the formula (III) wherein
n, m, R₁, R₂ and B have the meanings given in claim 4. 9. A process for the preparation of compounds according to claim 1, characterized in that tetracarboxylic acids or their anhydrides of the formula (IV) wherein
Ar₁, Ar₂ and B have the meanings mentioned in claim 1,
condensed with diamines of the formula (V) and / or (VI), wherein the sum of the diamines V and VI used two molar equivalents, based on the tetracarboxylic acid IV, and A₁ and A₂ have the meaning given above. 10. Compounds of formula IV wherein
Ar₁, Ar₂ have the meaning given in claim 1 and
B is a radical of the formula means. 11. Use of a compound according to claim 1 for the mass coloring of plastics. 12. Use according to claim 11, characterized in that the art fabric is a thermoplastic.   13. Use according to claim 11, characterized in that the fär plastic a vinyl polymer, especially polystyrene, or a poly is ester. 14. Plastics colored with at least one compound according to claim 1.