DE1569643A1 - Process for the production of metal-containing phthalocyanines - Google Patents

Description

BÄDISCHE ANILIN- & SODA «.FABRIK AG 1 569643

■ Our marks p.Z. 24 09I Hee / Bö Luawigshafen / ahein, February 2, 1966

Process for the production of metal-containing phthalocyanines

It has been found that metal-containing phthalocyanines can be prepared particularly advantageously by reacting phthalonitriles with metal salts in solvents which are inert under the reaction conditions, optionally in the presence of nitrogen bases, if the mixture of starting materials is heated to temperatures between 100 and 170.degree wherein one as long as the holding temperature in this range, has gone into solution to the suspension to form an intermediate product, and the reaction then completed at temperatures between I90 and 22O ⁰ C.

The metal salts used in the new process are e.g. anhydrous salts of copper, aluminum, iron, vanadium or manganese Consideration. The new process is particularly suitable for production of copper phthalocyanines, which are usually used copper salts such as copper acetate, copper sulfate and in particular Copper (l) and copper (II) chloride or mixtures of these Salts used.

As phthalonitrile, this is not the only thing that can be done technically to a large extent used unsubstituted phthalonitrile but it can too

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substituted phthalonitriles are used »Substituted Examples of phthalonitriles are halogenated phthalonitriles such as 1 to 4-fold chlorinated oäex brominated compounds in particular Tetrachlorophthalodinisril, also phenyl-substituted compounds such as 4-phenylphthalodinitrile.

Solutions that are inert under the reaction conditions are, for example aromatic compounds such as monochlorobenzene, trichlorobenzene and especially nitrobenzene. Compounds with boiling points are preferred above 170 C, especially between 190 and 220 C.

If metal halides are used as metal salts, the reaction is expediently carried out in the presence of nitrogen bases. These are, for example, ammonia or organic bases, in particular tertiary organic bases such as pyridine or fihinelin.

The ratio of metal salt to phthalonitrile is kept stoichiometric or the metal salt is used, but advantageously the dintrile, in a small, e.g. up to 20%, excess over the stoichiometric Lot. The amount of nitrogen base to be used can be within vary over a larger area. One can use the reaction mixture For example, saturate with ammonia or use only half the amount necessary for saturation. However, it is useful to add at least 0.1 mol and at most 2 mol based on the phthalonitrile of the nitrogen base. The amount of inert Solvent can, for example, be 2 to 8 times

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weight amount, "based on the phthalonitrile. It should expediently chosen so that the reaction mixture is sufficient remains thin. Larger amounts than the 8 times given above Amount are therefore not harmful, but generally not useful, because the greater dilution increases the reaction time will.

Hach a particularly useful embodiment of the invention leads «to the reaction in the presence of nitrogen bases and catalytic compounds, as described in the German patent ....... (patent application B 82 552 IVc / 22c) are mentioned. Such catalysts are, in particular, oxides and oxo acids or their salts, halides or carbonyl compounds des Titanium, molybdenum or iron can be considered. Of these, in turn, are those Carbonyl compounds of molybdenum or iron are particularly effective. " The following are specifically mentioned as catalytically active compounds: molybdenum oxide, molybdenum carbonyl, iron carbonyl, titanium tetrachloride, Phosphomolybdic acid and molybdic acid.

Of the catalytically active compounds, for example 0.1 to 2 mol, based on 1 mol of phthalonitrile, are used. Lesser ones Amounts of catalyst also lead to a considerable acceleration of the reaction; can, however, requires significantly longer response times. The addition of larger amounts of the catalytically active compound is not harmful, but does not lead to any further reduction the implementation period.

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The new procedure is carried out, for example, indeu. one the mixture the starting materials initially to temperatures between 100 and 170 ° C heated and held in this temperature range until the suspension passed into a solution with the formation of an intermediate product is. The formation of the soluble complex intermediate is generally also due to a color change or a color deepening of the reaction mixture recognizable. The temperature and the speed under which the so marked intermediate state is depends on the type of dinitrile, the solvent and the grain size of the metal salt. The partial implementation is finished after about 5 minutes to an hour. For example the intermediate product is formed from phthalonitrile and Copper (l) chloride in nitrobenzene and in the presence of ammonia and catalyst at 150 ° C in 5 to 10 minutes. In trichlorobenzene this implementation takes 15 minutes. If you use it instead of Phthalonitrile Tetrachlorophthalodinitrll, it takes up to 30 minutes for the intermediate product to form, reaction times from about 30 minutes to about an hour will be in use other metal salts, e.g. aluminum, iron or vanadium are required »

So that the components and components are suspended as homogeneously as possible so that a quick dissolution is achieved, it is advantageous if nan by rubbing or kneading the starting materials with the Solvent, excluding nitrogen base, makes a paste, this into the one with Rünrwer ·. provided and on the implementation

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temperature of the first stage enters the preheated reaction vessel and only then adds the base. If ammonia is used as the base, and If the process is carried out continuously, it is expedient if - the solvent is removed before the addition, e.g. through a mixing nozzle, saturates with the gas. The mixing nozzle can be designed as a radiator be sucked off by the ammonia gas released in the course of the reaction and fed back to the reaction mixture of the first stage will. The starting materials can, however, without any disadvantage be added to the reaction vessel in the solid state or suspended in the solvent.

After the intermediate product has formed, the reaction is completed at temperatures between 190 and 220.degree. In this temperature range, the strongly exothermic reaction for the formation of the metal-containing phthalocyanines begins, so that it can be completed without further heating. The insoluble phthalocyanines fall out of it and can in the usual manner, for example, _e be isolated by suction. The second step of the reaction, the heating of the dissolved reaction mixture to temperatures between 190 and 220 G, can be carried out in the same reaction vessel ^ egebane temperature level was auigeist. The conversion to metal-containing phthalocyanines ^ proceeds particularly quickly.

In the process of the invention, the metal-containing phthalocyanines are used in a very pure form and in worse yield than after the known .

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One-step procedure obtained »The metal content corresponds to the theoretical Values. Those made from the phthalocyanines obtained in this way Pigment inks distinguish themselves through graphic strength and high purity of the shade.

The parts given in the following examples are parts by weight. Parts of space relate to parts by weight as the liter to the kilogram.

example 1

51.2 parts of phthalonitrile, 10.9 parts of copper (I) chloride and 0.15 part of molybdic acid are suspended in 200 parts by volume of hydrobenzene in a glass flask equipped with a stirrer. Ammonia is introduced into the suspension to saturation. Now it is quickly heated to 145 C. With very vigorous stirring, the suspended particles go into solution within 5 minutes with an emerald green color. This solution is transferred into a pre-heated to 200 ⁰ C the reaction vessel, the copper-dinitrile Komplei formed as an intermediate in the tetramerizes immediately to copper phthalocyanine. After 5 minutes, the reaction is terminated by quenching with cold nitrobenzene. The dye is filtered off at approximately 100 ⁰ C and washed with a little nitrobenzene of approximately 100 C. The solvent is then displaced with methanol and the filter cake with dilute hydrochloric acid at about 9O ⁰ C extracted. With a yield of $ 84.2 (based on the phthalonitrile used), a copper phthalocyanine with a copper content of $ 10.95 is obtained.

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If the NH _x saturated «Sasy fusion of the starting materials, which has a temperature of about 45 ° C, is immediately placed in the reaction vessel preheated to 200 C, and if the rest of the procedure is as indicated above, only a yield of 67 ^ is achieved where the copper content of the product is $ 10.18 »

Example 2

In a mixer, 51 g of phthalonitrile, 10 g of copper chloride and 170 mg of molybdic acid are mixed thoroughly with 50 ml of nitrobenzene every hour and introduced into a well-stirred flask which is kept at 155.degree. At the same time, 150 ml of nitrobenaol, which has previously been saturated with ammonia, are run in per hour. The solution; The complex intermediate compound of emerald green color overflows into a second glass flask kept at 2O5 ° C, in which the solution reacts to form copper phthalocyanine. The suspension runs on a suction filter. After aspiration of the mother liquor is in the ratio 1: 1 (solid: nitrobenzene) _f n * chgewaschen. nitrobenzene subsequently displaced with methanol and the crude dye finally stirred with dilute hydrochloric acid at about ψϊ'Ζ.

Yield: ^Q 7 $ E> pferphthalocyanine (based on phthalonitrile) with a copper, -. ? stop of 11.01 fo.

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Claims (3)

Claims 1. A process for the preparation of metal-containing phthalocyanines by reacting Phthälodinitrilrn with metal salts in solvents which are inert under the reaction conditions, optionally in the presence of nitrogen bases, characterized in that the mixture of starting materials is heated to temperatures between 100 and 170 C, wherein one while maintaining the temperature 'in this area has gone into solution to the suspension to form an intermediate product, and the reaction then completed at temperatures between 19O and 22O ⁰ C. 2. The method according to claim 1, characterized in that the solution formed from the starting materials at temperatures between 100 and 170 C to complete the reaction is introduced into a reaction vessel which has been heated to temperatures between 190 and 220 C. 3. The method according to claim 1, characterized in that the metal salts used are copper chlorides and the reaction is carried out in the presence of nitrogen bases and oxides, oxo acids or their salts, halides or carbonyl compounds of titanium, molybdenum or iron. BADIAN ANILINE & SODA FACTORY Ate 009828 / U02