DE2637861A1 - PROCESS FOR THE PRODUCTION OF POLYHALOGEN-METAL PHTHALOCYANINES - Google Patents

Description

The invention relates to an improved process for the halogenation of metal phthalocyanines.

It is well known that metal phthalocyanines can be halogenated in a titanium tetrachloride medium. In this case, however, it is necessary to use superatmospheric pressure, which is undesirable for large-scale production is. It has now been found that the halogenation can be carried out at atmospheric pressure, when aluminum chloride is added to the titanium tetrachloride medium.

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-2-ORlGINAL WSPECTEO

According to the invention there is now a method of manufacture proposed by polyhalogenometal phthalocyanines, in which chlorine and / or bromine to one Metal phthalocyanine is added in a titanium tetrachloride medium containing aluminum chloride.

Particularly copper phthalocyanines are to be used as metal phthalocyanines cyanine and partly chlorinated copper phthalocyanine, such as monochloro copper phthalocyanine, but also partly brominated copper phthalocyanines and aluminum phthalocyanine can be mentioned.

The amount by weight of the titanium tetrachloride may be 0.5 to 20 times and preferably 6 to 10 times the amount by weight of the metal phthalocyanine.

It is often (for example to achieve a more homogeneous Reaction medium) desirably, one or more halides or oxyhalides of sulfur or phosphorus, e.g. Thionyl chloride, sulphuryl chloride, sulfur chlorides, phosphorus trichloride and Phosphoroxychlorld, to be added.

The halides or oxyhalides can expediently in amounts by weight up to 15 times the amount by weight of Aluminum chloride may be present, but 0.1 to 5 times the weight of the aluminum chloride is preferred. The amount by weight of the aluminum chloride together with the amount by weight of any halides that may be present or oxyhalides expediently 0.16 to 3 ^ times and preferably 0.5 to 5 times the amount by weight of the Metal phthalocyanine ♦

ORIGINAL

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Catalysts, such as, for example, iodine, sulfur, antimony trisulfide or antimony trichloride or pentachloride, can be added in amounts by weight which are expediently between 0.05 and k % by weight of the metal phthalocyanine.

The inventive method can be carried out by any convenient measure that is for the halogenation of Metal phthalocyanines is common. For example, the aluminum chloride, the halide or oxyhalide and the catalyst (if used) is added to the titanium tetrachloride, followed by the addition of the metal phthalocyanine followed and whereupon the temperature is then brought to the desired value and the chlorine or bromine is introduced. It it is often advisable to add the bromine all at once. However, the chlorine can be passed into the reaction mixture. The required amount of elemental chlorine or bromine is 1.5 to 6 atoms per halogenated metal phthalocyanine required atom.

Suitable reaction temperatures are performed 60 to 170 ⁰ C, in particular 100 to I ¹ JO ⁰ C. The reaction can optionally at superatmospheric pressure, however, it is preferred to operate at atmospheric pressure.

The process is particularly suitable for the production of halogenated metal phthalocyanines containing 1 to 16 halogen atoms contain per molecule, in particular for the preparation of compounds in which all halogen atoms consist of chlorine or in which 1 to 15 halogen atoms from bromine and the remaining halogen atoms from chlorine exist. For the latter compounds it is preferred to carry out the bromination before the chlorination. These connections are valuable green pigments.

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The halogenated metal phthalocyanines can be isolated by distilling the titanium tetrachloride separated off and the residue is brought together with an aqueous acid, from which the insoluble phthalocyanine is then separated off can be, for example by filtration.

The procedure is advantageous over such procedures, in which melts of the sodium chloride / aluminum chloride type are used as reaction media, as in the case of the Method the amount of aluminum chloride used is small and the titanium tetrachloride used in place of aluminum chloride is cheaper and more readily available than aluminum chloride and it is also easy to reuse can be recovered.

The invention is illustrated in more detail by the following examples, in which all parts and percentages are by weight are expressed unless otherwise specified.

EXAMPLE 1

30 parts of copper phthalocyanine are added to 90 parts of titanium tetrachloride containing 23 parts of aluminum chloride at 25 ^° C. with stirring. The temperature is raised to 150 ⁰ C, whereupon 150 parts of chlorine for 5 st are added at 14O-15O ° C. The titanium tetrachloride is allowed to distill off and the resulting melt is extracted with 300 parts of water containing 30 parts of sulfuric acid. The Polychloro-copper phthalocyanine containing 13 to 16 chlorine atoms per molecule is separated by filtration, washed and dried at 100 ⁰ C.

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EXAMPLE 2

90 parts of titanium tetrachloride, 90 parts of sulphuryl, 22.5 parts of aluminum chloride, 9 parts of bromine and 0.5 parts of iodine are mixed at 20 ⁰ C, is slowly added 30 parts of copper phthalocyanine vrorauf with stirring. The temperature is raised to 140.degree. C., whereupon 150 parts of chlorine are added over 5 hours at 140-150.degree. The titanium tetrachloride is allowed to distill off and the resulting melt is extracted with 300 parts of water containing 30 parts of sulfuric acid. The Polybromochloro-copper phthalocyanine is separated, washed and dried at 100 ⁰ C by filtration.

EXAMPLE 3

25.9 parts of copper phthalocyanine are added with stirring to 176 parts of titanium tetrachloride which contains 18.9 parts of aluminum chloride, 82.5 parts of sulphuryl chloride and 0.25 part of potassium iodide. The temperature is raised to 80 ⁰ C, after which 0.5 parts of iodine as a solution in 10 parts of sulphuryl added dropwise, the temperature being maintained at 80-85 ⁰ C. The temperature is then raised to 135 ° C. over 30-60 minutes and maintained at this value, during which time 300 parts of chlorine gas are added over 6 hours. The titanium tetrachloride is then allowed to distill off and the resulting melt is extracted with 300 parts of water containing 30 parts of sulfuric acid. The Polychloro-copper phthalocyanine is collected, washed and dried at 100 ⁰ C by filtration.

EXAMPLE k

.176 parts of titanium tetrachloride, 1.67 parts of sulphuryl chloride, 2.57 parts of Alumiftiurtichtö * ict and 00S "parts of iodine are used in

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2O ⁰ C were mixed together, after which 25.7 parts Kupferphthalocyanln are slowly added with stirring. The temperature is raised to 150 ^° C., whereupon 150 parts of chlorine for 5 hours

C can be added. The titanium tetrachloride is allowed to distill off, and the polychlorocopper phthalocyanine is obtained according to Example 1.

EXAMPLE 5

176 parts of titanium tetrachloride, 700 parts of sulphuryl, 16 * J parts of aluminum chloride, 0.5 part of iodine and 6 parts of bromine are mixed together at 20 ⁰ C, after which 25.7 parts of copper phthalocyanine are added slowly with stirring. The temperature is raised to 150.degree. C., whereupon 150 parts of chlorine are added over 5 hours at 140.degree.-150.degree. The titanium tetrachloride is allowed to distill off and the polychlorobromo-copper phthalocyanine is obtained according to the procedure of Example 1.

EXAMPLE 6

264 parts of titanium tetrachloride and 18.9 parts of aluminum chloride are ^{mixed together at 20 °} C., whereupon 25.7 parts of copper phthalocyanine are added with stirring. The temperature is raised to 75 ⁰ C, whereupon 83.5 parts sulphuryl during 30 min added. The temperature between 75 and 8O ⁰ C. The temperature is then raised to 130 ⁰ C, whereupon 150 parts of chlorine for 5 st are added at 13O-l4O ° C. The titanium tetrachloride is allowed to distill off and the polychlorocopper phthalocyanine is obtained according to the procedure of Example 1.

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EXAMPLE 7

258 parts of titanium tetrachloride, 23.8 parts of aluminum chloride and 50 parts of thionyl chloride are mixed ^{at 20 ° C.} # whereupon 25.7 parts of copper phthalocyanine are added with stirring. The temperature is raised to 125 ° C., whereupon 150 parts of chlorine are added at 125-135 ° C. over 5 hours. The titanium tetrachloride is allowed to distill off and the polychlorocopper phthalocyanine is obtained according to the procedure of Example 1.

EXAMPLE 8

55 parts of sulphuryl, 1 part of aluminum chloride and 1 part sulfur are mixed together at 20 ⁰ C. After the initial reaction has subsided, 258 parts of titanium tetrachloride are added, followed by the addition of 19.7 parts of aluminum chloride. Then 25.7 parts of copper phthalocyanine are added with stirring. The temperature is raised to 135 ° · C whereupon 150 parts of chlorine during, 5 st at 135-1 ^{1 0} IO C. The polychlorocopper phthalocyanine is obtained as described in Example 1.

EXAMPLE 9

1 part of sulfur dioxide is introduced into 33 parts of sulphuryl chloride, which is stirred at 20 ° C. 23.8 parts of aluminum chloride, 6 parts of bromine and 215 parts of titanium tetrachloride are added, followed by the addition of 25.7 parts of copper phthalocyanine. The temperature is raised to 135 ° C whereupon 150 parts of chlorine are introduced at 135-1 st ¹ IO ⁰ C in Fig.5. The titanium tetrachloride is allowed to distill off, "and the polychlorobromo-kupferphthalo-

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cyanine is then obtained according to the procedure of Example 1.

EXAMPLE 10

400 parts titanium tetrachloride, 200 parts of sulphuryl, 17 parts of phosphorus oxychloride, and 40 parts of aluminum chloride are mixed together at 20 ⁰ C with each other, after which 40 parts Kunferohthalocyanin are slowly added with stirring. The Temneratur is raised to 140 ⁰ C, whereupon 150 parts of chlorine for 5 st be initiated at l4O-15O ° C. The titanium tetrachloride is then allowed to distill off and the polychlorocopper phthalocyanine is obtained according to the procedure of Example 1.

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Claims (12)

PATENT CLAIMS 1; Process for the preparation of polyhalometal phthalocyanines by adding chlorine and / or bromine to a metal phthalocyanine in a titanium tetrachloride medium, characterized in that the titanium tetrachloride medium contains aluminum chloride. 2. The method according to claim I _1, characterized in that the metal phthalocyanine consists of copper phthalocyanine. 3. The method according to claim 1 or 2, characterized in that the amount by weight of the titanium tetrachloride is 0.5 to 20 times the amount by weight of the metal phthalocyanine. 4. The method according to claim 1 or 2, characterized in that that the amount by weight of the titanium tetrachloride is 6 to 10 times the amount by weight of the metal phthalocyanine . 5. The method according to any one of the preceding claims, characterized in that one or more halides or oxyhalides of sulfur or phosphorus are present. 6. The method according to claim 5, characterized in that the halides or oxyhalides of sulfur or phosphorus in amounts by weight up to 15 times the amount by weight 709810/1 118 of aluminum chloride are present. 7. The method according to claim 5, characterized in that that the amount by weight of the halides or oxyhalides of sulfur or phosphorus is 0.1 to 5 times the amount by weight of aluminum chloride. 8. The method according to any one of the preceding claims, characterized in that the amount by weight of the aluminum chloride together with the amounts by weight of any halides or oxyhalides of sulfur or phosphorus present are 0.16 to 3 ² J times the amount by weight of the metal phthalocyanine. 9. The method according to any one of the preceding claims, characterized in that the amount by weight of the Aluminum chloride together with the amounts by weight of any halides or oxyhalides present of sulfur or phosphorus be 0.5 to 5 times the amount by weight of the metal phthalocyanine. 10. The method according to any one of the preceding claims, characterized in that a catalyst is present. 11. The method according to any one of the preceding claims, characterized in that the reaction temperature is 60 to 170 ⁰ C. 12. The method according to any one of the preceding claims, characterized in that the reaction temperature 100 to 140 ° C. 709810/1118 Method according to one of the preceding claims
for the preparation of chlorobromometal phthalocyanines having 1 to 15 bromine atoms, characterized in that the bromination is carried out before the chlorination. Method according to one of the preceding claims,
characterized in that the titanium tetrachloride is recovered by distillation. DR. -ING. H. FINCKE, DIPL .. ING. Mr. QS STAEGER, DR. R * r. nat. R. 709810/1118