RU2352571C1 - Receiving method of metal phthalocyanine - Google Patents

Abstract

FIELD: metallurgy.

SUBSTANCE: method is implemented by means of interaction phthalic anhydride or its mixture with derivative phthalic acid with carbamide and metal salt at the temperature 190-220°C at presence of catalyst in organic solvent medium, corresponding technological mixture of diisopropyl benzol. By described method there are received phthalocyanine of copper, cobalt, iron, vanadyl, nickel and tin of high-fidelity with high yield. After implementation of condensation constructio solvent is vacuum removed.

EFFECT: it is improved method of receiving metal phthalocyanine.

1 cl, 9 ex, 1 tbl

Description

The aim of the invention was the development of a universal, high-performance and economical method for producing high quality metal phthalocyanines in high yield.

The essence of the invention lies in the fact that the interaction of phthalic anhydride, urea and a salt of the corresponding metal is carried out in the presence of a catalyst in a solvent medium, which is a technical mixture of diisopropylbenzenes with a boiling point of 190-220 ° C. The use of this solvent allows the process to be carried out at a sufficiently low temperature when the solvent is boiling, to remove the solvent under vacuum after synthesis, to isolate the product in solid form, to simplify the hardware design of the process, eliminating the stages of filtration, processing with a low boiling solvent, followed by filtration and drying from an organic solvent (table )

The invention relates to the chemical industry, in particular to a technology for the production of metal phthalocyanines, which are intermediates in the synthesis of phthalocyanine dyes and pigments, and are also used as catalysts in oil and gas purification processes, components of electrophotographic devices.

Metal phthalocyanines (PCMe) are predominantly prepared by reacting phthalic acid or its salts, or anhydride, or imide, or phthalic acid nitrile (as well as their monohalogen derivatives) with a nitrogen source, for example, carbamide, metals or their salts in the presence of a catalyst (molybdenum, tungsten compounds, titanium, boron, etc.).

The methods for producing PCMe conventionally, according to the technological design, are divided into two groups: the interaction of the starting components in high-boiling organic solvents or when they are “baked” at high temperatures without using a solvent.

Thus, methods are known for producing PCMe in nitrobenzene, kerosene, trichlorobenzene (W. Herbst, K. Hunger "Industrielle Organische Pigmente: Herstellung, Eigenschaften, Anwendung", 2., vollst. Überarb. Aufl., S. 439-441, Weinheim; New York; Basel; Cambridge; Tokyo: VCH, 1995). These methods provide the possibility of obtaining high-quality end products, however, the concentration of reacting substances in the reaction mass is low and, accordingly, the productivity of the equipment is low. In addition, there is a problem of separating the solvent from the target product, which is technologically ensured either by distillation of the solvent with water vapor, which leads to the formation of contaminated wastewater and additional energy costs, or by treatment with a low boiling solvent, followed by filtration and drying from an organic solvent.

The principal disadvantages of these methods are low yields in the synthesis of cobalt and nickel phthalocyanines and the inability to obtain iron phthalocyanine.

In addition, the most commonly used solvents (trichlorobenzene and nitrobenzene) are highly toxic.

Ways of "baking" productive (US Pat. Germany DE 2657139 A1, class C07D 487/22, op. 22.06.78; Pat. GDR No. 221189, class C09B 47/06, op. 17.04.85), however, they do not provide for the production of high-quality metal phthalocyanines due to uneven heating of the reaction mass and the formation of difficult to separate impurities.

There is also a method of producing PCMe by heating a mixture of reagents through microwave radiation to a temperature of 180-300 ° C for 5-10 minutes, followed by cooling and purification of the melt (Pat. RU No. 2045555, IPC ⁶ C09B 47/06, op. 10.10.95 g .)

The disadvantages of this method are the high energy intensity and the need to use hard-to-reach unconventional equipment.

The closest in technical essence and the resulting effect is a method for producing metal phthalocyanines according to the patent (Pat. RU 2148582 C1, class C07D 487/22, application 15.04.1999, op. 10.05.2000, (prototype), BI No. 13).

According to this method, metal phthalocyanines are obtained by the interaction of phthalic anhydride or its mixtures with chlorine derivatives of phthalic acid with carbamide and metal salts at elevated temperatures (mainly 130-255 ° C) in the presence of a catalyst in an organic solvent medium, which is a mixture of normal structure aliphatic hydrocarbons with the number carbon atoms C ₁₂ -C ₁₆ with a boiling point of 250-290 ° C.

The method protects the production of a large group of metal phthalocyanines of practical importance in the art.

Despite the high quality of the products provided by this method, it has significant disadvantages:

- high temperature of the process (200-255 ° C), which leads to additional energy costs;

- carrying out the process at temperatures below the boiling point of the solvent (250-290 ° C), which requires the use of additional technical devices to maintain the necessary temperature conditions;

- the selection of final products is carried out by filtration or jointing, which requires additional physical and mechanical equipment;

- a paste of a product containing a working solvent is isolated by repulpation in a low-boiling solvent - isopropanol, followed by filtration and washing with a solvent;

- drying of the final product is carried out from isopropanol, which easily forms explosive mixtures with air;

- in the process of separation mixtures of organic solvents are formed, which require the organization of a technological scheme for their separation.

The aim of this invention was the development of a universal, high-performance and environmentally friendly method for producing high quality PCMe.

The essence of the invention lies in the fact that the interaction of phthalic anhydride or its mixtures with chlorine derivatives of phthalic acid with carbamide and metal salts is carried out at an elevated temperature in the presence of a catalyst in an organic solvent, which is a technical mixture of diisopropylbenzenes. This solvent is released in a large-tonnage process for the production of phenol and acetone by the "cumene" method.

The technical result achieved using this method is expressed in the following:

- the final products after synthesis and removal of the solvent under vacuum are isolated in the form of an easily evacuated solid powder;

- in the process of synthesis of metal phthalocyanines no by-products are formed that require special techniques for their removal;

- the number of technological stages compared to the prototype is reduced by 5 times (reduced filtration, repulpation, filtration, washing, drying) with the same quality of products;

- provides all practically important products based on metal phthalocyanines, including iron phthalocyanine;

- the process does not require technical means to maintain the temperature, since it is carried out at the boiling point of the solvent.

The positive effect of the application of this method is expressed in the following:

- high quality and yield of target products is ensured;

- excludes the formation of wastewater and gas emissions;

- the solvent can be used repeatedly without purification, as it is not contaminated with reaction products;

- the process does not use an additional solvent to isolate products;

- no additional technological schemes are required for the separation of solvents and the capture and regeneration of a low boiling solvent (isopropanol) used to isolate products.

The proposed method is as follows:

the solvent and the starting compounds: phthalic anhydride or its mixture with phthalic acid chlorine derivatives, a salt of the corresponding metal, and a catalyst are charged into a heated reactor equipped with a stirrer, a thermometer, and a reflux condenser. When using derivatives of chlorophthalic acid, ammonium chloride is additionally charged. With constant stirring, heat the reaction mass to 120-135 ° C and give exposure for 1-2 hours, then raise the temperature to 160-170 ° C and give exposure for 1-2 hours, then heat the mass to a boiling point of solvent 190- 220 ° C and maintained at this temperature, depending on the product obtained for 1-10 hours. At the end of the exposure, the reaction mass is cooled to 160-170 ° C and the solvent is distilled off under vacuum, after which the finished product is evacuated.

The proposed method for producing metal phthalocyanines is illustrated by the following examples:

Example 1. Obtaining copper phthalocyanine.

62 ml of solvent are charged into a three-necked flask equipped with a mechanical stirrer, a thermometer and a reflux condenser, and the starting reagents are charged with stirring according to the table. Then begin the slow heating of the reaction mass at a rate of not more than 10 ° C per hour to 135 ° C. At a temperature of 130-135 ° C give an exposure of 1 hour. At the end of the exposure, the mass is heated to 195 ° C at a speed of 10 ° C per hour. When the temperature reaches 195 ° C, an exposure time of 1-5 hours is obtained until the content of copper phthalocyanine in the reaction mass reaches at least 65%, then the flask is evacuated and diisopropylbenzene is distilled off. The dry product is unloaded. 51.48 g of copper phthalocyanine is obtained with a basic substance content of 66%, the yield, counting on phthalic anhydride, is 92.6%.

Example 2. Obtaining copper monochlorophthalocyanine.

Under the conditions of Example 1, 70 ml of a solvent, phthalic anhydride 42.8 g (0.29 g / m), monosodium salt of 4-chlorophthalic acid 21.57 g (0.0965 g / m), and copper monochloride 10.02 were charged into a flask g (0.101 g / m), urea 85.49 g (1.424 g / m), ammonium chloride 8.02 g (0.15 g / m), ammonium molybdate 0.189 g. Copper monochlorophthalocyanine is obtained with a basic substance content of 68% the yield is 92%, the content of bound chlorine is 6.5%.

Example 3. Obtaining cobalt phthalocyanine.

Under the conditions of Example 1, 80 ml of diisopropylbenzene, 37.03 g (0.25 g / mol) of phthalic anhydride, 7.85 g (0.047 g / mol) of cobalt dichloride, 76.6 g (1.28 g / mol) urea and 1.04 g of ammonium molybdate. The mixture is heated with stirring to 120 ° C for 2 hours and maintained at this temperature for 2 hours. Then heated for 2 hours to 160-165 ° C and incubated for 2 hours. After that, the temperature is raised to 200-215 ° C and maintained for 6 hours. At the end of the exposure, the mass is cooled to 160-170 ° C and begin to distill off diisopropylbenzene under vacuum at a temperature in pairs at the end of the distillation of 150-160 ° C. 56.4 g of product are obtained with a basic substance content of 74.1%, and a yield of 94.3%.

Example 4. Obtaining monochlorophthalocyanine cobalt.

Under the conditions of Example 1, 100 ml of diisopropylbenzene was charged into a flask, 56 g (0.375 g / m) of phthalic anhydride, 153 g (2.15 g / m) of urea, 15.7 g (0.1 g / m) of two-water were charged with stirring cobalt chloride, 13.45 g (0.25 g / m) of ammonium chloride, 28.15 g (0.125 g / m) of the monosodium salt of chlorophthalic acid and 1.2 g of ammonium molybdate. The synthesis is carried out at a temperature of 190-220 ° C for 9 hours. 129 g of product are obtained with a basic substance content of 50%; the yield calculated for the monosodium salt of chlorophthalic acid is 87%.

Example 5. Obtaining cobalt dichlorophthalocyanine.

Under the conditions of Example 1, 100 ml of diisopropylbenzene was charged into a flask, 37.03 g (0.25 g / m) of phthalic anhydride, 153 g (2.15 g / m) of urea, 15.7 g (0.1 g) were charged with stirring / m) of two-water cobalt chloride, 25.3 g (0.47 g / m) of ammonium chloride, 56.3 (0.25 g / m) of the monosodium salt of chlorophthalic acid and 2.08 g of ammonium molybdate. The mixture is heated for 2 hours to 130-135 ° C and stirred for 2 hours. Then the mass is heated for 2 hours to 160-165 ° C and maintained at this temperature for 2 hours. Then heated for 2 hours to 200 ° C and maintained for 10 hours. At the end of the exposure, the mass is cooled to 160-170 ° C and begin to distill off diisopropylbenzene under vacuum at a temperature in pairs at the end of the distillation of 150-160 ° C.

154 g of product are obtained with a basic substance content of 45%, the yield calculated for the monosodium salt of chlorophthalic acid is 84.5%.

Example 6. Obtaining iron phthalocyanine.

Under the conditions of Example 1, 80 ml of diisopropylbenzene, 37.03 g (0.25 g / mol) of phthalic anhydride, 10.8 g (0.0666 g / mol) of anhydrous ferric chloride, 55.4 g (0.923 g / mol) urea and 1.04 g of ammonium molybdate. The mixture is heated with stirring to 170 ° C for 2 hours and maintained at this temperature for 1 hour. Then heated for 2 hours to 200 ° C and maintained for 10 hours. At the end of the exposure, the mass is cooled to 160-170 ° C and begin to distill off diisopropylbenzene under vacuum at a temperature in pairs at the end of the distillation of 150-160 ° C. 46.85 g of product are obtained with a basic substance content of 60.7%, the yield is 80%.

Example 7. Obtaining phthalocyanine vanadyl.

Under the conditions of Example 1, 40 ml of diisopropylbenzene, 44.85 g (0.3 g / mol) of phthalic anhydride, 13.44 g (0.062 g / mol) of vanadyl sulfate, 71.25 g (1.19 g / mol) are charged into the flask ) urea and 1.485 g of ammonium molybdate. The mixture is heated with stirring to 120 ° C for 2 hours and maintained at this temperature for 2 hours. Then heated for 2 hours to 160-165 ° C and incubated for 2 hours. After that, the temperature is raised to 200-215 ° C and incubated for 2 hours. At the end of the exposure, the mass is cooled to 160-170 ° C and begin to distill off diisopropylbenzene under vacuum at a temperature in pairs at the end of the distillation of 15 0-160 ° C. 56.4 g of product are obtained with a basic substance content of 74.1%, and a yield of 94.3%.

Example 8. Obtaining phthalocyanine nickel.

Under the conditions of Example 1, 80 ml of a solvent, 37.03 (0.25 g / mol) of phthalic anhydride, 16.85 g (0.06 g / mol) of nickel heptahydrate, 76.6 g (1.28 g) are charged into a flask / mol) urea and 1.04 g of ammonium molybdate. The process is carried out at a temperature of 190-220 ° C for 9 hours. 34.86 g of product are obtained with a basic substance content of 73%, yield 72%.

Example 9. Obtaining tin phthalocyanine.

Under the conditions of Example 1, 100 ml of a solvent, 37.03 (0.25 g / mol) of phthalic anhydride, 11.38 g (0.06 g / mol) of tin dichloride, 76.6 g (1.28 g / mol) urea and 0.8 g of ammonium molybdate. The process is carried out at a temperature of 190-220 ° C for 12 hours. 36 g of product are obtained with a basic substance content of 43%, yield 37%.

Claims (1)

A method of producing metal phthalocyanines by reacting phthalic anhydride or a mixture thereof with chlorine derivatives of phthalic acid, urea and metal salts in the presence of a catalyst when heated in an organic solvent, characterized in that a mixture of diisopropylbenzenes is used as the solvent.