The method of obtaining metal phthalocyanines

 

(57) Abstract:

The objective of the invention was to develop a versatile, high-performance, environmentally friendly method of producing phthalocyanine metal of high quality. The essence of the invention lies in the fact that the interaction of phthalic anhydride, urea and salts of the corresponding metal is carried out in the presence of a catalyst in the environment of high-boiling solvent which is a mixture of aliphatic hydrocarbons of normal structure with the number of carbon atoms WITH12-C16with a boiling point of 250 - 290oC. Technical result achieved by using the specified solvent, is expressed in the following: end-products form of a thin suspension in the solvent, which allows their separation by ordinary filtering or jointing; exclude adverse reactions of chlorination phenyl nuclei of the phthalocyanine, leading to a sharp deterioration in the coloristic properties phtalocyanine dyes and pigments; performance standard equipment increases 4 to 5 times; the proposed solvent does not contain aromatic compounds and belongs to the 4th (most Nizkor technologies for metal phthalocyanines, which are intermediates in the synthesis of phtalocyanine dyes and pigments and are used as catalysts in the process of refining oil and gas.

Typically, metal phthalocyanines (PcMe) produced by interaction of phthalic acid or anhydride, or imide, or nitrile phthalic acid (and their monochloropropane) with a nitrogen source such as urea, metals or their salts in the presence of a catalyst (compounds of molybdenum, tungsten, titanium and others).

Methods of obtaining PcMe conventionally, technological design, are divided into two groups: the interaction of the initial components in a high-boiling organic solvents or when they are fused at high temperatures without the use of solvent.

Thus, known methods for producing PcMe in nitrobenzene (Venkataraman "the Chemistry of synthetic dyes" volume II, page 1290, L.-D., Chemistry, 1957), kerosene (Potnis SP, A. Daruwala Century Painindia, 1969, 19, N 8), trichlorobenzene (Ed. mon. USSR N 362858 MKI3C 09 B 47/06, Z. 7.08.70 g, op. 20.12.72, BI N 3 (1973 ), ed. mon. USSR N 411110, 09 At 47/06, Z. 05.06.72 g, op. 15.11.74, BI N 2 (1974). These techniques offer the possibility of obtaining a final product of high quality, however, the concentration of the reacting substances in the mass difficult to separate, causing the solvent is distilled off with steam, which leads to the formation of polluted waters and leads to high energy costs.

A significant drawback of these methods are low outputs in the synthesis of phthalocyanines, cobalt and Nickel and the impossibility of obtaining the iron phthalocyanine.

An additional difficulty is the high toxicity of the most frequently used solvents (nitrobenzene and trichlorobenzene).

"Sintering" or get PcMe Plav productive (U.S. Pat. Czechoslovakia N 124140, CL 22 7/02, op. 15.08.67,, Vestnik, 15 srpnu, 1967), but do not provide the possibility of obtaining a final product of high quality due to uneven heating of the reaction mixture and education are difficult to separate impurities.

Known for high-performance method of obtaining PcMe by heating a mixture of the raw materials by microwave radiation to a temperature of 180-300oC for 5-10 minutes, followed by cooling and cleaning of the alloy (U.S. Pat. EN N 2045555, IPC609 In 47/06, Z. 30.03.93 g, op. 10.10.95, BI N 28).

The disadvantage of this method is the high energy consumption and the need for hard-to-use neotraditional get PcCu according to the U.S. patent (U.S. Pat. US 4140695, NCI 540-141, MKI 09 In 47/04, Z. 15.12.1977 g, op. 20.02.1979, (prototype), Officiul gazette of the US patent, No. 3, V. 979 (1974)).

According to this method PcCu receive when interacting phthalic anhydride or phthalimide with copper compounds and urea in the presence of a catalyst in the environment polyalkylbenzenes at a temperature of 130-280oC, mostly in 160-250oC, the duration of the synthesis of 2-8 hours, at atmospheric or increased pressure.

Polyalkylbenzene have at least 2 alkyl groups with carbon atoms of C1-C3.

Despite the high quality of the product provided by the method, it has significant drawbacks:

- explosion process, due to the formation at a high temperature of hydroperoxides;

- high toxicity of chlorinated aromatic compounds;

- the high cost of the solvent;

- the need to use high blood pressure;

the separation of the final product and solvent by distillation, the last under reduced pressure;

the method protects only the synthesis of PcCu.

The objective of the invention was to develop a versatile, high-performance and sustainable ciscogate interaction of phthalic anhydride or its mixtures with chlorinated phthalic acid with urea and salts of metals is carried out at an elevated temperature in the presence of a catalyst in the environment of an organic solvent, representing a mixture of aliphatic hydrocarbons of normal structure with the number of carbon atoms C12-C16. This solvent does not contain aromatic compounds and belongs to the 4th (lowest) category of toxicity.

Technical result achieved when using this method, is expressed in the following:

- end products form a thin slurry in a solvent that allows selection of conventional filtration or jointing;

- excluded adverse reactions of substitution of the phenyl nuclei of the phthalocyanine (chlorination, sulfonation), leading to a sharp deterioration in color phtalocyanine dyes and pigments;

performance standard equipment increases 4-5 times;

- provides the possibility of obtaining iron phthalocyanine, the synthesis of which other techniques to carry out is almost impossible.

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

- eliminated the formation of contaminated wastewater;

- provides high quality end-products;

the deep branch of the solvent from the target product allows you receive the tel can be reused without cleaning, so as not contaminated with reaction products.

The proposed method is as follows:

the reactor is heated, equipped with a stirrer, thermometer and air refrigerator, download the solvent and the source connection: phthalic anhydride or its mixture with gliftalevoj acid, salt of the corresponding metal and the catalyst. With constant stirring, for 6 hours, raise the temperature to 160oC, then in the next 5 hours to 200-260oC and kept at this temperature for another 5 hours. After aging the reaction mass is then cooled and filtered. Sediment metal phthalocyanines repulping in isopropanol, filtered and washed on the filter with another portion of isopropanol. The pasta is dried at a temperature of 70-120oC and get the final product.

The proposed method of producing phthalocyanine metals is illustrated by the following examples:

Example 1. Obtaining of copper phthalocyanine.

In a 4-necked flask equipped with electric stirrer, air refrigerator and thermometer, pour 120 ml of solvent and the source reagents according to the table.

With constant stirring the reaction mass raise temperame 5 hours. After aging the reaction mass is then cooled and the precipitate is filtered on a Buechner funnel, get 95 ml of the filtrate, which without distillation return for the next synthesis. The precipitate from the filtrate repulping in 50 ml of isopropanol, filtered and washed on the filter with 25 ml of isopropanol.

The paste is dried at 70-80oC and get to 29.7 g of copper phthalocyanine with a basic substance content of 70%, the output (counting on phthalic anhydride) was 82%.

Example 2. Getting monochlorotoluene copper.

In the conditions of example 1 in a flask is charged with 120 ml of solvent, phthalic anhydride 19,45 g (0,1312 g/m), mono-Na salt of 4-gliftalevoj acid 9,74 g (0,04376 g/m), copper chloride 4.5 g (0.05 g/m), urea 36,7 g (0,642 g/m), ammonium molybdate and 0.08 g

The reaction and aging is carried out at a temperature of 240oC.

Received of 32.5 g of the final product with a basic substance content of 62.8%, the yield of 76.3%, a combined chlorine content of 6.5%.

Example 3. Getting PcCu.

In the conditions of example 1 in a flask is charged with 125 ml of solvent, of 25.5 g (0.18 g/m) of phthalic anhydride, 42.5 g (0.7 g/m) of urea, 6.8 g (0,04244 g/m) sulfate copper and 0.08 g of ammonium molybdate.

Synthesis and extract the reaction mixture is carried out at those who d 74,8%.

Example 4. Getting PcCo.

In the conditions of example 1 in a flask is charged to 25.2 g (0.172 g/m) of phthalic anhydride, of 38.7 g (0,6366 g/m) of urea, 4,08 g (0,03183 g/m) cobalt chloride and 0.08 g of ammonium molybdate.

The synthesis was carried out at a temperature of 250oC. Obtained 30.0 g of the final product, the content of the basic substance 65,8%, output 61,25%.

Example 5. Getting monochlorotoluene cobalt.

In the conditions of example 1 in a flask is charged with 120 ml of solvent, 16,47 g (0,1112 g/m) of phthalic anhydride, 7,298 g (0,0328 g/m) sodium salt of 4-gliftalevoj acid, 36.5 g (0.6 g/m) of urea, of 12.76 g (0,04385 g/m) CoCl26H2O, 0.08 g of ammonium molybdate. The synthesis is carried out at 250oC.

Get to 20.5 g of product with a basic substance content of 60%, the output is 50%.

Example 6. Getting Dichlorotoluene cobalt.

In the conditions of example 1 load of 11.15 g (0.075 g/m) of phthalic anhydride, 14.6 g (0,0656 g/m) sodium salt of 4-gliftalevoj acid, of 12.76 g (0,04385 g/m) CoCl26H2O, 37.5 g (0,06095 g/m) of urea, 0.2 g of ammonium molybdate in 125 ml of solvent. The synthesis is carried out at a temperature of 240-250oC.

Obtain 22 g of the product with the content of the basic substance is 59%, the output is 50%.

Example 7. Getting the FTA " who/m) urea, the 5.65 g (0.02 g/m) semimodule Nickel sulfate, 0.1 g of ammonium molybdate and 60 ml of solvent. The process is conducted at a temperature of 240-250oC.

Get 11,58 g of product with a basic substance content of 72.9%, exit - 71,16%.

Example 8. Getting iron phthalocyanine.

In the conditions of example 1 in a flask is charged to 24.7 g (rate 0.162 g/m) of phthalic anhydride, 36.5 g (0.6 g/m) of urea, a 8.34 g (0.03 g/m) semimodule of ferrous sulfate, 0.2 g of ammonium molybdate and 115 ml of solvent. The process is conducted at a temperature 245-255oC.

Get 39,1 g of product with a basic substance content of 40%, the yield was 70%.

Example 9. Obtaining vanadium phthalocyanine (vanadyl phthalocyanine).

In the conditions of example 1 in a flask is charged with 7.4 g (0.05 g/m) of phthalic anhydride, 18.0 g (0.3 g/m) of urea, of 2.92 g (0.025 g/m) of ammonium Vanadate, 0.1 g of ammonium molybdate and 50 ml of solvent. The process is conducted at a temperature 245-250oC.

Obtain 5.9 g of product with a basic substance content of 61%, the output of 49.9%.

Example 10. Getting phthalocyanine tin.

In the conditions of example 1 in a flask is charged with 12.3 g (of 0.081 g/m) of phthalic anhydride, 20.2 g (0.3 g/m) of urea, 3.8 g (0.02 g/m) douglasthe tin, 0.1 g of ammonium molybdate and 60 ml of solvent. The process is carried out by the

The method of obtaining metal phthalocyanines interaction of phthalic anhydride or mixtures thereof with chlorinated phthalic acid, urea and salts of metals in the presence of a catalyst when heated in the organic solvent, wherein the solvent a mixture of aliphatic hydrocarbons of normal structure with the number of carbon atoms C12-C16.

 

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