JPS5851970B2 - Production method of copper phthalocyanine - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to an improved process for producing copper phthalocyanine.

The method currently widely adopted industrially for producing copper phthalocyanine is a method called a solvent method using phthalic anhydride and urea as raw materials.

That is, l) a method of heating and reacting phthalic anhydride, urea, a copper compound, and a catalyst in an organic solvent; 2) a method in which phthalic anhydride is first converted to phthalimide with ammonia in an organic solvent, and then urea, a copper compound, and There are two methods: adding a catalyst and carrying out a heating reaction.

There have been numerous reports and patents regarding these methods, and various improvements have been proposed regarding solvents, copper compounds, and especially catalysts in order to improve the yield of copper phthalocyanine.

The general reaction method of the solvent method in the phthalic anhydride-urea method is to prepare phthalic anhydride, urea, a copper compound, and a catalyst in a high-boiling organic solvent, and gradually raise the temperature to 170 to 2
Either react at 00°C for several hours, or prepare phthalic anhydride in an organic solvent and pass ammonia scum through it at 150 to 160°C to form phthalimide, then add urea, a copper compound, and a catalyst and raise the temperature. 170 to 200℃
It takes several hours to react.

The produced copper phthalocyanine is completely insoluble in organic solvents and water, so after the reaction is complete, L) filtrate and then steam distill the cake and filter it, 2) V5 filtrate and wash the cake with alcohol, or 3) The organic solvent is removed by means such as distillation and steam distillation followed by filtration.

Next, this cake was placed in 3 ml of sulfuric acid and heated for about 1 hour at 90°C.
After heating to 95°C, filtration is performed while hot, and the cake is washed with boiling water and dried to obtain blister copper phthalocyanine.

Here, the yield of blister copper phthalocyanine relative to phthalic anhydride is defined as the crude yield.

This blister copper phthalocyanine was dissolved in 20 times the volume of concentrated sulfuric acid,
The copper phthalocyanine precipitated by pouring into 200 times the volume of cold water is filtered, thoroughly washed with water, and dried to obtain purified copper phthalocyanine.

The yield of refined steel phthalocyanine relative to phthalic anhydride is defined as the pure yield (by the sulfuric acid method).

Now, when we examine in detail the synthesis methods described in numerous documents and determine their pure yields, we find that cuprous chloride gives the best yield as a copper source.

In addition, the influence of the catalyst on the pure yield is extremely significant, with ammonium molybdate or titanium tetrachloride being particularly good.

That is, the cuprous chloride-ammonium molybdate method provides a pure yield of 84-85%, and the cuprous chloride-titanium tetrachloride method provides a pure yield of 90-91%.

As a result of our basic research on the phthalic anhydride-urea solvent method, we have developed a method for obtaining copper phthalocyanine from phthalic anhydride or phthalimide in a higher yield than previously known methods. was completed.

That is, the present invention is characterized in that when phthalic anhydride or phthalimide is heated to react with urea, a copper compound, and a catalyst in an organic solvent, the reaction is carried out in the presence of an iodine compound. The present invention provides a method for obtaining copper phthalocyanine with high purity and extremely high yield.

The organic solvent used in the present invention is a high boiling point solvent that does not participate in the reaction normally used in copper phthalocyanine synthesis, such as nitrobenzene, trichlorobenzene, kerosene, dodecylbenzene, diisopropylbenzene, diisopropyltoluene, chlornaphthalene,
Examples include methylnaphthalene, isopropylnaphthalene, phenylxyl ethane, alkyl biphenyl, and hydrogenated terphenyl.The appropriate amount of solvent used is 2 to 5 times the amount of phthalic anhydride or phthalimide.

The copper compounds used in the present invention include cuprous chloride, cupric chloride, cuprous oxide, cupric oxide, copper sulfate, copper carbonate, copper hydroxide, copper acetate, copper powder, and cuprous bromide. , cupric iodide, etc., and the amount used is 0.25 copper atoms per phthalic anhydride or phthalimide, which is sufficient.

Next, the iodine compounds used in the present invention include cupric iodide, ammonium iodide, iodide, potassium iodide, sodium iodide, lithium iodide, magnesium iodide, calcium iodide, barium iodide, Strontium iodide, thimonium iodide, aluminum iodide, iron iodide (n), titanium iodide, zirconium iodide (IV), tin iodide (n), zinc iodide (n), lead iodide (If) etc., and the amount used is 0.005 iodine per phthalic anhydride or phthalimide.
0.25 to 0.25 atoms is sufficient, and it is wasteful to use more than this.

That is, 0.01 to 0.1 atom of iodine is particularly suitable.

The amount of urea used in the present invention is 3 to 4 moles relative to phthalic anhydride, and 2 to 3 moles relative to phthalimide.
Moles are sufficient.

Catalysts used in the present invention include molybdenum compounds such as ammonium molybdate, molybdic acid, molybdenum trioxide, and phosphomolybdic acid, titanium compounds such as titanium tetrachloride, metatitanic acid, and titanate esters, zirconium tetrachloride, and zirconyl carbonate. , zirconyl hydroxide,
Zirconium compounds such as zirconium oxychloride, iron(II) chloride, iron chloride (110), zinc chloride, aluminum chloride, etc. are particularly effective, and one or more of these catalysts may be used.

Furthermore, adding ammonium chloride to these catalysts in an amount of 1 mole or less relative to phthalic anhydride or phthalimide has a positive effect.

Since the reaction of the present invention proceeds at a temperature of 170 to 190°C, the reaction system is heated to 170°C, and further heated to 170 to 200°C for 3 to 4 hours.

To isolate copper phthalocyanine from the reaction system, remove the organic solvent by filtration or distillation as described above, boil it with tertiary sulfuric acid, heat-time it, wash with boiling water and dry to obtain blister copper phthalocyanine. get it.

(Calculate roughness rate). Next, 5 g of crude copper phthalocyanine is dissolved in 100 g of concentrated sulfuric acid, poured into 1 l of cold water, filtered, washed with water, dried, and the purified steel phthalocyanine is weighed to determine the purification yield.

The pure yield of copper phthalocyanine relative to phthalic anhydride or phthalimide is determined by the formula: crude yield of copper phthalocyanine x purified yield - pure yield.

When copper phthalocyanine is synthesized in an organic solvent using phthalic anhydride or phthalimide as a raw material by the method of the present invention, a high purity yield that cannot be achieved by conventionally known methods can be obtained. It is a surprising technological progress that it has become possible to achieve a yield of 93-94% and a pure yield of 99-10% using a titanium tetrachloride catalyst.

Furthermore, since the reaction rate of the copper compound is high, the amount of unreacted copper compound flowing into the post-treatment wastewater is also significantly reduced.

Although it is still difficult to fully explain the action of the iodine compound that exerts the characteristic effect in the method of the present invention, it is as follows based on our experiments.

1--Amino-3-iminoisoindolenine produced from phthalic anhydride or phthalimide and urea is deammoniated and condensed to form a four-molecule condensate, which is combined with 1-amino-3-iminoisoindolenine and copper. Either a copper complex is produced from the compound and further deammoniated condensation is performed, or l-amino-3-iminoisoindolenine is deammoniated and condensed to produce a 4-molecular condensed cyclized product, and this and 1-amino-3- A copper complex is produced by a complexing reaction from iminoisoindolenine and a copper compound.

Next, in the process of producing copper phthalocyanine molecules by redox reaction, the redox reaction proceeds after the iodine anion is exchanged with l-amino-3-iminoisoindolenine bonded to copper, so that ■-amino-3-
It is considered that since iminoindolenine is effectively converted to copper phthalocyanine, the yield of copper phthalocyanine is significantly improved.

1 Furthermore, the copper phthalocyanine obtained by the method of the present invention is an extremely pure crystal, and according to analysis results does not contain iodine or chlorine atoms, and can be advantageously used as a raw material for pigments and dyes.

Next, the present invention will be specifically explained using examples.

Example 1 100 g of nitrobenzene and 37.0 g of phthalic anhydride in a 200CC four-bottle flask equipped with a condenser, thermometer, and stirrer.
, urea 60g, cuprous chloride 6.4g, ammonium iodide 3.63,9. Ammonium chloride (the amount shown below) and ammonium molybdate (0.15.9%) are charged, the temperature is raised to 170°C in 1 hour, and the mixture is heated and stirred at 170 to 200°C for 4 hours.

During this time, the internal temperature gradually rises as the reaction progresses.

After the reaction is completed, the mixture is cooled and diluted with 80 cc of methanol to remove the copper phthalocyanine, followed by washing with methanol teeth.

This cake is placed in 500cc of trivalent sulfuric acid, heated and stirred at 95°C for 1 hour, filtered while hot, washed with 500cc of boiling water, and dried to obtain blister copper phthalocyanine.

After dissolving 5.01 g of this crude copper phthalocyanine in 100 g of concentrated sulfuric acid, it is poured into 1 liter of cold water, the precipitate is filtered off, washed with 1 liter of water until neutral, and dried to obtain purified copper phthalocyanine.

θ, urea 60g, cuprous chloride 6.4g, iodine compound (
The procedure is as in Example 1 using 6.7 g of ammonium chloride (below) and 4.75 g of tetrahydral ossified titanium.

Reference example 2 (publicly known method) In the method of Example 3, iodine compounds and * *Omit the use of ammonium chloride and perform the same procedure.

Example 4 100 g of nitrobenzene, 37.0 g of phthalic anhydride
It is heated to 50 to 160°C and ammonia gas is passed through it to form phthalimide.

After adding 45 g of urea, 6.49 g of cuprous salt, 4.2 g of potassium iodide, 6.7 g of ammonium chloride, and a catalyst (described below), the mixture is heated and operated in the same manner as in Example 1.

Further, under the conditions of layer 4-2 above, potassium iodide was added at 1.0
Copper phthalocyanine was obtained in a pure yield of 94.71% by the same procedure except that 5.9 was used.

Example 5 100 g of nitrobenzene, 37.0 g of phthalic anhydride, 60 g of urea, copper compound (below), iodine compound (below),
The procedure is as in Example 1 using 6.7 g of ammonium chloride and 0.15 g of ammonium molybdate.

Reference example 3 (publicly known method) In the method of Example 5, Use of iodine compounds* Operate in the same manner, omitting *.

Example 6 100 g of nitrobenzene, 37.0 g of phthalic anhydride
It is heated to 50 to 160°C and ammonia gas is passed through it for 1 hour to obtain phthalimide.

After adding 45**g of urea, a copper compound (see below), an iodine compound (see below), 6.7g of ammonium chloride, and 0.15.9g of ammonium molybdate, the temperature was raised and Example
Operate in the same way.

Example 7 Kerosene 100g, phthalimide 36.8,9. urea 4
5g of cuprous chloride, 6.4g of cuprous chloride, an iodine compound (described below), 6.7g of ammonium chloride, and 0.15g of ammonium molybdate.

Claims (1)

[Scope of Claims] 1. A copper compound characterized in that the reaction is carried out in the presence of an iodine compound in the reaction of reacting phthalic anhydride or phthalimide with urea, a copper compound, and a catalyst to synthesize copper phthalocyanine in an organic solvent. Method for producing phthalocyanine. 2. The production method according to claim 1, wherein copper iodide, ammonium iodide, sodium iodide, potassium iodide, zinc iodide, or iodide is used as the iodine compound. 3. The production according to claim 1, in which one or more of ammonium molybdate, molybdic acid, molybdenum dioxide, ammonium phosphomolybdate, titanium tetrachloride, zirconium tetrachloride, iron chloride, or zinc chloride is used as a catalyst. Law. 4. The production method according to claim 3, wherein the reaction is carried out by further adding ammonium chloride.