JPS5851971B2 - 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 used industrially for producing copper phthalocyanine is a method called a solvent method using phthalic anhydride and urea as raw materials.

Namely, ■) 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 into phthalimide with ammonia in an organic solvent, and then urea, a copper compound, and a catalyst are added thereto. There are two methods: a heating reaction method.

Many papers and patents have been published regarding these methods, and various improvements have been made to 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 200°C.
Either by reacting for several hours at 150-160°C, or by preparing phthalic anhydride in an organic solvent and passing ammonia gas through it at 150-160°C to form phthalimide, then adding urea, a copper compound and a catalyst and raising the temperature to 170-160°C. The reaction is carried out at 200°C for several hours.

Since the produced copper phthalocyanine is completely insoluble in organic solvents and water, after the reaction is completed, 1) filtration and then steam distillation of the cake and filtration, 2) filtration and washing the cake with alcohol, or 3) The organic solvent is removed by means such as distillation and steam distillation followed by filtering.

Next, this cake was placed in 3-polysulfuric acid and heated for about 1 hour at 90~
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 fucuric anhydride is defined as the blister ratio.

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 purified copper phthalocyanine relative to phthalic anhydride is defined as the pure yield (according to 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 cupric chloride gives the best yield as a copper source.

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

That is, the cuprous chloride-ammonium molybdate method gives a pure yield of 8 to 85 φ, while the cuprous chloride-titanium tetrachloride method gives 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 producing 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 a bromine 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 directly participate in the reaction, such as those normally used in copper phthalocyanine synthesis, such as 21-lobenzene, trichlorobenzene, kerosene, dodecylbenzene, diisopropylbenzene, diisopropyltoluene, Examples include chlornaphthalentutylnaphthalene, isopropylnaphthalene, phenylxylylethane, alkyl biphenyl, and hydrogenated terphenyl, and the appropriate amount of solvent to be 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.

Bromine compounds used in the present invention include copper bromide, ammonium bromide, bromine, potassium bromide, sodium bromide, lithium bromide, magnesium bromide, calcium bromide,
barium bromide, strontium bromide, antimony bromide,
Aluminum bromide, iron bromide, titanium bromide, zirconium bromide, tin bromide, zinc bromide, lead bromide, iodine bromide, etc. are used, and the amount used is 0 as bromine compared to phthalic anhydride or phthalimide. 0.005 to 0.25 atoms are sufficient, and 0.01 to 0.1 atoms as bromine are particularly suitable.

The amount of urea used in the present invention is sufficient to be 3 to 4 moles relative to fucuric anhydride, and 2 to 3 moles for phthalimide.

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 carbonic acid. Zirconium compounds such as zirconyl, zirconyl hydroxide, zirconium oxychloride,
Iron chloride (n), iron chloride value), 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 mol or less relative to fucuric 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 170C, and further heated to 170 to 200C for 3 to 4 hours.

To isolate copper phthalocyanine from the reaction system, remove the organic solvent by the filtration method or distillation method as described above, boil it with 3 ml of sulfuric acid, filter it while hot, wash it with boiling water and dry it to obtain blister copper. Obtain phthalocyanine (calculate roughness rate).

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

Next, the pure yield of copper phthalocyanine with respect to phthalic anhydride or phthalimide is determined by the formula: roughness ratio of copper phthalocyanine x purified yield x 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 major technological advance that a pure yield of 96 steam can be achieved using a polytitanium tetrachloride catalyst with a 92 yield.

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.

The method of the present invention (the action of the bromine compound that exerts the characteristic effect here) is still difficult to fully explain, but based on our experiments, it is as follows.

1-Amino-3-iminoisoindolenine produced from fucuric anhydride or phthalimide and urea undergoes deammonization condensation t2 to form a four-molecule beam combination, and from this, 1-amino-3-iminoisoindolenine and a copper compound. A copper complex is generated and further deammoniated condensation is performed, or 1
-Amino-3-iminoisoindolenine is deammoniated and condensed to form a 4-molecular cyclized product, and a copper complex is formed by complexing reaction with this from 1=amino-3-iminoisoindolenine and a copper compound. generate.

Next, during the redox reaction (thus, in the process of producing copper phthalocyanine molecules), the bromine anion exchanges considerably with 1-amino-3-iminoisoindolenine bound to copper before the redox reaction proceeds. Since amino-3-iminoisoindolenine is effectively converted to copper phthalocyanine, it is considered that the yield of copper phthalocyanine is significantly improved.

In addition, the copper anine obtained by the method of the present invention is an extremely pure crystal, and according to analysis results, it does not contain bromine or chlorine atoms, so it can be advantageously used as a raw material for pigments and dyes. be.

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

Example 1 In a 200 cc fourth flask equipped with a condenser, thermometer, and stirrer, 100 g of nitrobenzene and 37.0 g of phthalic anhydride were added.
g, 609 g of urea, 64 g of cuprous chloride, bromine compound (amounts shown below), 6.7 g of ammonium chloride, and 0.15 g of ammonium molybdate were charged, and the temperature was raised to 170'C in 1 hour, and then from 170 to 200°C. Heat and stir for 4 hours.

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

After the reaction is completed, it is cooled, diluted with 80 cc of methanol, filtered to remove copper phthalocyanine, and washed with 100 cc of methanol.

This cake is placed in 50cc of trivalent sulfuric acid, heated and stirred at 95°C for 1 hour, filtered while hot, washed with 80Qcc of boiling water, and dried to obtain blister copper phthalocyanine.

This blister copper phthalocyanine 5.00.9 was added to 100g of concentrated sulfuric acid
After dissolving in water, pour into 1 liter of cold water, filter the precipitate once, and add 1 liter of water.
Wash and dry until neutral in Step 1 to obtain purified copper phthalocyanine.

The results are as follows.

Reference Example 1 (Known Method) The following results were obtained by performing the same procedure as in Example 1 except for omitting the use of the bromine compound.

Example 2 The procedure was as in Example 1 using 100 g of nitrobenzene, 37.0 g of phthalic anhydride, 605' of urea, 8.97 g of cuprous bromide, 6:7 g of ammonium chloride and 0.159 g of ammonium molybdate. The following results were obtained.

Example 3 Nitrobenzene 100g, phthalic anhydride 37.0g, urea 60g, cuprous chloride 6.4g, ammonium bromide 2.
45 g, ammonium chloride 6.7 g and titanium tetrachloride 4
．． The following results were obtained using Example 759 in the same manner as in Example 1.

Reference Example 2 (Known Method) The method of Example 3 (here, the use of the bromine compound and ammonium chloride was omitted and the same procedure was performed to obtain the following results).

Example 4 Nitropenbenzene 100g, Fucric anhydride 37.0g
is heated to 150 to 160°C and ammonia gas is passed through to form phthalimide.

45 g of urea, 6.4 g of cuprous chloride, 2.9 g of potassium bromide
8g, ammonium chloride 6-7g and catalyst (amounts below)
was added, the temperature was raised, and the same procedure as in Example 1 was carried out to obtain the following results.

Also, under the conditions of 442 above, the amount of potassium bromide was reduced to 0.
By carrying out the same procedure except that the amount was changed to 9 g, copper phthalocyanine was obtained with a pure yield of 94.2%.

Example 5 Nitrobenzene 100. ! 9. Fucric anhydride 37.0g
The following results were obtained in the same manner as in Example 1 using 52.5 g of urea, 6.4 g of cuprous chloride, 4 g of bromine, 6.7 g of ammonium chloride, and 0.15 g of ammonium molybdate.

Claims (1)

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