JPH0653941B2 - Manufacturing method of metal phthalocyanine - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to improvements in the production of metal phthalocyanines.

West German Patent Application Publication No. 2006663 describes a process for producing metal phthalocyanines from aromatic o-dinitriles and powdered metals or specific compounds of these metals.
In that case, the reaction is carried out in the presence of an alkali metal or metal-earth metal hydroxide, oxide, peroxide or carbonate in an amount of 10 to 10.
It is carried out in an organic solvent at 100 ° C. The yield of metal phthalocyanine is about 70 to 75 based on the used o-dinitrile.
%. This method is disclosed in West German Patent Application Publication 200670.
According to the method known from U.S. Pat. No. 7, the addition of complexing compounds for metals to the reaction mixture is improved. Thus, the yield of metal phthalocyanine is improved to 93%. Both methods clearly show that the product is contaminated with phthalimide, metal isoindoline and triazine, and the yield of metal phthalocyanine in many metals is 9
The disadvantage is that it is 0% or less.

The object of the present invention was to improve the known process in such a way that the metal phthalocyanines can be obtained in high purity and good coloristic properties in as quantitative a yield as possible.

We have used a hydrogen-releasing anode and an inert cathode, while introducing hydrogen in the absence of oxygen, in the presence of an alkali metal alcoholate or alkali metal amide, in a solution or suspension in an essentially water-free solvent. When an aromatic o-dinitrile in the form of a suspension is electrochemically reacted with a water-free metal compound, the aromatic o-dinitrile in an organic solvent is present in the presence of an alkaline agent.
It has been found that a highly valuable metal phthalocyanine can be obtained by reacting dinitrile.

According to the method of the present invention, metal phthalocyanine can be obtained in a yield of 90% or more, often 95% or more, and of high purity (95% or more).
% Or more, 98.5% or more in the case of copper phthalocyanine). The product of the process is easy to disperse in its particles and thus in the medium used. The metal phthalocyanines obtained by the process according to the invention give a deep and glossy colouration.

The method of the present invention is generally carried out as follows. In a cell containing an inert cathode and a hydrogen-releasing anode, a solution or suspension of o-dinitrile in an organic solvent is charged together with an alkali metal alcoholate or alkali metal amide and a water-free metal compound. . In order to enhance the conductivity, preferably a conductive compound (hereinafter referred to as a conductive salt) is added, and oxygen is removed from the solution / suspension by an inert gas. Electrolysis is performed at room temperature to 250 while introducing hydrogen.
C., preferably 80.degree. C. or higher, particularly preferably 100 to 250.
It is carried out in an atmosphere of inert gas at a temperature of ° C. The precipitated product is isolated by a conventional method.

As the aromatic o-dinitrile, for example, the following ones are used. O-phthalodinitrile optionally substituted by an alkyl group, an alkoxy group, a chlorine atom, a bromine atom or a phenyl group, for example o-phthalodinitrile, mono-,
Di-, tri- and tetrachloro-o-phthalodinitrile, mono- and dibromo-o-phthalodinitrile, methyl- and dimethyl-o-phthalodinitrile, methoxy-
o-phthalodinitrile, phenyl- and diphenyl-o
-Phthalodinitrile (in which case the mono- and disubstituted dinitriles preferably have substituents at the 4 or 5 or 4 and 5 positions), and also naphthalene-
1,2-dinitrile and naphthalene-2,3-dinitrile. Unsubstituted o-phthalodinitr is excellent as the dinitrile.

The following are used as the organic solvent for this method. Primary alkane residue may be straight-chain or branched, and tertiary _C 1 _{-C 12} - _alkanols, C 2 -C ₆
- _alkanediols, C 3 -C ₆ - alkane triol, and their di - monoalkyl ethers and triols, poly _-C 2 -C ₆ - alkanediols, polyethylene _-C 3 -C ₆ - alkane _triol, C 1 -C ₃ - alkanoic acid _N-C 1 _{~C 4} - alkylamides and N, N-
Bis - _(C 1 ~C ₄ - alkyl amide) or a mixture thereof liquids. Specific examples of the organic solvent include the following.

C ₁ -C ₁₂ - alkanols: methanol, ethanol, propanol, isopropanol, butanol, isobutanol, secondary butanol, tert-butanol, amyl alcohol, isoamyl alcohol, secondary amyl alcohol, n- hexanol, isohexanol, n- heptanol , Isoheptanol, n-octanol, isooctanol, 2-ethyl-hexanol, n-nonanol, isononanol, n-decanol, isodecanol, n-dodecanol and isodecanol.

C ₂ -C ₆ - alkanediols and _C 3 -C ₆ - alkane triol and polyether: ethylene glycol, diethylene glycol, triethylene glycol,
Polyethylene glycol having 4, 5, and 6 glycol units, propylene glycol-1,2, propylene glycol-1,3, dipropylene glycol,
Polypropylene glycol having 3 to 6 propylene glycol units, glycerin, butane-1,2,4-
Triol, butanediol-1,4, butanediol-1,3, pentanediol-1,5 and hexanediol-1,6.

Aliphatic carboxylic acid amide: N-methylformamide,
N, N-dimethylformamide, N-ethylformamide, N, N-diethylformamide, N, N-dipropylformamide, dimethylacetamide, N, N-diethylacetamide, N, N-dipropylacetamide,
N, N-dimethylpropionamide, N, N-diethylpropionamide and N, N-dipropylpropionamide.

As the organic solvent, C ₁ -C ₆ -alkanol and ethylene glycol monoalkyl ether are excellent,
C 3 _-C 6 _- alkanols example propanol, isopropanol, n- butanol, secondary butanol, isobutanol, tert-butanol, amyl alcohol, isoamyl alcohol, n- hexanol, secondary hexanol, isohexanol and 2-ethylhexanol and ethylene The monoethyl- and monobutyl ethers of glycols are excellent. This is because a high yield of phthalocyanine is obtained in this solvent, and the work-up of the reaction mixture can be carried out by simple drying of the organic liquid adhering to the phthalocyanine.

The amount of the solvent is not strictly limited as long as the reaction mixture can be well mixed before, during and after the reaction. Usually, the solvent is 4 to 40 times, preferably 10 to 20 times the o-dinitrile.
Use double weight.

As the metal compound, a water-free metal salt or metal oxide of an inorganic acid or a carboxylic acid is used. Examples are sulfates, chlorides, phosphates, carbonates, nitrates, formates, acetates, propionates, stearates, palmitates, sulfonates, as well as hydroxycarbonates and oxide hydrates. Can be given.

Preferably metal salts are used in the form of complex compounds with ammonia and / or amines. In that case, complex compounds of carboxylic acid metal salts such as acetate, formate, propionate and hexanoate with aminocarboxylic acids such as glycine, sarcosine, valine, α-alanine and α-aminohexanoic acid are particularly excellent. .

These metal complex compounds can be produced electrochemically by carrying out metal dissolution at the anode in a water-free organic electrolyte, which preferably contains carboxylic acids or ammonium and / or amine salts of carboxylic acids. Suitable solvents for this purpose are, for example, C ₁ -C ₆ -alkanols, dimethylformamide, N-methylpyrrolidone, dimethylacetamide and N-formylmorpholine. The electrolysis is carried out in the presence of air or oxygen and the metal complex compound is obtained in a yield of about 98%.

The following are used as alkali metal alcoholates and alkali metal amides for the method of the present invention. Compounds of potassium and lithium amides, preferably sodium amides, potassium of C ₁ -C ₆ -alkanols as alcoholates, especially lithium. Sodium methylate, sodium ethylate, sodium propanolate, sodium- and potassium-tertiary butyrate are recommended due to the ready availability of these alcoholates. The amount of these alkaline-acting compounds is generally 0.01 to 1.5 mol, preferably 0.4 to 0.6 mol, per mol of the aromatic o-dinitrile.

As a cathode, 250 mV, which is inert to the electrolyte
Above, a material having a hydrogen overvoltage (measured with respect to a standard hydrogen electrode) not exceeding 600 mV is used. 8-12% by weight
Chromium-nickel-steel having a nickel content of 100 and nickel-iron alloys containing 30-70% by weight of nickel are excellent.

Suitable anode materials for hydrogen release are, for example, graphite or graphite coated with nickel boride (NiB, Ni ₂ B).
It is a titanium carrier or a zircon carrier. The electrode material can be used as a tight body or in the form of a porous tube. When using a porous tube, the gas treatment of the electrolyte is carried out through the electrode by placing the interior space of the tube further under a hydrogen atmosphere, avoiding the deposition of metal phthalocyanine on its surface.

The synthesis of metal phthalocyanines is preferably carried out in the presence of substances which serve as catalysts such as urea, ammonium carbamate, pyridine, quinoline, hydroquinone or alkylamines such as triethylamine, tripropylamine or di- or tributylamine. The concentration of the catalyst may be 0.001 to 5% by weight, preferably 0.05 to 0.5% by weight, based on the reaction mixture.

In order to increase the conductivity of the reaction mixture, it is advantageous to add to it a conductive compound (conductive salt), preferably a quaternary ammonium salt. The individual examples are as follows. Tetraethylammonium salt of ethylsulfuric acid, o- and p-toluolsulfonic acid, p-butylbenzolsulfonic acid or p-hexylbenzolsulfonic acid. Among these compounds, tetraethylammonium ethylsulfate, tetrapropylammonium propylsulfate or tetrabutylammonium butylsulfate is excellent.

In the examples below,% relates to weight.

Example 1 Nickel 40% Nickel iron alloy cathode and Graphite tube anode whose surface was coated with nickel boride (surface area 2
7-dm ² ), an o-phthalodinitrile 52
A solution from 3 g, 9000 g n-butanol, 46 g sodium as sodium propylate, 3 g urea, 40 g triethylamine and 159 g anhydrous copper sulphate and 20 g tetraethylammonium sulphate are charged. Electrolysis is carried out at a current density of 280 A / m ² while introducing hydrogen at 108 ° C.

The reaction ends after 53.6 Ah. 580 g of Cu-phthalocyanine (purity: 98.5%) are obtained from the reaction mixture as a very finely dispersible and finely divided product. The yield is 99% based on copper sulfate.

Example 2 In the same electrolytic cell as in Example 1, o-phthalodinitrile 523 was added.
g, ethylene glycol monobutyl ether 9000
g, sodium as sodium propylate 46
g, urea 3 g and anhydrous cobalt sulphate 155.1 g and tetraethylammonium sulphate 20 g. Electrolysis is carried out at 110 ° C while introducing hydrogen at 280A /
It is performed at a current density of m ² .

The reaction ends after 53.6 Ah. From the reaction mixture, 540 g of Co-phthalocyanine (purity: about 98%) is obtained.
The yield is 92.6% based on cobalt sulfate.

Example 3 In the same electrolytic cell as in Example 1, o-phthalodinitrile 512 was added.
g, 9000 g of hexanol, 5 g of sodium as sodium propylate, copper (II) acetate in hexanol
The solution is charged with a solution from 185 g of anhydrous diamine-copper (II) acetate prepared by pressing in ammonia gas. Electrolysis is carried out at 110 ° C, while introducing hydrogen, 300A
It is performed at a current density of / m ² . The reaction ends after 53 Ah. 570 g of copper phthalocyanine with a purity of 99.5% is isolated from the reaction mixture. Yield 96.5% based on copper salt
Is.

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Peter Thoma Germany 6710 Frankenthal Peter Skopfushiuturase 2 (56) References Japanese Patent Publication Sho 59-12696 (JP, B2)

Claims (7)

[Claims] 1. A solution or suspension in an essentially water-free solvent in the presence of an alkali metal alcoholate or alkali metal amide using a hydrogen-releasing anode and an inert cathode while introducing hydrogen in the absence of oxygen. Aromatic o-dinitriles in the presence of alkaline agents are characterized in that the aromatic o-dinitriles in the form of a suspension are reacted electrochemically with a water-free metal compound in the presence of an alkaline agent. By reacting,
Manufacturing method of metal phthalocyanine. 2. The method according to claim 1, wherein the reaction is carried out in a solvent having a water content of 0.08% by weight or less. 3. A primary, secondary or tertiary C as an organic solvent.
₁ -C ₁₂ - _alkanols, C 2 -C ₆ - _alkanediols, C 3 -C ₆ - alkane triols, poly _-C 2 ~
C ₆ - alkanediol, the poly _-C 3 -C ₆ - alkane _{triol, C 1 ~C 3 - N-} C 1 ~C 4 alkanoic acid
- _alkylamide, C 1 -C ₃ - alkanoic acid N, N-
Bis -C 1 _-C 4 _-, characterized by using an alkylamide or mixtures thereof, The method according to paragraph 1 or 2 claims. 4. A C ₃ -C ₆ -alkanol, ethylene glycol monoethyl ether and / or ethylene glycol monobutyl ether is used as the organic solvent, according to claim 1 or 2. The method described. 5. A water-free metal salt of an inorganic acid or a carboxylic acid is optionally used in the form of an amine complex compound or a metal oxide as the metal compound. The method according to any one of item 4. 6. The method according to any one of claims 1 to 5, wherein the solvent contains a conductive compound. 7. The method according to claim 6, characterized in that a tetraalkylammonium salt is used as the conductive compound.