DE2403706A1 - PROCESS FOR THE PRODUCTION OF CHLORINATED COPPER PHTHALOCYANINES - Google Patents

Description

2Λ03706

-R Έ HOECHST AG

Date: January 25, 197 ^Z *

File number: HOE Jk / F 024 Dr.OT / Fu

Ver f a lead for the manufacture ung l v on. chlorinated copper rphth alocy anines

Various reaction media have become known for the chlorination of copper phthalocyanine with chlorine. For example, the chlorination can be carried out in chlorosulfonic acid according to US Pat. No. 2 6δ2 85 and according to German Pat. No. 922,081. C

These processes have the disadvantage that the production of a chlorinated copper phthalocyanine with a constant chlorine content and degree of purity requires a complicated temperature control _. and trotadem © ine partially oxydati \ ^y e destruction URXD Õîä considerable Suifierung of Kupferphthaiocyanine non ™

509833/0766, '

** fce ⁴ ^

are moidable. Another method is chlorination of copper phthalocyanine with gaseous chlorine in oleum, which is described in German Patent No. 1 210 111 will. In this process, gaseous chlorine is produced in the presence of iodine and at a low temperature passed through a solution of copper phthalocyanine in oleum, until the desired degree of chlorination is reached. The reaction mixture is then poured into an excess of water stirred in * the chlorine-containing copper phthalocyanine is sucked off and after being washed neutral with water, subjected to an additional treatment with aqueous sodium hydroxide solution.

This process also has significant disadvantages * The chlorination of copper phthalocyanine to a chlorine content of 5-8 % t, corresponding to 1 chlorine atom per molecule of copper phthalocyanine, according to the information in this patent, requires chlorination times of 7 to 10 hours, which significantly limits the economic efficiency of the process. In contrast, the introduction of more than 2 atoms of chlorine per molecule of copper phthalocyanine is not possible according to the information in this patent. In addition, a considerable excess of chlorine gas is required in all cases, which has an oxidizing effect on the copper phthalocyanine for a long period of time and leads to considerable losses in yield. The removal of the unused chlorine requires additional technical effort.

The chlorination rate is i.a. essentially of the

509833/0766 / γ

The activity of the chlorination catalyst and the solubility of the chlorine in oleum are determined in the process mentioned In particular, the optimal activity of the catalyst is not given * Also the solubility of chlorine in oleum can only be influenced to a limited extent when working under normal pressure. Therefore i & t it according to the German patent specification no. 1 210 111 not possible, copper phthalocyanine reproducible and to chlorinate to a defined chlorine content within an economically reasonable time "

Finally, when working up the chlorinated copper erphthalocyaiiins, large amounts of very dilute sulfuric acid fall and caustic soda. The elimination of these waste materials requires an extraordinary technical and economic effort if there is a high level of wastewater pollution should be avoided.

The listed disadvantages of the process described in German patent specification No. 1 210 111 therefore close its technical usability to a large extent.

It has now been found that, while avoiding the disadvantages listed, chlorinated copper with a chlorine content of up to 20 % is obtained in a reproducible manner if a solution of copper phthalocyanine in oleum with chlorine in the presence of a chlorine carrier at a temperature of up to 20 ° is obtained Cunter Dx-uck chlorinated.

5098 3 3/0766 _{/ k}

In the claimed process, the copper phthalocyanine is used initially in up to 10 times the weight of 9-6 to 100%, preferably 100% sulfuric acid suspended or dissolved.

The preferred copper phthalocyanine is unsubstituted Copper phthalocyanine is used, according to the usual manufacturing process and can be purified or unpurified. For the production of the more highly chlorinated Phthalocyanines can also be a chlorine-containing copper phthalocyanine Use with low chlorine content.

Iodine is used as a chlorine carrier in an amount of 0.05 to 0.5X

based on the copper phthalocyanine used, used where the preparation of an optimally effective catalyst solution is of decisive importance:

In a concentrated sulfuric acid or low-percentage oleum, iodine has only a minimal catalytic activity due to its low solubility. If, on the other hand, iodine is introduced into oleum which is sufficiently concentrated for its complete solution, a catalyst solution is obtained which contains the iodine in a form that is catalytically optimally effective. The oleum concentration which is favorable for the preparation of the catalyst is 20-65%, preferably 20%. The amount of oleum is chosen so that after the addition of the catalyst solution to the solution or suspension of copper phthalocyanine in sulfuric acid, a final concentration of oleum of 0.5 to 5 % is achieved. With this procedure, the optimal catalytic activity of the iodine is fully retained even in the dilute oleum.

509833/0766. _{/ 5}

After the addition of the catalyst solution in oleum for solution or suspension of copper phthalocyanine in sulfuric acid is passed under stirring dry chlorine gas at a temperature to 20 ⁰ C ₁ is preferably 10 ° to 15 ° C in a closed vessel with a pressure of preferably 0.1 to 2 atmospheres in the solution*

The amount of chlorine is selected up to a maximum of 10 % higher than the theoretically required amount. The chlorination time depends essentially on the viscosity of the chlorination solution, the chlorine pressure used and the desired degree of chlorination of the copper phthalocyanine. It is chlorinated until the amount of chlorine required for the desired degree of chlorination has been consumed. This gives chlorinated copper phthalocyanines with a chlorine content of up to 20 % . Superphthalo-ryanines with a chlorine content of between 2.5 and 6 % or 1k and 20 % are preferably produced, since products with this chlorine content are of particular practical interest.

After the chlorination is complete, any small amount of unreacted chlorine is blown out with air or odex nitrogen and the reaction mixture is brought to a sulfuric acid concentration of 80 to 88 % at 20 ° to 80% by adding the calculated amount of water, with the sulfate of the chlorinated copper phthalocyanine precipitating .

In order to achieve crystal growth, the suspension

50983 3/0766 '

dos sulfate of chlorinated copper phthalocyanine mchrex-e Hours at 60 to 80 ° C. After cooling down the sulfate is isolated at room temperature and the product washed with 80 to 88% strength sulfuric acid in water hydrolyzed.

The isolation of the copper phthalocyanine sulfate as 80 to 88% sulfuric acid obtained from the filtrate is concentrated by the Pauling method or by Recovered distillation in the form of 96 to 98% sulfuric acid. The regeneration of the sulfuric acid can also take place by means of the thermal cleavage process. At dar Only hydrolysis of the copper phthalocyanine sulfate occurs so small an amount of dilute sulfuric acid that too this without affecting the economic viability of the process can be concentrated and used again. Also, the dilute acid can be used in place of water too directly to the precipitation of the sulfate of the chlorinated copper phthalocyanine be used.

The isolated by filtration, acid washed free aqueous filter cake of the chlorinated copper phthalocyanines _t is present, especially in the more highly chlorinated Kupferphthalocyanxnen been to pigment form, aur achieving can be especially more transparent, and high color products in form of a very concentrated aqueous suspension or in admixture with a water-soluble organic medium of Subsequent treatment can be subjected to grinding or kneading, whereby for the grinding

509833/0766 _/

A bead mill or a vibrating mill is preferably used will. An additional aftertreatment of the aqueous filter cake is also necessary to influence the pigment properties or the product subjected to grinding with additive of water or organic liquids at elevated temperature possible.

The products obtained by the process according to the invention are, in contrast to the described conditioning process, brilliant, strongly colored, crystallization and flocculation-stable pigments of the highest light and wet fastness. The low-chlorinated products with a chlorine content of preferably 2.5 to 6 % are distinguished by a reddish-blue shade which is of interest in practice. They are suitable for pigmenting varnishes of all kinds, for the production of printing inks, glue dyes or paints <and for the mass coloring of synthetic, semi-synthetic or natural macromolecular substances. They can also be used for spin dyeing natural, regenerated or artificial fibers and for printing textiles and paper. They can also be used for the production of aqueous pigment suspensions. The greenish-blue copper phthalocyanine having a chlorine content between LA and 2O56, as they are obtained in de-W present methods, are also suitable especially for the coloring of metal effect coatings and are characterized in particular by the fact that they these colorations one from the perspective of the viewer independent, consistent

509833/076 _6/8

Give nuance.

In contrast to the process described in German Patent No. 1 210 111, which works at normal pressure with a catalyst that is not optimally effective and which allows only up to a maximum of 2 atoms of chlorine per molecule of copper phthalocranine to be introduced in a poorly reproducible manner with high chlorine consumption es, with the method described above due to the special way of preparing the catalyst in connection with the performance of the chlorination under pressure with very good yield within a short time while largely avoiding the oxidative decomposition of the copper phthalocyanines with little more than the theoretically required amount of chlorine for each chlorine content chlorinate up to 20 %. Another advantage of the process is that the optimal effectiveness of the specially prepared catalyst is fully retained even after the catalyst solution in 20% oleum has been added to the solution of the copper phthalocyanine in sulfuric acid, which means that the chlorination of the copper phthalocyanine to the desired chlorine content with an extremely low oleum content the chlorination solution from 0.1 to 5 5 · only made possible. Compared to carrying out the chlorination in high-percentage oleum, this has considerable economic and ecological advantages. Since a slight degree of sulfation is absolutely desirable for flocculation stabilization, especially in the case of the low-chlorinated copper phthalocyanines, the claimed process has additional ones. Advantage that due to the defined reaction

509833/0766 / 9

conditions an optimally favorable »reproducible content of copper phthalocyanine sulfonic acids is achieved.

The sulfur content caused by these sulfonic acids is a chlorination degree of 2.5 to 6% with a maximum O ₁ I% sulfur.

This sulfur content is sufficient on the one hand to ensure the production of flocculation-stable pigment dyes and, on the other hand, has no adverse effect on the color or on the dispersibility of the pigments.

Unless otherwise noted, in the following examples, parts are parts by weight and the percentages are percentages by weight. . ...-. _- _: ■ -. . "'-"

509833/0766 _{/ ± Q}

Examples;

Example 1. :

In a glass autoclave with a capacity of 2 liters, 1800 parts of 100% sulfuric acid are placed. 200 parts of copper phthalocyanine, which was produced, for example, by condensation using the phthalic anhydride process and has a degree of purity of 95.9, are dissolved therein. Now a solution of 0.2 parts of iodine in 200 parts of 20 tiger oleum is added at room temperature, the autoclave is closed and, at a chlorine pressure of 1 atmosphere, 12 parts of chlorine gas are pressed into the mixture, which has been cooled to 15 ~ 16 C. recorded from 1 hour. The mixture is then stirred for a further 2 hours with the cooling switched off, any traces of chlorine gas and some of the hydrochloric acid gas formed are removed using a nitrogen stream and 330 parts of water are then added dropwise. * while stirring

The mixture is then subsequently stirred at 70 to 0 ° C. for 3 hours. After the mixture has cooled to room temperature, the copper phthalocyanine sulfate is filtered off and washed with 900 parts of 80% strength sulfuric acid. The filter cake is then stirred into 2000 parts of water, filtered off with suction and washed acid-free with water.

A dried sample of the phthalocyanine contains 3 % chlorine and 0.03 % sulfur.

509833/0766 / ii

- 1Λ -

The approx. Δθ S & Lge sulfuric acid of the filtrate of the copper phthalocyanine sulfate filtration is regenerated by distillation.

Example 2.:

Example 2 is carried out as described in Example i, with the difference that 2k parts of chlorine gas are introduced within 2.5 hours.

A dried sample of the copper phthalocyanine chlorinated in this way contains 6 % chlorine and 0.06 % sulfur.

Example 3 «:

Example 3 is carried out according to the information in Example 1, with the difference that instead of 200 parts of copper phthalocyanine 330 parts of copper phthalocyanine are used and

; ■ ■ TeUc

put 12 parts of chlorine gas 20y \ chlorine gas used. The chlorine

recording takes place within 3.5 hours.

The final dried product contains ~ 3 % chlorine and 0.05 % sulfur.

509833/0766 /

example ki

In a glass autoclave, 1800 parts of 100% sulfuric acid are used submitted. 200 parts of copper phthalocyanine are dissolved with stirring (in the form of a dry commercial product, which is manufactured according to the phthalic anhydride process and diluted with Hydrochloric acid was boiled) and the solution is added

of 0.2 parts of iodine in 200 parts of 20% oleum. *) then with a solution

77 parts of dry chlorine gas are then pressed into the solution over the course of 7 hours at 12-15 ° C. and a chlorine pressure of 0.5 to 1.0 atmospheres, with thorough stirring. The mixture is stirred for a short time at 15 ° C. , unconverted chlorine and some of the hydrochloric acid gas formed are blown out with the aid of a nitrogenous stroine and 330 parts of water are carefully added with stirring. After the addition of water is complete, the mixture is stirred for 3 hours at 70 ~ 80 ° C, then cooled to room temperature and the copper phthalocyanine sulfate is filtered through an acid-proof filter. It is washed with 400-500 parts of 80% sulfuric acid. The filter cake is then stirred into 2000 parts of water at room temperature, filtered off with suction and washed acid-free with water.

The aqueous filter cake of a chlorinated copper phthalocyanine which, after drying, has a chlorine content of 14.5 % , is obtained in very good yield.

The product, dried in vacuo at about 60 ° C., colors stoving enamels in brilliant, strongly colored greenish-blue shades of high transparency. The shade that was obtained with the

5098 3 3/0766 / ₁₃

- ί3 "

Pigment-made coloring of metal / effect paints always shows the same nuance regardless of the perspective of the observer *

Those involved in isolating and washing the copper phthalocyanine sulfate accruing sulfuric acid is according to your Pauling-

Process regenerated and can be used again. Regeneration is also possible by distillation * The in the hydrolysis of copper phthalocyanine sulfate Diluted sulfuric acid is regenerated using a combination of immersion burner and Pauling processes.

Example 5 » %

120 parts of an aqueous filter cake produced according to Example k with a solids content of 33 % are ground with 120 parts of water and 1200 parts of quartzite beads with a diameter of approx. 1 mm for 8 hours in a porcelain mill on a vibrating table *

The pigment is separated from the grinding media, filtered and dried in vacuo at 60 ° C *

The pigment powder obtained in this way can be used to color stoving enamels in brilliant, greenish-blue tones that are still are stronger in color and more transparent than those according to Example 1 received products.

509833/0766 '/ ik

With the pigment powder, metallic effect paints can be produced in brilliant, Color greenish-blue tones. The nuance is independent of the viewer's point of view.

Example 6.;

Example 6 is carried out as described in Example k , with the difference that 107 parts of chlorine gas are passed into the solution of copper phthalocyanine in oleum over the course of 9 hours.

The pigment, dried in vacuo at 60 ° C., has a chlorine content of 18-20 % and colors stoving lacquers in brilliant, greenish-blue tones of high transparency Nuance*

509833/0766

Claims (8)

Claims 1. A process for the preparation of chlorinated copper phthalocyanines with a chlorine content of up to 20 % by chlorination of copper phthalocyanine in oleum rait chlorine uad in the presence of a chlorine carrier, characterized in that chlorination is carried out at a temperature of up to 20 ° C under pressure. 2. The method according to claim 1, characterized in that the oleum content of the copper phthalocyanine solution is up to 5.0 % « 3 · Ancestors according to claims 1 and 2 _5, characterized in that the chlorination temperature is 10 to 15 ° C. 4. The method according to claim 1 to 3, characterized in that the chlorination at a chlorine pressure of up to 2.0 Atmospheres * 5 »Method according to claim 1 to 4, characterized in that that one uses iodine as a chlorine carrier, which the Chlorination batch is added in the form of a solution in oleum. 6 * Process according to claims i to 5i, characterized in that copper phthalocyanine up to a content of 6 % chlorine 509833/0766 / - ItT- is chlorinated and sulfated to a content of 0.1% sulfur. 7. Process according to Claims 1 to 5, characterized in that copper phthalocyanine is chlorinated to a chlorine content of 3.4 to 20%. 8. Use of the chlorinated ICupf erphthalocyanine ^ produced according to claims ί to 7 » zvtm pigmenting of paints, printing inks, paints, metallic effect lacquers and for mass coloring of polymers, polycondensates and polyaddition products. 509833/0766