CS247750B1 - Continuous method of tetrasulphonated phthalocyanines production - Google Patents

Description

The present invention relates to a continuous process for the production of tetrasulfonated phthalocyianins from the ammonium salts of phthalane hydride sulfonation products containing ammonium sulfate, urea, heavy metal compounds and additives to facilitate the formation of a phthalocyianine moiety, which comprises reacting the stirred components during the horizontal passage.

Tetrasulfonated phthalocyanines are produced by a sustained, long-term polysulfonation of phthalocyanines at elevated temperatures (literature: reports to the German industry BIOS 960, 56; FIAT 1313 III, 305); the continuous conduction of such polysulfonations is technically relatively demanding. Another seed alternative for the preparation of tetrasulfonated phthaccyamines is the condensation of salts of sulfophthalic acids with urea, heavy metal compounds, and additives to facilitate the formation of a phthalocyamine moiety. Kagaku Zasshi 76, 1378 (1955), Nippon Kagaku Zasshi 79, 396 (1953), ibid 980; CA 51 (1957), 11154, CA 51 (1957), 12,729, CA 51 (1957), 17,945, CA 54 (1960), 4,612], In the case of solvent-free operation, it occurs during condensation to melt the batch, the melt foams, and then solidifies, and it is in the solidification phase that the formation of a phthalocyanine skeleton can be inferred from the color change. This method of preparation has not yet achieved the technical importance of the sulfomation process, since successful removal of the solvent-free condensation process is dependent on ensuring the inherent contact of the components throughout the course of the reaction.

By homogenizing the drawbacks of said batch condensation variants, it is limited by the addition of a suitable solvent to render the reaction suspension miscible (see Japan Kokai 78, 66 938 [CA 89, 1978, 1310711). However, the necessary regeneration of the R-solvents complicates the technology, leads to the expansion of the production equipment and to the increased energy consumption, which results in an increase in the total production cost.

To date, efforts to introduce a continuous process for the production of tetrasulfonated phthalocyianines have encountered technical problems that prevented the rational production of this important product.

According to the present invention, tetrasulfonated phthalocyamines can be produced continuously from the ammonium salts of phthalic anhydride sulfonation products, urea, heavy metal compounds, and phthalocyanine grouping aids defined in AO 247 731 by interacting with the ammonium salts of 4- and 3-sulfo-phthalic acids. , with ammonium sulphate prepared according to AO 236 112 and the constituents defined in AO 247 731, stirred - preferably under an inert atmosphere - during the passage through a horizontal reaction zone at a temperature of 90 to 250 ° C with a residence time of hodin2 to hours Crushing filling of mineral, ceramic - or metal character.

Accordingly, the present invention provides a continuous process for the production of tetrasulfonated phthalocyanines from the ammonium salts of phthalic anhydride sulfonation products, urea, heavy metal salts, and phthalocyainine-enhancing additives by reacting 10 parts by weight of technical ammonium salts of sulfophthalic acids. The sulphosers are 7.0 to 9.0: 0.5 to 3.0, optionally containing up to 1 part by weight of ammonium salt of phthalic acid, 5.0 to 30.0 parts by weight of ammonium sulfate, 5.0 to 15% by weight. 0.0 parts by weight of urea, 0.20-0.30 moles of heavy metal compounds, calculated on 1 mol of sulfophthalic acid salts employed and 0.005 to 0.200 parts by weight of catalyst, optionally in the presence of water at a temperature of from 90 to 250 ^° C, by allowing the components to react during the passage through a stirred horizontal or inclined reduction zone, in the case of crushed fillings of mineral, ceramic or metal character.

Technical mixtures of ammonium salts of 4- and 3-sulphophthalic acids with ammonium sulphate, prepared according to AO 236 112, show favorable proportions of components and the contained ammonium sulphate assumes the function of a solvent (facilitates homogenization in the system during melting of the heated reactive mixture) Surprisingly, it was found that during the passage of the molten mixture through the reactor horizontally or obliquely deposited under the influence of ammonium sulfate, the degree of foaming was greatly reduced and the product emerged from the reaction zone in powder to lump form.This unexpected, experimentally proven findings enabled the production of tetrasulfonated phthalocyanines continuously. It is also possible to use aqueous solutions of technical mixtures of ammonium salts obtained by dilution and amcimacalization of the reaction mixtures after the sulfonation of phthalic anhydride. other distillation concentration can be carried out outside the continuous reactor or in the inlet part of the reaction zone, where the temperature may be lower - for example 150 ° C. ° C, while it may be up to 250 ° C at the reactor outlet.

Other reaction components can be used either in the form of pure chemicals or in the quality of technical products complying with the prescribed standard (urea, heavy metal salts, etc.). Of the heavy metal compounds, any of those commonly used in the manufacture of phthalocyamines, such as oxides, chlorides, bromides, sulfates, phosphates, carbonates, and other inorganic compounds, or ethanes, sulfates, tartrates, citrates, sulfonates, and other inorganic compounds can be applied. similar organic compounds. Of the phthalocyanine grouping additives, practically all known compounds used hitherto in the synthesis of phthalocyanine pigments, such as ammonium, molybdic or phosphomolybdic acid, molybdenum trioxide, antimony oxide, arsenic, zinc, lead, titanium and many others are suitable. known catalysts (literature: MOSER FH, Thomas AL: Phthalooyauine Compounds, Reinhlold Ruble. Corp. NY, Chapmann and Hall Lid., London, 1963).

The continuous production process has a positive effect on the reduction of the oxygen content in the working space or its removal from the gas phase of the reaction zone; it is therefore appropriate to introduce one of the inert materials into the reactor.

The residence time of the reaction mixture in the reaction zone is temperature-dependent, with increasing temperature the residence time can be reduced to + hours (at 250 ° C). However, due to the satisfactory thermal stability of tetrasulfophthalocvauin, the stay can be extended up to 5 hours.

Since the system undergoes a melt stage during the reaction, with subsequent solidification of the products, it is advantageous to carry out the continuous production process according to the invention in horizontal or oblique crushed rotary reactors such as in a venulose filled with porcelain or metal spherical bodies. cylindrical shape.

The continuous process for the production of tetrasulfonated phthalocyanines exhibits a number of advantages over batch processes. For example:

- the new process provides the final product in free-flowing form, so that it is easy to exit from the reactor and the particle size is favorable for rapid dissolution in water, which may be useful in eventual subsequent refining of the crude product - ammonium sulphate present in technical mixtures of ammonium salts of sulphophthalic acids according to AO 236 112 both accelerates the formation of phthalocyanine skeleton and unexpectedly positively affects the homogenization of the components in the primary reaction study, during which the stirred system passes through the melt stage. In the batch process, the concentration equalization is achieved only by relatively slow diffusion - ammonium sulphate limits foaming of the reaction mixture during the passage through the reactor - in the event that there is a crushing agent (eg porcelain or metal spheres) in the reaction zone a synthesis stage where the system is transformed into a solid granular mass that is pulverized; this facilitates the passage of mass through the reactor and improves heat transfer, both leading to more viable technology.

The example below illustrates an embodiment of the invention.

Example

Homogenizate consisting of 7,79 kg technical grade ammonium sulphate and 45,8% of ammonium salts of 4- and 3-sulphophthalic acids with a ratio of 76: 24 of 4- and 3-sulphoisomers, obtained by AO 236 112, 2,52 kg of urea 303 g of cuprous chloride, and 10.5 g of ammonium molybdate were continuously fed into an electrically heated horizontal cylindrical reactor tangentially stirred, with a temperature in the reaction zone of 200 + 15 ° C with a stirring time of 3 hours. During synthesis, nitrogen was introduced into the workspace. A granular, loose dark blue product is dropped from the reactor outlet (the sample is well dissolved in water to a turquoise blue solution). A total of 7.40 kg of crude product was obtained, containing 70.5% of the theory of ammonium salts of tetrasulfonic copper phthalocyanines, predominantly with the sulfo groups at the 4-position.

If the temperature in the reaction zone was increased to 250 ° C, a residence time of V2 hours was sufficient for a satisfactory conversion.

In place of cuprous chloride, an equivalent of other copper compounds or other heavy metal compounds may be used to prepare the corresponding tetrasulfophthalicyanines.

SUBJECT

A continuous process for the production of tetrasulfolinated phthalocyanines from the ammonium salts of phthalic anhydride sulfonation products, urines of heavy metal compounds and additives to facilitate the formation of a phthalocyanine moiety, by reacting the 10 wt. parts of technical ammonium salts of sulfophthalic acids, wherein the ratio of 4- and 3-sulfoisoraers is 7.0 to 9.0: 0.5 to 3.0, optionally containing up to 1 wt. % ammonium salt of phthalic acid, 5.0 to 30.0 wt. parts of ammonium sulphate

Claims (1)

Of the invention, 5.0 to 15.0 wt. parts of urea, 0.20 to 0.30 moles of heavy metal compounds, calculated per 1 mol of sulfophthalic acid salt employed, and 0.005 to 0.2000 wt. % of the catalyst, optionally in the presence of water at a temperature of 90 to 250 ° C, characterized in that the components are reacted during the passage through a stirred horizontal or inclined reaction zone, optionally containing a crushing charge of mineral, ceramic or metallic character.