DE1261611B - Process for the preparation of copper polybromochlorophthalocyanines - Google Patents

Description

FEDERAL REPUBLIC OF GERMANY

GERMAN

PATENT OFFICE

EDITORIAL

Int. Cl .:

Number:
File number:
Registration date:
Lay-out day:

C09b

German class: 22 e - 7/02

1261611
J20785IVc / 22e
November 6, 1961
February 22, 1968

The invention relates to a method of manufacture of halogenated phthalocyanine pigments.

It is known that Rupferpolychlorphthalocyanine are valuable green pigments and that Kupferpoiyhalögenphthälocyänine, which contain both chlorine and bromine are also useful as pigments which are more yellow in color are than the corresponding pigments where all halogen is chlorine. Copper polybromomehlorphthaiocyanine, in which the total halogen content corresponds to 15 to 16 halogen atoms per molecule and of of which about 8 to about 15 are bromine atoms, are particularly valuable pigments and are used in the UK U.S. Patent 925,266.

It has been shown that the use of polybromochlorophthalocyanines in the production process of elemental bromine has hitherto been expensive because of the large excess of bromine, which would have to be used, especially if it is desired, copper polybromochlorophthalocyanines containing more than about 8 bromo atoms per molecule. British patent specification 925 266 describes a process for the production of halogenated phthalocyanine pigments in such a way that one can obtain a stable metal phthalocyanine or an incompletely halogenated derivative of which with chlorine in the presence of aluminum chloride and at least 1 mol of an alkali metal bromide treated per mole of phthalocyanine. In this process, bromine is added to the reaction mixture in the form an Xlkalimetallbrömdds supplied, and if large Amounts of alkali metal bromide can be applied To obtain products which contain larger amounts of bromine, correspondingly large amounts of aluminum chloride must be obtained can be used to provide a liquid reaction medium.

The present invention relates to a process for the preparation of Kupferpolychlorbromphthalocyaöin, in which it is not necessary to use a larger amount of aluminum chloride than normal for the production of copper polychlorophthalocyanines is used.

The process according to the invention for the preparation of copper polybromochlorophthalocyanines is described in carried out by using copper phthalocyanine or an incompletely halogenated derivative thereof in a melt of aluminum chloride and one Alkali metal chloride with chlorine and at least ten atomic parts of bromine per molecule of copper phthaloeyanine up to the introduction of at least 15 halogen atoms per molecule ICupferpolybromchlorphthaloeyänin treated, treatment with bromine method of manufacture

of copper polybromochlorophthalocyanines

Applicant:

Imperial Chemical Industries Limited, London

Representative;

Dr.-Ing. H. Fincke, Dipl.-Ing. H. Bohr

and Dipl.-Ing. S. Staeger, patent attorneys,

8000 Munich 5, Müllerstr. 31

Named as inventor:

Robert Faezaekerley;

Arnold Kershäw,

Manchester, Lancashire (UK)

Claimed priority:

Great Britain 11 November 1960,

dated October 13, 1961 (38 783)

is done either before or at the same time as the treatment with chlorine.

Examples of alkali metal chlorides which can be used in the process of the invention, are potassium chloride and especially sodium chloride. Although the amount of aluminum chloride and alkali metal chloride in the melt as used in the process of the invention is not critical, and

all quantities which give a liquid melt can be used, so those quantities become in the vicinity of a eutectic mixture is preferred.

Examples of incompletely halogenated phthalocyanine derivatives, which in the process according to the Invention can be used are the chlorine ', bromine' and chlorobromo derivatives, which one to twelve directly to each phthaloeyanine molecule contain bound halogen atoms.

To carry out the process according to the invention, the phthalocyanine, which is preferably used in powder form, can first be suspended or in a melt of aluminum chloride and alkali metal chloride be dissolved, or it can optionally be a mixture of phthalocyanines, aluminum chloride and alkali metal chlorides are heated until it becomes liquid. Expediently, 12 to 30MoI

809 509/298

3 4

Aluminum chloride used for each phthalocyanine By adjusting the bromine and chlorine hydrogen chloride employed for each mole of phthalocyanine in the process of the invention, with amounts of 14 to 20 moles of aluminum being preferred. Copper bromochlorophthalocyanines can be obtained with very, if necessary, in the presence of various additional bromine and chlorine contents, for example organic solvents. For example, a polybromochlorophthalocyanine such as nitrobenzene or small amounts of other polybromochlorophthalocyanine containing inorganic salts, for example chlorides 7 to 8 bromine atoms per molecule, can be obtained from iron or copper. Then bromine can be added using ten atomic amounts of bromine per phthalocyanine solution or suspension and then phthalocyanine molecule in the process according to the ßend chlorine, or bromine and 10 invention, and a polybromochlorophthalo-chlorine can be introduced at the same time. Bromine cyanine obtained with a content of 14 bromine atoms can optionally be added in liquid form by using twenty-one atomic or expediently introduced amounts of bromine per molecule of phthalocyanine, by passing a carrier gas, such as nitrogen, through The method according to the invention is very valuable liquid bromine and passing the i ₅ thus obtained, if it is used, copper bromochlorophthalo gas mixture through the phthalocyanine solution or cyanine with a content of at least 15 halogen suspension. Optionally, a mixture, which atoms per molecule can be obtained, of which at least by mixing bromine and chlorine (for example 8 and more, in particular at least 13 bromine atoms, a gaseous mixture, as is passed through. Such copper bromochlorophthalocyanines can conduct chlorine through liquid bromine obtained _ao can be obtained more economically by the present process) is obtained in the phthalocyanine are obtained than after being introduced into the British solution or suspension. In the process described in patent specification 925 266, because in general it is desirable that bromine can be added to the phthalo- a smaller amount of aluminum chloride in the pre-cyanine solution or suspension in the course of lying processes and several hours, for example not less than _a5 because bromine per se less expensive starting 3 hours and preferably no less than 5 hours fuel than the alkali metal bromide that is introduced. The products obtained by the process of the present invention can be dispersed at any desired temperature above the melting Temperatures between 140 and 250 ⁰ C, in particular with concentrated sulfuric acid, oleum or chlorine between 160 and 200 ⁰ C, and especially between sulfonic acid, adding the mixture obtained in this way 160 and 170 ° C, can be carried out. to water and then filtering off and drying the To determine when a copper polybromochloro-deposited pigment. Appropriately, phthalocyanine with a content of at least 35, the products are produced, however, according to the method of British 15 halogen atoms per molecule, patent specification 719 072 are dispersed by stirring the test samples taken from the reaction mixture polybromochlorophthalo.cyaninaluminiumchlorid-Reak- and the phthalocyanine is isolated and analyzed. It has been found that if the treatment with medium, for example chlorobenzene and then chlorine, is continued for too long a period of time, the complex compound from the phthalo has already entered the phthalocyanine nucleus and aluminum chloride with water. Optionally, bromine begins to be replaced by chlorine. As a result, the products can be appropriately dispersed, whose elemental bromine appears in the outflowing gases, by pouring the polybromochlorophthalocyanine alum and causing a further treatment of the miniumchloride reaction mixture in water, adding a weight loss to the reaction mixture with chlorine, adding an organic liquid, filtering, Er In practice, therefore, the end point of the heating of the pigment can be determined with the same or a different procedure, either by determining the organic liquid and then isolating the total weight of the reaction mixture or, pigment by removing the organic liquid if chlorine alone during the Final stages in this, for example, by steam distillation. The orga-reaction mixture is initiated by simple 50 niche liquids, which are intended for use when visually observing the gases flowing out. This latter dispersion process are suitable, After carrying out the process according to the are those which are suitable for the so-called Flushing invention, the bromochlorophthalocyanine pigment of a phthalocyanine pigment can be isolated from an aqueous slurry by pouring the reaction mixture thereof and are particularly suitable in water or dilute mineral acid, filtering off 55 such liquids as benzene, toluene, xylene, the separation, wash acid-free and given .Chlorbenzol, o-dichlorobenzene, trichlorobenzene, nitrofalls drying. benzene, o-nitrotoluene and p-chlorotoluene.

It is of course known that by mixing the parts given in the examples

Bromine and chlorine bromine monochloride is produced by weight,

(See, for example, Inorganic and Theoretical Chemical Example 1 mistry by J. W. M eil or, Supplement II, Part I,

P. 478 published by Longmans, Green & Co., 104.5 parts copper phthalocyanine, 91.5 parts sodium-1956). It follows that the bromine monochloride monium chloride and 437.5 parts of anhydrous aluminum part in the method according to the invention as starting chloride are mixed together and used on a gear material, especially when the method 65 is heated temperature 160-170 ⁰ C until which is completely liquid by passing a mixture of chlorine through it. Then the mixture obtained and bromine is stirred through the phthalic mixture at 160 to 170 ⁰ C and 480 parts, cyanine solution or suspension is carried out. liquid bromine added over 31 hours.

5 6

A test sample taken at this point in time was isolated and according to that described in Example 1

contains 12.5 atoms of bromine and 0.4 atoms of chlorine per method treated.

Molecule. There are 338 parts of a strong yellowish green

Then gaseous chlorine is passed in until the pigment is obtained, which 14.0 atoms of bromine and mixture does not experience any further increase in weight. 5 contains 1.9 atoms of chlorine per molecule.
That takes about 25 parts of chlorine, and treatment. .
takes about 3 hours. The example thus obtained
liquid melt is poured with stirring into a mixture of 115.2 parts of copper phthalocyanine, 91.5 parts of sodium from 4500 parts of cold water and 110 parts of concentrated chloride, 3.6 parts of anhydrous ferric chloride and trated hydrochloric acid, and the deposit is 437.5 parts of anhydrous aluminum chloride are filtered, washed acid-free with cold water and mixed and sucked together to a temperature between the wet filter material as dry as possible. 160 and 170 ⁰ C heated until a completely liquid

The wet filter material is weighed and received when the room melts. 77 parts of chlorine are through

temperature to a stirred mixture of 310 parts 160 parts of liquid bromine between 29 and 31 ° C back

Chlorobenzene, enough water to increase the 15 blown through and the gas mixture thus obtained through

Weight of the filter material to 1364 parts, 6.2 parts of the melt between 160 and 170 ° C with stirring

Oleic acid, 9.3 parts rosin and 75 parts one were passed through for about 8 hours. Then it will be

32 ° / _o aqueous sodium hydroxide solution was added. gaseous chlorine passed into the melt until a

Then the mixture will not gain any further weight for 3 hours while passing it back through

Nut heated to the boil and stirred. The chlorobenzene 20 causes. That requires about 137 parts of chlorine, which

is removed by steam distillation and which is passed through over the course of about 8 hours.

The solid is filtered off, alkali-free with cold water. The product is isolated and prepared according to the method in Example 1

washed and dried at 100 ° C. described method.

There are 306 parts of a very yellowish green · There are 290 parts of a yellowish green pigment

Pigments with a content of 14.3 atoms of bromine »5 with a content of 7.8 atoms of bromine and 8.0 atoms

and 0.6 atoms of chlorine per molecule of copper phthalochlorine per molecule.

obtained cyanine. _,. .

Example5

Example 2 _n5 ^ ₂ ^. ^ _{Copper phthalocyanine 915 parts of sodium} .

115.2 parts of copper phthalocyanine, 91.5 parts of sodium chloride and 437.5 parts of anhydrous aluminum

Umchlorid and 437.5 parts of anhydrous aluminum chloride are mixed and together on one

chloride are mixed and heated together to a temperature between 160 and 170 ° C until a

Temperature between 160 and 170 ° C heated until the completely liquid melt is obtained. 120 parts

Mixture is completely liquid. Then the chlorine will be between 272 parts of liquid bromine

Mixture stirred at 160 to 170 ° C, and 320 parts 35 29 and 31 ° C blown through and the resulting

liquid bromine are in the course of about 18 hours gas mixture in the melt with stirring at 160

the added. One withdrawn at this point in time up to 170 ° C was initiated in the course of about 14 hours.

Test sample contains 9.5 atoms of bromine and 0.4 atoms. Then gaseous chlorine is passed through the mixture

Chlorine per molecule. until there is bromine in the outflowing gases

Then gaseous chlorine will appear in the mixture 4 °, as described in Example 2. That requires

initiated. First of all, the outflowing contains about 20 parts of chlorine, which in the course of about

Gases little bromine, but if no inorganic gases are passed through for 3 hours. The product

More bromine compounds in the reaction mixture are isolated and followed according to that described in Example 1

left behind, chlorination takes place, and while method is treated.

During this time the outflowing gases do not contain 45. 333 parts of a strongly yellowish-green longer bromine. If bromine reappears in the outgoing pigment with a content of 12.1 atoms of bromine gases, this is a sign of this, and 3.6 atoms of chlorine per molecule are obtained,
that bromine entered the phthalocyanine nucleus. .
is replaced by chlorine. Passing through chlorine example ö
is then canceled. About 146 parts of chlorine are used, 50 to 72 parts of copper phthalocyanine, 102 parts of sodium and the procedure is carried out for about 16 hours of chloride and 547 parts of anhydrous aluminum chloride. The product is isolated and after being mixed and treated to a temperature between the method of Example 1. 160 and 170 ° C heated until completely liquid

320 parts of a very yellowish-green melt are obtained. 62 parts of chlorine are through

Pigments with a content of 13.5 atoms of bromine and 55,200 parts of liquid bromine between 34 and 36 ° C

2.1 atoms of chlorine per molecule of copper phthalocyanine blown through and the gas mixture thus obtained

obtain. in the melt with stirring at 160 to 17O ⁰ C im

Example 3 courses of about 17 hours initiated. Then it will be

gaseous chlorine through the melt-

115.2 parts of copper phthalocyanine, 91.5 parts of sodium 60 passed until no more passed through

umchloride, and 437.5 parts of anhydrous aluminum caused weight gain. That requires about

Chloride are mixed and taken together to a temperature of 8 parts of chlorine, which over the course of about 3 hours

Temperature between 160 and 170 ⁰ C heated until the Ge can be passed through. The product is isolated and

mix is completely liquid. 149 parts of chlorine are loaded according to the method described in Example 1

between 29 and 31 ⁰ C by 336 parts of liquid bromine 65 acts.

blown, and the gas mixture thus obtained is in there are 215 parts of a very yellowish green

Pass for 21 hours at 160 to 170 ° C under pigments containing 15.0 atoms of bromine and

Stirring passed into the melt. The product will contain 0.8 atoms of chlorine per molecule.

Example 7

115.2 parts of copper phthalocyanine, 91.5 parts of sodium "ünichlorid, 0.5 part of anhydrous copper (II) chloride and 437.5 parts of anhydrous aluminum chloride are mixed and ^{heated together to a temperature between 160 and 170 0} C until a 88 parts of chlorine are blown through 288 parts of liquid bromine between 34 and 36 ° C. and the resulting gas mixture is passed through the melt for about 19 hours with stirring a further introduction does not cause any further increase in weight. This requires about 30 parts of chlorine, which are passed through in the course of about 10 hours. The product is isolated and treated according to the method described in Example 1.

There are 344 parts of a very yellowish green pigment containing 14.0 atoms of bromine and get 1.8 atoms of chlorine per molecule.

Example 8

115.2 parts of copper phthalocyanine, 101 parts of sodium chloride and 482 parts of anhydrous aluminum chloride are mixed and heated together to a temperature between 160 and 17O ⁰ C, is obtained until a completely liquid melt. A slow stream of nitrogen is introduced into 288 parts of bromine under boiling and directed the gas mixture through the stirred melt at 160 to 170 ⁰ G in the course of about 14 stood. Chlorine is then passed into the melt until bromine reappears in the exhaust gases, as described in Example 2. This requires about 130 parts of chlorine, which are added over the course of about 16 hours. The product is isolated and treated according to the method described in Example 1.

There are 340 parts of a strongly yellowish green pigment containing 13.4 atoms of bromine and Get 2.4 atoms of chlorine per molecule,

Example 9

115.2 parts of copper phthalocyanine, 2.3 parts of sodium sulfate decahydrate, 0.6 part of copper (II) chloride dehydrate, 91.5 parts of sodium chloride and 437.5 parts of anhydrous aluminum chloride are ^{heated together to a temperature between 160 and 170 0} C until a completely liquid melt is obtained. 171 parts of liquid bromine is added to the stirred mixture and between 17O ⁰ C in the course of 8 hours, parts of gaseous chlorine is then introduced into the mixture until in the exiting gases bromine appears again, as described in Example 2. FIG. About 21 hours are required for this. The product is isolated and treated according to the method described in Example 1.

There are 285 parts of a yellowish green pigment With a content of 8.0 atoms of bromine and 7.8 Ate * men receive chlorine per molecule.

Claims (7)

Patent claims: 1. Method of making copper poly Bromochlorophthalocyanines, characterized in that copper phthak> cyanine or an incompletely halogenated derivative thereof in a melt of aluminum chloride and alkali metal chloride with chlorine and at least 10 atomic amounts of bromine per molecule of copper phthalocyanine up to the introduction of at least 15 halogen atoms per molecule of copper polybromochlorophthalocyanine treated, whereby the treatment with bromine is carried out either before or at the same time as the treatment with chlorine whxL 2. The method according to claim 1, characterized in that the alkali metal chloride is sodium chloride used. 3. The method according to claim 1 and 2, characterized ^ that one has 12 to 30 moles of aluminum chloride used per mole of phthalocyanine. 4. The method according to claim 1 and 2 _S, characterized in that snail uses 14 to 20 moles of aluminum chloride per mole of phthalocyanine. 5. The method according to claim 1 to 4, characterized in that the process is carried out at a temperature between 160 and 200 ⁰ C. 6. The method according to claim 1 to 5, characterized in that the method at a Temperature between 160 and 170 ° C, 7. The method according to claim 1 to 6, characterized characterized »that the treatment with bromine in the course of not less than 5 hours carries out » Pamphlets considered; French patent specification No. 815 088> When the registration was announced, a coloring table with explanations was laid out, 809 509/298 2.68 © Bundesdruckerei Berlin