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Process for the Production of Copper Phthalocyanine

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^ ^ ^ ^ I ^ ^ ^ ^ ^ ^ II ^ ^ ^ II ^ II ^ ^ ^ ^ ^ ^ ^ ^ ^ I ^ European Patent Office Office europeen des brevets EP 0 878 514 A2 EUROPEAN PATENT APPLICATION (43) Date of publication: (51) |nt CI.6: C09B 47/06 18.11.1998 Bulletin 1998/47 (21) Application number: 98303542.9 (22) Date of filing: 06.05.1998 (84) Designated Contracting States: (72) Inventors: AT BE CH CY DE DK ES Fl FR GB GR IE IT LI LU • Endo, Atsushi MC NL PT SE 3-13 Kyobashi 2-chome, Chuo-ku, Tokyo (JP) Designated Extension States: • Suda, Yasumasa AL LT LV MK RO SI 3-13 Kyobashi 2-chome, Chuo-ku, Tokyo (JP) (30) Priority: 12.05.1997 JP 120386/97 (74) Representative: Woods, Geoffrey Corlett J.A. KEMP & CO. (71) Applicant: TOYO INK MANUFACTURING CO., 14 South Square LTD. Gray's Inn Tokyo (JP) London WC1 R 5LX (GB) (54) Process for the production of copper phthalocyanine (57) A process for the production of copper phthalo- thereof with ammonia to form phthalimide; cyanine or a derivative which process avoids problems (B) adding at least a part of the urea to the thus ob- associated with build up of phthalimide in a reactor ves- tained phthalimide and melting the thus obtained sel, the process comprising: mixture to form a homogeneous slurry; and (C) contacting the copper or copper compound and (A) reacting the phthalic anhydride or derivative any remaining urea with the thus obtained slurry to form a copper phthalocyanine or a derivative there- of in the presence of a catalyst. CM < lo oo oo o a. LU Printed by Jouve, 75001 PARIS (FR) 1 EP0 878 514 A2 2 Description phthalocyanine having a high purity can be industrially stably produced at high yields. Field of the Invention According to the present invention, there is provid- ed a process for the production of copper phthalocya- The present invention relates to a process for the 5 nine or its derivative from phthalic anhydride or a phthal- production of copper phthalocyanine or a copper ic anhydride derivative, ammonia, copper or a copper phthalocyanine derivative from phthalic anhydride or a compound, and urea, phthalic anhydride derivative, ammonia, copper or a the process comprising the steps of copper compound, and urea, which method enables the stable production of a high-purity copper phthalocya- 10 (A) reacting the phthalic anhydride or the phthalic nine having a clear color tone. anhydride derivative with ammonia to form phthalimide, Prior Art of the Invention (B) adding part or all of the urea to the phthalimide obtained in step (A) and melting the mixture under As a conventional method for the production of cop- is heat to form a homogeneous slurry, and per phthalocyanine, there is known a method in which (C) adding the copper or the copper compound and phthalic anhydride, urea and copper or a copper com- remaining urea if any to the slurry obtained in step pound are allowed to react under heat in an inert solvent (B) and forming a copper phthalocyanine or a cop- in the presence of a catalyst. For decreasing the amount per pthalocyanine derivative in the presence of a of urea to be used, JP-A-51 -34926 discloses a method 20 catalyst. in which the reaction is carried out in the following sep- arate two steps. That is, the method comprises a first Detailed Description of the Invention step of reacting phthalic anhydride or a phthalic anhy- dride derivative with ammonia and a second step of re- In the present invention, the phthalic anhydride or acting the resultant reaction mixture with urea and a 25 the phthalic anhydride derivative includes a phthalic an- copper compound in the presence of a catalyst. Further, hydride or a phthalic anhydride whose benzene ring when ammonia generated in the second step is recycled contains a halogen atom such as chlorine or bromine, to the first step to continuously carry out the reaction in an alkyl group such as methyl, ethyl or propyl, a alkoxy the first step, industrially advantageously, it is made group such as methoxy or ethoxy, an aryl group which easy to dispose of the generated gas, and the produc- 30 may have a substituent, a carboxyl group, a sulfone tivity is also improved. group or a nitro group. However, the above method has the following prob- The copper compound can be selected from all the lem. Phthalimide formed in the first step adheres to the copper salts which are generally used for the synthesis wall of a reactor and a stirring blade, and therefore, the of copper phthalocyanine. The copper compound in- reaction in the second step does not smoothly proceed, 35 eludes copper halides, copper oxide, copper phosphate, which decreases the yield and the purity of the resultant copper nitrate, copper hydroxide, copper acetate and pigment. In particular, when the first step and the second copper sulfate. Of these, copper (I) chloride is the most step are continuously carried out in two separate reac- preferred. tors connected to each other, part of the phthalimide re- The catalyst can be selected from all the catalyst mains in the reactor used in the first step, and it is there- 40 which are generally used for the synthesis of copper fore required to adjust the amount ratio of raw materials phthalocyanine. The catalyst includes molybdenum to be used in the second step. It is therefore difficult to compounds such as ammonium molybdate, molybdic attain a high yield and a high purity industrially stably. acid, ammonium phosphomolybdate and molybdenum The above phenomenon particularly dominantly ap- oxide, tungsten compounds such as ammonium tung- pears when the inert solvent used for the reaction is a 45 state and ammonium phosphotungstate, an arsenical hydrocarbon solvent having a relatively low polarity vanadium compound, boric acid, and halide or oxyhali- such as paraffin, naphthene, kerosene or alkylbenzene. de of titanium, tin or antimony. Of these, ammonium mo- lybdate works excellently. Summary of the Invention In the present invention, the ammonia gas may be so a mixture of it with an inert gas such as a nitrogen gas. In the method comprising the above two reaction Industrially advantageously, a gas composed mainly of steps, since phthalimide formed in the first step adheres ammonia and a carbon dioxide gas generated in the to the wall of a reactor and a stirring blade, the reaction step (C) can be used as it is. in the second step does not smoothly proceed, so that In the present invention, the reaction may be carried the yield and the purity of the resultant pigment are low. 55 out in the absence of a solvent, while it is industrially It is therefore an object of the present invention provide advantageous to use an inert solvent such as nitroben- a process for the production of copper phthalocyanine, zene, trichlorobenzene, chloronaphthalene, methyl- in which the above defect can be overcome and copper naphthalene, naphthalene, alkylbenzene, paraffin, 2 3 EP0 878 514 A2 4 naphthene or kerosene. The above solvents may be actor 2) connected to each other through a connection used alone or in combination. When the solvent is used, tube were used for continuously carrying out reactions the solvent may be added in any step of the steps (A) by the following procedures. to (C). It is particularly preferred to continuously add the 148 Parts of phthalic anhydride and 148 parts of t- solvent in the step (A), since the adherence of phthalim- 5 pentylbenzene were charged into the reactor 1 and ide to a reactor is decreased in this case. melted by heating them to 130°C, and then, 25 to 35 In the present invention, the reaction temperature parts of ammonia was introduced over 3 hours. The re- in the step (A) is 1 20 to 230°C, preferably 1 30 to 1 80°C. action temperature was maintained at 1 30 to 1 80°C, the The reaction pressure in the step (A) is 1 to 20 kg/cm2, reaction pressure was maintained at 2 to 3 kg/cm2, and preferably 2 to 5 kg/cm2. In the step (A), unreacted 10 excess ammonia and formed water were discharged phthalic anhydride or phthalic acid formed as a byprod- through a discharge outlet equipped with a pressure-ad- uct may remain. However, when the amount of the un- justing valve. After the reaction, it was found that part of reacted phthalic anhydride or the phthalic acid is too formed phthalimide adhered to the wall of the reactor large, it is difficult to decrease the amount of urea to be and a stirring blade. The reaction mixture was cooled to used in the steps (B) and (C). Preferably, the amount of is 130°C, 138 parts of urea was added, the mixture was remaining phthalic anhydride or phthalic acid is 5 mol% stirred at 1 30°C for 1 hour, and the reaction mixture was or less based on the charged phthalic anhydride. re-charged into the reactor 2 while retaining the above In the present invention, the temperature for the temperature. In this case, almost no substance was melting under heat in the step (B) is 1 20 to 1 60°C, pref- found to be adhering to the wall of the reactor 1 and the erably 130 to 140°C. When the above temperature is 20 stirring blade. lower than 120°C, no sufficient fluidity can be obtained, 148 Parts of phthalic anhydride and 148 parts of t- and no homogeneous slurry is formed. When the above pentylbenzene were again charged into the reactor 1 temperature is higher than 160°C, undesirably, the and melted under heat.
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  • Intercalation of Copper Phthalocyanine Within Bulk

    Intercalation of Copper Phthalocyanine Within Bulk

    Intercalation of Copper Phthalocyanine Within Bulk Graphite as a New Strategy Toward the Synthesis of CuO-Based CO Oxidation Catalysts Gaëlle Couvret, Ghislain Genay, Cerise Robert, Loic Michel, Valérie Caps To cite this version: Gaëlle Couvret, Ghislain Genay, Cerise Robert, Loic Michel, Valérie Caps. Intercalation of Copper Phthalocyanine Within Bulk Graphite as a New Strategy Toward the Synthesis of CuO-Based CO Oxidation Catalysts. Frontiers in Chemistry, Frontiers Media, 2020, 8, 10.3389/fchem.2020.00735. hal-02928127 HAL Id: hal-02928127 https://hal.archives-ouvertes.fr/hal-02928127 Submitted on 2 Sep 2020 HAL is a multi-disciplinary open access L’archive ouverte pluridisciplinaire HAL, est archive for the deposit and dissemination of sci- destinée au dépôt et à la diffusion de documents entific research documents, whether they are pub- scientifiques de niveau recherche, publiés ou non, lished or not. The documents may come from émanant des établissements d’enseignement et de teaching and research institutions in France or recherche français ou étrangers, des laboratoires abroad, or from public or private research centers. publics ou privés. ORIGINAL RESEARCH published: 31 August 2020 doi: 10.3389/fchem.2020.00735 Intercalation of Copper Phthalocyanine Within Bulk Graphite as a New Strategy Toward the Synthesis of CuO-Based CO Oxidation Catalysts Gaëlle Couvret, Ghislain Genay, Cerise Robert, Loïc Michel and Valérie Caps* ICPEES (Institut de Chimie et Procédés pour l’Energie, l’Environnement et la Santé), Université de Strasbourg - ECPM / CNRS UMR 7515, Strasbourg, France Graphite is a widely available natural form of carbon with peculiar chemical and surface properties. It is essentially hydrophobic and consists in very stable stacks of graphene layers held together by highly delocalized π-π interactions.