Patent GB-453767-A (GB)
Title: Improvements in the manufacture and production of dyestuffs
IPC: C09B47/04
Filed: 1935-02-13
Abstract: Phthalocyanine dyes are prepared by heating at least one diamide or dinitrile of an aromatic o-dicarboxylic acid or an o-cyano compound of an aromatic carboxylic acid amide, or a substitution product thereof, with a metal or metal compound taking part in the formation of the dyestuff in the presence of an oxide or salt of a metal of groups I to IV of the Periodic System which oxide or salt is solid at the reaction temperature and is inert with respect to the reaction and is used as a diluent.  The term "metal or metal compound taking part in the formation of the dyestuff" includes substances which enter into the dyestuff itself and which accelerate the reaction or enable it to take place; copper, nickel, iron, magnesium, antimony, sodium or their compounds, such as cuprous chloride, nickelous chloride, cobaltous chloride, stannous chloride, magnesium oxide, alkali metal hydroxides and alcoholates are mentioned.  Suitable solid inert substances are salts of alkali and alkaline earth metals such as sodium chloride or sulphate, potassium chloride or sulphate, calcium sulphate, barium sulphate, alumina, titanium dioxide and silicon dioxide of any origin (for the purposes of the invention silicon being regarded as a metal); these prevent any sudden rise of temperature and permit the process to be carried out continously; thus the mixture may be arranged on iron pans on a car or conveyer band and thus passed through an externally heated open or closed space.  In examples: (1) phthalodinitrile, copper tetrammine chloride and sodium chloride are heated to 180--190 DEG  C. and the mixture introduced into water on completion; sodium acetate, potassium chloride or sulphate may replace sodium chloride, and copper sulphate or acetate may replace the copper compound; (2) phthalodinitrile is ground in a ball mill with cuprous chloride and anhydrous sodium sulphate and heated to 200 DEG  C., the mass being then introduced into water; (3) phthalodinitrile and cuprous chloride are ground with alumina (or barium sulphate, or titanium dioxide or kieselguhr) and the mixture heated to 170 DEG  C.; (4) phthalodinitrile, a cuprous chloride-pyridine compound and anhydrous sodium sulphate are heated to 180 DEG  C. for half an hour and the mass then introduced into water; (5) phthalodimitrile, aluminium chloride and anhydrous sodium sulphate is heated to 200 DEG  C. for half an hour and the mass then boiled with water; (6) phthalodinitrile, silicon dioxide and cuprous chloride is heated to 200 DEG  C. for 30 minutes and the mass ground in a ball mill, boiled with water and the dye separated by elutriation if desired in presence of a dispersing agent; or the mass is treated with concentrated sulphuric acid and the filtered acid solution then diluted to precipitate the dye; (7) phthalodinitrile, an aluminium chloride-carbamic acid chloride addition compound, and anhydrous sodium sulphate is heated to 180--190 DEG  C. and the pigment separated by boiling the mass in water and filtering; (8) phthalodinitrile is ground with sodium amylate and mixed with anhydrous sodium sulphate and heated at 170--200 DEG  C. for 20 minutes; the dye is separated by introducing into water and filtering; sodium or potassium compounds of other alcohols and sodium or potassium hydroxide may be used instead of sodium amylate and a mixture of 3- and 4-chlorophthalodinitriles may similarly be treated; (9) phthalodinitrile, zinc chloride (or cobaltous, nickelous, manganous or stannous chlorides) and anhydrous sodium sulphate is heated to 200 DEG  C.; (10) phthalodinitrile, cuprous chloride and anhydrous sodium sulphate is spread on iron sheets and passed continuously through an oven at 200--230 DEG  C.; copper, copper oxides, cuprous bromide, copper chloride, copper sulphide, copper sulphate or copper acetate may replace cuprous chloride.  The Provisional Specification refers to the heating of mixtures of the above derivatives of aromatic carboxylic acids with solid inert neutral inorganic salts or oxides, with or without substances taking part in the formation of the dyes.