pr

2,925,423 Patented Feb. 16, 1960

1. A further object of this invention is to provide prac tical processes for synthesizing compounds of the above S 2,925,423 - formula. Various additional objects and achievements SOLVENTSOLUBLE METAL PATHALOCYANNE of this invention will appear as the description proceeds. COMPOUNDS AND PROCESS OF MAKING THE My preferred process for manufacturing said com nés comprises heating a metal phthalocyanine poly Wiktor Weinmayr, Landenberg, Pay-assignor to E. I. du li-metal salt thereof, or an ester - Pont de Nemours and Company, WiWiig, ibi. r of 1 to 4 Catoms in the alkyl . corporation of Delaware M alocyanine polysulfonyl chloride

lyselfonamide, or a nuclear halogen derivative of NoDrawing Applicati any such compound in a mixture of sulfur tetrafluoride . .andhyarogen fluoride in a sealed-vessel, at a temperature of 100° to 175°C., for a convenient length of time, say 1 to 8 hours. said initial phthalocyanine This invention relates to a novel series offraetal m . . . . 2 of those above mentioned, 'phthalocyanine derivatives which are soluble in organic balt. The number of sulfo “solvents such as acetone, alcohol, benzene and pyridine. groups per molectile (using this term to embrace both For simplicity of reference, acetone will be used herein the sulfonic acid radical and its functional derivatives as after as typical of said group of organic solvents, and above specified) is preferably not less than 2 per mole 2a substance will be considered as soluble in this standard, 20 cute. Customarily, however, it will be 3 to 4. if it dissolves therein to the extent-of at least 0.1% by eady indicated, the initial material may be en *weight, although at 20° C. some of the compounds dis of halogen in the nucleus, or it may contain -fcuissed hereinbelow will dissolve to ana extent as high as - 16-in) halogen atoms (F, Clor Br) per mole 10% or even higher...... ; cule, in being the number of sulfo groups in the molecule. phthalocyanine,As is well known, nickel metal phthalocya phthalocyanine such as copper av gether, the initial material may be defined by the

(II) perature or at it wherein. MPc, in and Xhave the same meaning as in , ) is a perceptib Formula I, the subscript z may have a value from zero to . atives of said compounds, such (16 in): inclusive, while:Z stands for OH, OM1 (M1=an. o, alkoxy, phenyl, phenoxy, ani 3-alkali metal), OR (R=alkyl-of-1 to 4 C-atoms), Clor. fonated copper phthalocyanine is soluble NH. the degree of sulfonation is high enough;but The process; above-outlined not-only, converts the SOZ phthalocya fine derivatives soluble in organic solvents groups into SQF groups, but also tends to introduce have been scarce. . . . . fluorine into the Bznuclei. As a consequence, y in the Fn U.S. Paterit 2,227,628, fluorinated copper phthalo 40 final-product (Formula I above) will generally be greater cyanine 'containing up to 7-fluorine atoms permolecule than 2 in the initial material. (Formula II), provided z and polychloropolyfluoro copper phthalocyanines have. is not near-its upper limit of (16 -n). been described. But these compounds are pigments, in Furthermore, where the initial-material has no halo 'soluble in water and in organic solvents. gen-at-all or only a low contentithereof, the product of In the case of chlorinated derivatives, copper phthalo -the-autoclaving treatment-may be subjected to halogena cyanines having various C1 contents, from 0.5 atom (on 45 tion in known manner to introduce additional halogen the average) to 15.5 or even 16 atoms permolecule have: atoms; into the nuclei, which halogen atoms may be been known for a longtime. But in their solubility char chlorine, bromine or more fluorine. - s 'acteristics they are true to the "rule: They are insoluble in Finally, I may treat the initial material-of Formula II water and in organic solvents. . , ' , " ...... 50 above with agents adapted only to replace Z in the group r. This inventionisi based on the amazing discovery that SOZ by fluorine, i.e., without achieving simultaneous 3 metal phthalocyanines icontaining both fluorostilfonyl. fluorination in the ring. If the initial material has no groups and nuclear:halogeni Substituents, there being at nuclear halogen (i.e., z=0, in Formula II), the product least: two SOF groups and at leastCone nuclear halogen of this treatment may be isolated, and then treated with atom: per molecule, are: soluble in organic solvents, as 55 agents adapted to introduce halogen (F, Clor, Br) into typified by a solubility of at least 0.1% by weight in the Bz-rings. A simple illustration of such alternative acetone and often rising to more than 10%. This is true: process is the treatment of copper phthalocyanine tetra particularly where the nuclear halogenis fluorine, chlorine sulfonyl chloride in an autoclave with a solution of potas 3 or bromine. (In other words, it has an atomic number sium fluoride in hydrogen fluoride, recovering the result not exceeding 35) ...... opper phthalocyanine tetrasulfonyl fluoride and re objectAccordingly, the production this invenition of hoveliconipoun embra asE. its inci al 60 acting upon the... " latter withP . . . a. desirable. . . . s - halogenating.e. ' agent,- - - .is . suchuch as chlorine, bromine, sulfur monochloride or sulfur expressed by the general formula ... tetrafluoride, in hydrogen fluoride. ... It will be clear from the aforegoing available methods : sor). of synthesis that X in the formula of the product is . not limited to representing a single halogen; instead, it may represent various combinations of Cland F, Brand

"wherein-MPc designates the molecule of a metal-phthalo F, or Cl, Brand F, whose total number per molecule . cyanine, M beinga-metal of the group consisting of cop -per, nickel and cobalt, X designates halogen-selected from 70 The quantities of SF, and HF to be employed in my 'preferred process above set forth may vary from 1 to a theis a groupnumeral consisting-of from 2 to 4, fluorine and y ischlorine a numeral and not bromine, less than in preferred10 parts (byprocess weight) above of setSF, forti and from - 0.5- - - to- - - - -50 - - - - parts- ... 2,935,433 ------. . . - 3 4. - of HF per part of initial polysulfo metal phthalocyanine. tained was extracted with acetone. Upon evaporation The preferred duration of the heating is best determined of the acetone, 4.9 parts of a fluorinated copper phthalo by experiment and observation of the results. One hour cyanine was obtained. will give a quantity of acetone-soluble product in some Analyses of the new blue dye showed a N:F ratio cases, but a longer period generally increases the yield. of about 1:1. Inasmuch as there are 8 N-atoms per Two to six hour may be taken as an optimum period molecule, and inasmuch as the initial material contained, for most cases. on the average, only about 2.4 sulfo groups per molecule, The theory of the reaction is not altogether clear to and since it appears logical that each SO3Na group is me, and should not be taken in any sense as a limitation converted in the above reaction to SOF, it follows from upon this invention. But for the sake of making the 0. the above analysis that considerable nuclear fluorination understanding thereof clearer, I offer the following as a has taken place, resulting in fact in some 5 to 6 nuclear probable hypothesis for the course of the reaction. F-atoms per molecule...... The sulfur tetrafluoride acts on the SOZ groups, con The acetone and benzene solutions of the reaction verting them into SOF groups, and in combination product were blue; sulfuric acid solutions were green. with HF it acts further on the benzene nuclei to replace The product showed also marked solubility in many some of the H-atoms (if such are still available) by other organic solvents. It was also highly resistant to fluorine. oxidation with a hot dilute sulfuric acid-ceric sulfate solu An incidental, equally unexpected, but most valuable tion, whereas the starting material was readily oxidized in property of my novel compounds is that they possess ; this solution at room temperature. The new product increased resistance to oxidation. Thus, whereas copper 20 was also very resistant to oxidation with boiling 95% phthalocyanine and copper phthalocyanine sulfonic acids nitric acid. Upon oxidation with fuming nitric acid, a are readily oxidized by acidic, aqueous, ceric sulfate solu high yield of a sulfonyl fluoride of phthalimide was tions at room temperature, and whereas even polychlo obtained. - rinated copper phthalocyanine containing as high as 14 The fluorinated copper phthalocyanine of this example Cl-atoms per molecule is quickly oxidized by ceric sul 25 did not lose its solubility in organic solvents by heating fate solutions upon slight warming, many of the novel it in 100% sulfuric acid to 130 C. and drowning the compounds of this invention will withstand heating in solution on ice. Neither did it become water- or am boiling ceric sulfate solution (110° C.) for several hours monia-soluble by that treatment. without being changed to any perceptible degree. Example 2 This valuable collateral property makes my novel com pounds useful in many fields where hitherto known Twenty parts of the potassium salt of a copper phthalo phthalocyanine compounds have not been applicable. cyanine tetra(4)sulfonic acid (made from 4-sulfophthalic For instance, inasmuch as the novel compounds of this acid), 60 parts of anhydrous hydrogen fluoride, and 30 invention are not attacked by peroxides, they may be: parts of sulfur tetrafluoride were heated in a nickel bomb incorporated as colorants into monomers which are to be to 150° C. for 6 hours, After isolation of the reaction polymerized by the aid of dibenzoyl peroxide or similar product and extraction with acetone as described in catalysts into plastics. - - Example 1, 7.5 parts of acetone-soluble blue product My novel compounds may also be utilized where their were obtained. : Analyses of the new blue dye gave a solubility in organic solvents shows up to advantage..., N:F ratio of 1:1, which indicates that the product is For instance, they may be applied to textile fibers from 40 copper tetrafluoro-phthalocyanine tetrasulfonyl fluoride. organic solvent solution, to produce brilliant blue to The tetrasulfo starting material was readily oxidized green, and usually light-fast dyeings on most of them. by aqueous, acidic, ceric sulfate at room temperature, They may also be incorporated into inks and lacquers, but the fluorinated reaction product was oxidized in the from which printings can be made exhibiting the excep same medium only upon heating. Upon oxidation of the tional light-fastness and pleasing brilliance of the phthalo new soluble, dye with fuming nitric acid at the boil, a cyanine colors in general. On the other hand, they may sulfonyl fluoride of phthalimide was obtained. also be used as pigments, like hitherto known phthalo The soluble dye of this example was also stable upon cyanines, but with the added advantage that the result heating to 130 C. in 100% sulfuric acid, and remained ing prints or coatings possess high stability to fading. water- and alkali-insoluble, and organic-solvent-soluble by oxidiation. after that treatment. Without limiting this invention, the following examples Example 3 are given to illustrate my preferred mode of operation. Two parts of a copper phthalocyanine sulfonyl chloride Parts mentioned are by weight. . containing an average of three sulfonyl chloride groups for molecule, and made by reacting copper phthalo Example 1 cyanine with chlorosulfonic acid, 20 parts of anhydrous Ten parts of the sodium salt of sulfonated copper hydrogen fluoride, and 7 parts of sulfur tetrafluoride were phthalocyanine (obtained by direct sulfonation of copper heated at 150 C. for six hours, and the reaction product phthalocyanine and containing an average of 2.4 sulfo was isolated, as described in Example 1.1.4 parts of groups per molecule), 90 parts of anhydrous hydrogen acetone-soluble fluorinated reaction products were ob fluoride, and 30 parts of sulfur tetrafluoride were charged 60 tained, whose analyses showed a N:F ratio of 1:1. It into a stainless steel bomb which had been cooled in a also contained chlorine. The acetone-soluble product was Dry Ice-acetone mixture and had been swept with nitro insoluble in hot dilute aqueous ammonia. It was soluble gen. The bomb was closed and put into an oil bath in 100% sulfuric acid and was recovered from it (by where it could be agitated. The temperature of the . drowning in water and filtration) in its original, water oil bath was raised to 150° C. over a period of about 65, insoluble, organic-slovent-soluble form. four hours and the bomb was agitated at an oil bath Example 4 temperature of 150 to 155 C. for six hours. After cooling the bomb to room temperature it was cooled Two parts of the potassium salt of nickel phthalo further in iced water and the remaining pressure, mainly cyanine disulfonic acid (prepared by sulfonating nickel due to an excess of sulfur tetrafluoride, was released. 70. phthalocyanine in 20 parts of 10% oleum, drowning in The reaction mass was then poured onto about 200 parts dilute KCl solution, filtering and washing with 15%. KCl of ice, filtered, washed nearly acid free, slurried in 200 solution), 20 parts of anhydrous hydrogen fluoride, and parts of dilute aqueous ammonia to neutralize all hydro 5 parts of sulfur tetrafluoride were heated at 150 C. gen fluoride, filtered and washed again with water, and under autogenous pressure for six hours. Upon dilution dried at 80° to 90° C. The deep blue solid thus ob 5 and extraction with acetone in the manner hereinabove a,985,428 :

ietforth,s' Y - 0.3-part-of-material dissolvingdissol in acetone, and The hydrogen fluoride employed in some of the above 'other organic solvents, with a blue coller was obtained examples has been specified as anhydrous; in other ex amples, technical hydrogen fluoride has been used by Examples. S. me. The latter, contains traces of moisture. Thus, an Fifteen parts of a mixture of copper phthalo hydrous HF is not an absolute requirement for this reac polysulfonyl chlorides (being ture of tri tion, but is a desirable goal from the practical viewpoint, sulfonyl chlorides, and con th the inasmuch as, hydrogen fluoride containing water is highly . isomers), 10 parts of potas St. Goride dihydrate corrosive to equipment." - (KF2HO) and 80 parts of anhydrous hydrogen fluoride In the synthesis employing metal phthalocyanine sul were heated in a closed nickel vessel at 150 C. for 4 10 fonic acids or salts thereof, the reaction mass should con hours. The reaction mass was then cooled, and poured tain at least 0.5 part by weight of HF and at least 1.0 - on ice. The blue precipitate was filtered, washed acid part of SF per part of the initial metal phthalocyanine free, and dried over calcium chloride in an evacuated des compound. But I know of no theoretical upper limit, iccator at room temperature. 8.4 parts of a compound except the obvious consideration that the larger the ex analyzing essentially as a copper phthalocyanine polysul 15 cess of either gas employed, the larger the expense of sub fonyl fluoride were obtained. The product was very sequent recovery. Consequently, upper limits of 50 parts slightly soluble in acetone. The compound was insoluble of HF by weight and 10 parts of SF are recommended in warm dilute ammonium hydroxide while the starting as a matter of economy. - material, the copper phthalocyanine sulfonyl chloride, I claim as my invention: dissolved instantly to a blue solution in dilute aqueous 20 1. A compound of the formula ammonia. S. Higher yields were obtained in this example when S OF) anhydrous potassium fluoride was used instead of the di p? hydrate. Y, Example 6 25 wherein MPc designates the molecule of a metal phthalo Five parts of copper phthalocyanine polysulfonyl fluo cyanine, M being a metal of the group consisting of ride prepared as described in Example 5 and 75 parts of copper, nickel and cobalt, X designates halogen selected anhydrous hydrogen fluoride were cooled in a nickel ves ... from the group consisting of fluorine, chlorine and isel in a Dry Ice-acetone bath, and 5 parts of chlorine 30 bromine, n is a numeral from 2 to 4, and y is a numeral ... were added. The vessel was closed and the charge was not less than 1, said compound being characterized by then heated over a period of two hours to 100 C. and greater solubility in acetone and by increased resistance agitated at 100 C. for two hours. The reaction mass. to oxidation in acidic aqueous ceric sulfate solution com was then poured on ice, and 4 parts of a dark green solid pared to the corresponding unsubstituted phthalocyanine were isolated and then extracted with acetone. Upon 35 compound of form MPc. evaportalion of solvent from the green solution, a green 2. Copper polyhalogeno-phthalocyanine polysulfonyl -- solid containing 20% chlorine was obtained. This prod fluoride, wherein the halogen is of atomic number not uct was readily soluble in acetone with a green color, exceeding .35, said compound being characterized by while the unchlorinated starting material was only slightly greater solubility in acetone and by increased resistance soluble in acetone with a blue color. 40 to oxidation in acidic aqueous ceric sulfate solution com Example 7 pared to copper phthalocyanine...... 3. Copper polychloro-phthalocyanine tetrasulfonyl Five parts of a mixture of copper phthalocyanine poly fluoride, the number of chlorine atoms being not less than sulfonyl fluoride as obtained in Example 5 were added to 4 and not more than 12 per molecule, said compound 25 parts of sulfur dichloride which had been cooled in a being characterized by greater solubility in acetone and stainless steel bomb in a Dry Ice-acetone mixture. 90 45 by increased resistance to oxidation in acidic aqueous parts of hydrogen fluoride were then added, and the ceric sulfate solution compared to copper phthalocyanine. charge was heated at 150° C. for six hours, under auto 4. Copper tetrafluoro-phthalocyanine ... tetrasulfonyl genous pressure. The reaction mass was cooled, poured fluoride, said compound being characterized by greater on ice and the precipitate was isolated in the usual man solubility in acetone and by increased resistance to oxida ner. This precipitate amounted to 4 parts and was con 50 tion in acidic aqueous ceric sulfate solution compared to taminated with elemental sulfur. Upon extraction with copper phthalocyanine. acetone and evaporation of solvent from the green solu 5. The process of producing an acetone-soluble metal tion, a green solid was obtained which analyzed as having phthalocyanine, which comprises heating together under a ratio of N:Cl:F-8:12.2:55. 55. autogenous pressure a metal phthalocyanine compound Example 8 of the group consisting of metal phthalocyanine poly Three parts of bromine were put into a nickel vessel Sulfonic acids, their alkali-metal salts, metal phthalo and cooled in a Dry Ice-acetone mixture. 5 parts of a mix cyanine polysulfonyl chlorides, metal phthalocyanine ture of copper phthalocyanine polysulfonyl fluorides from polysulfonamides, metal, phthalocyanine polysulfonic Example 5 were added, followed by 60 parts of anhydrous 60 acid esters and the nuclear halogen derivatives of any of . hydrogen fluoride. The charge was heated in the closed these, and a mixture of sulfur tetrafluoride and hydrogen : nickel vessel at 150° C. for six hours and then poured on fluoride, whereby to obtain a nuclearly fluorinated metal, , , , ice. The precipitate was isolated in the usual manner and . phthalocyanine polysulfonyl fluoride...... - - - 4 parts of a green solid were obtained. Upon extraction: 6. A process as in claim 5, including the further step with acetone (deep green solution) and evaporation of 65 of reacting upon the compound thus produced with a . solvent, a green product readily soluble in acetone with halogenating agent of the group consisting of brominat a green color was obtained. ing and chlorinating agents, whereby to introduce addi It will be understood that the details of procedure may tional halogen into the Bz-nuclei of the compound. be varied widely within the skill of those engaged in this 7. A process as in claim 5, wherein the reaction is: art. If nickel chloride or cobalt chloride is used in lieu achieved by heating a mixture of the reactants, under of the copper salt in the synthesis of the phthalocyanine 70 autogenous pressure at a temperature between 100 and compound, the resulting metal polysulfophthalocyanine, 175°C. when carried through the procedures of the above ex 8. The process of producing an acetone-soluble copper. amples, will lead to acetone-soluble derivatives of nickel phthalocyanine, which comprises heating together under and cobalt-phthalocyanine, respectively. 75 autogenous pressure copper phthalocyanine-tetrasulfonic 2,925,428 - 7 8 acid and a mixture of hydrogen fluoride and sulfur tetra- 2,227,628. - Calcott ------Jan. 7, 1941 fluoride, whereby to produce copper tetrafluoro-phthalo- 2,702,306 ... Gallet al. ------Feb. 15, 1955 cyanine tetrasulfonyl fluoride. w FOREIGN PATENTS France ------Apr. 15, 1940

References Cited in the file of this patent 5 E; Great Britain ------Nov. 20, 1939 UNITED STATES PATENTS siss37 Great Britain. ------Dec. 11, 1939 2,225,441 Braun et al.------Dec. 17, 1940 281990 , Switzerland.------Mar. 31, 1952