US2216868A - Manufacture of coloring matters - Google Patents
Manufacture of coloring matters Download PDFInfo
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- US2216868A US2216868A US238809A US23880938A US2216868A US 2216868 A US2216868 A US 2216868A US 238809 A US238809 A US 238809A US 23880938 A US23880938 A US 23880938A US 2216868 A US2216868 A US 2216868A
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- Prior art keywords
- ammonium
- acid
- nickel
- metal
- phthalocyanine
- Prior art date
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- 238000004040 coloring Methods 0.000 title description 8
- 238000004519 manufacturing process Methods 0.000 title description 6
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 21
- 238000000034 method Methods 0.000 description 15
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 14
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 14
- 229910052751 metal Inorganic materials 0.000 description 13
- 239000002184 metal Substances 0.000 description 13
- 239000000463 material Substances 0.000 description 12
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 12
- 150000003839 salts Chemical class 0.000 description 12
- 229910021529 ammonia Inorganic materials 0.000 description 10
- NAYYNDKKHOIIOD-UHFFFAOYSA-N phthalamide Chemical compound NC(=O)C1=CC=CC=C1C(N)=O NAYYNDKKHOIIOD-UHFFFAOYSA-N 0.000 description 9
- IIACRCGMVDHOTQ-UHFFFAOYSA-N sulfamic acid Chemical compound NS(O)(=O)=O IIACRCGMVDHOTQ-UHFFFAOYSA-N 0.000 description 9
- GEHMBYLTCISYNY-UHFFFAOYSA-N Ammonium sulfamate Chemical compound [NH4+].NS([O-])(=O)=O GEHMBYLTCISYNY-UHFFFAOYSA-N 0.000 description 8
- CHCFOMQHQIQBLZ-UHFFFAOYSA-N azane;phthalic acid Chemical class N.N.OC(=O)C1=CC=CC=C1C(O)=O CHCFOMQHQIQBLZ-UHFFFAOYSA-N 0.000 description 7
- 150000001875 compounds Chemical class 0.000 description 7
- 229910052742 iron Inorganic materials 0.000 description 7
- 229910052759 nickel Inorganic materials 0.000 description 7
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 description 6
- 239000002253 acid Substances 0.000 description 6
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 description 6
- LGRFSURHDFAFJT-UHFFFAOYSA-N Phthalic anhydride Natural products C1=CC=C2C(=O)OC(=O)C2=C1 LGRFSURHDFAFJT-UHFFFAOYSA-N 0.000 description 5
- JHIWVOJDXOSYLW-UHFFFAOYSA-N butyl 2,2-difluorocyclopropane-1-carboxylate Chemical compound CCCCOC(=O)C1CC1(F)F JHIWVOJDXOSYLW-UHFFFAOYSA-N 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 5
- XKJCHHZQLQNZHY-UHFFFAOYSA-N phthalimide Chemical compound C1=CC=C2C(=O)NC(=O)C2=C1 XKJCHHZQLQNZHY-UHFFFAOYSA-N 0.000 description 5
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 4
- 229910017052 cobalt Inorganic materials 0.000 description 4
- 239000010941 cobalt Substances 0.000 description 4
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 4
- 230000018044 dehydration Effects 0.000 description 4
- 238000006297 dehydration reaction Methods 0.000 description 4
- 150000002739 metals Chemical class 0.000 description 4
- IEQIEDJGQAUEQZ-UHFFFAOYSA-N phthalocyanine Chemical class N1C(N=C2C3=CC=CC=C3C(N=C3C4=CC=CC=C4C(=N4)N3)=N2)=C(C=CC=C2)C2=C1N=C1C2=CC=CC=C2C4=N1 IEQIEDJGQAUEQZ-UHFFFAOYSA-N 0.000 description 4
- KMHSUNDEGHRBNV-UHFFFAOYSA-N 2,4-dichloropyrimidine-5-carbonitrile Chemical compound ClC1=NC=C(C#N)C(Cl)=N1 KMHSUNDEGHRBNV-UHFFFAOYSA-N 0.000 description 3
- STQPCKPKAIRSEL-UHFFFAOYSA-N 2-cyanobenzamide Chemical class NC(=O)C1=CC=CC=C1C#N STQPCKPKAIRSEL-UHFFFAOYSA-N 0.000 description 3
- 150000007513 acids Chemical class 0.000 description 3
- WDEQGLDWZMIMJM-UHFFFAOYSA-N benzyl 4-hydroxy-2-(hydroxymethyl)pyrrolidine-1-carboxylate Chemical compound OCC1CC(O)CN1C(=O)OCC1=CC=CC=C1 WDEQGLDWZMIMJM-UHFFFAOYSA-N 0.000 description 3
- 239000003153 chemical reaction reagent Substances 0.000 description 3
- 150000004820 halides Chemical class 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 239000000049 pigment Substances 0.000 description 3
- 238000006467 substitution reaction Methods 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- GVTLFGJNTIRUEG-ZHACJKMWSA-N (e)-n-(3-methoxyphenyl)-3-phenylprop-2-enamide Chemical compound COC1=CC=CC(NC(=O)\C=C\C=2C=CC=CC=2)=C1 GVTLFGJNTIRUEG-ZHACJKMWSA-N 0.000 description 2
- DTNSDCJFTHMDAK-UHFFFAOYSA-N 2-cyanobenzoic acid Chemical class OC(=O)C1=CC=CC=C1C#N DTNSDCJFTHMDAK-UHFFFAOYSA-N 0.000 description 2
- QIMMUPPBPVKWKM-UHFFFAOYSA-N 2-methylnaphthalene Chemical compound C1=CC=CC2=CC(C)=CC=C21 QIMMUPPBPVKWKM-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 2
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 150000003868 ammonium compounds Chemical class 0.000 description 2
- 150000003863 ammonium salts Chemical class 0.000 description 2
- MWPLVEDNUUSJAV-UHFFFAOYSA-N anthracene Chemical compound C1=CC=CC2=CC3=CC=CC=C3C=C21 MWPLVEDNUUSJAV-UHFFFAOYSA-N 0.000 description 2
- SARKQAUWTBDBIZ-UHFFFAOYSA-N azane;2-carbamoylbenzoic acid Chemical compound [NH4+].NC(=O)C1=CC=CC=C1C([O-])=O SARKQAUWTBDBIZ-UHFFFAOYSA-N 0.000 description 2
- 239000001056 green pigment Substances 0.000 description 2
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- -1 phthalmide Chemical compound 0.000 description 2
- 239000007858 starting material Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 230000001052 transient effect Effects 0.000 description 2
- JTPNRXUCIXHOKM-UHFFFAOYSA-N 1-chloronaphthalene Chemical compound C1=CC=C2C(Cl)=CC=CC2=C1 JTPNRXUCIXHOKM-UHFFFAOYSA-N 0.000 description 1
- SDGNNLQZAPXALR-UHFFFAOYSA-N 3-sulfophthalic acid Chemical class OC(=O)C1=CC=CC(S(O)(=O)=O)=C1C(O)=O SDGNNLQZAPXALR-UHFFFAOYSA-N 0.000 description 1
- BTTRMCQEPDPCPA-UHFFFAOYSA-N 4-chlorophthalic anhydride Chemical compound ClC1=CC=C2C(=O)OC(=O)C2=C1 BTTRMCQEPDPCPA-UHFFFAOYSA-N 0.000 description 1
- MMVIDXVHQANYAE-UHFFFAOYSA-N 5-nitro-2-benzofuran-1,3-dione Chemical class [O-][N+](=O)C1=CC=C2C(=O)OC(=O)C2=C1 MMVIDXVHQANYAE-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 239000005749 Copper compound Substances 0.000 description 1
- XFXPMWWXUTWYJX-UHFFFAOYSA-N Cyanide Chemical compound N#[C-] XFXPMWWXUTWYJX-UHFFFAOYSA-N 0.000 description 1
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- WWPPGEJAMWSVJJ-UHFFFAOYSA-N [Na].[K].[K] Chemical compound [Na].[K].[K] WWPPGEJAMWSVJJ-UHFFFAOYSA-N 0.000 description 1
- 150000001242 acetic acid derivatives Chemical class 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000008064 anhydrides Chemical class 0.000 description 1
- 150000001454 anthracenes Chemical class 0.000 description 1
- OSKNUZYLXFBIHL-UHFFFAOYSA-N azanium;hydron;phthalate Chemical compound N.OC(=O)C1=CC=CC=C1C(O)=O OSKNUZYLXFBIHL-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000001055 blue pigment Substances 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 description 1
- MPMSMUBQXQALQI-UHFFFAOYSA-N cobalt phthalocyanine Chemical compound [Co+2].C12=CC=CC=C2C(N=C2[N-]C(C3=CC=CC=C32)=N2)=NC1=NC([C]1C=CC=CC1=1)=NC=1N=C1[C]3C=CC=CC3=C2[N-]1 MPMSMUBQXQALQI-UHFFFAOYSA-N 0.000 description 1
- 229940097267 cobaltous chloride Drugs 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 150000001880 copper compounds Chemical class 0.000 description 1
- 230000006240 deamidation Effects 0.000 description 1
- KCGUMCUABUTCJM-UHFFFAOYSA-N disulfosulfamic acid Chemical compound OS(=O)(=O)N(S(O)(=O)=O)S(O)(=O)=O KCGUMCUABUTCJM-UHFFFAOYSA-N 0.000 description 1
- 230000008030 elimination Effects 0.000 description 1
- 238000003379 elimination reaction Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 229960002089 ferrous chloride Drugs 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- RBTKNAXYKSUFRK-UHFFFAOYSA-N heliogen blue Chemical compound [Cu].[N-]1C2=C(C=CC=C3)C3=C1N=C([N-]1)C3=CC=CC=C3C1=NC([N-]1)=C(C=CC=C3)C3=C1N=C([N-]1)C3=CC=CC=C3C1=N2 RBTKNAXYKSUFRK-UHFFFAOYSA-N 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- PVFSDGKDKFSOTB-UHFFFAOYSA-K iron(3+);triacetate Chemical compound [Fe+3].CC([O-])=O.CC([O-])=O.CC([O-])=O PVFSDGKDKFSOTB-UHFFFAOYSA-K 0.000 description 1
- 239000011133 lead Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 239000011572 manganese Substances 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 229910052976 metal sulfide Inorganic materials 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 150000002790 naphthalenes Chemical class 0.000 description 1
- 150000002816 nickel compounds Chemical class 0.000 description 1
- KERTUBUCQCSNJU-UHFFFAOYSA-L nickel(2+);disulfamate Chemical compound [Ni+2].NS([O-])(=O)=O.NS([O-])(=O)=O KERTUBUCQCSNJU-UHFFFAOYSA-L 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- XQZYPMVTSDWCCE-UHFFFAOYSA-N phthalonitrile Chemical compound N#CC1=CC=CC=C1C#N XQZYPMVTSDWCCE-UHFFFAOYSA-N 0.000 description 1
- 229920006391 phthalonitrile polymer Polymers 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 150000003458 sulfonic acid derivatives Chemical class 0.000 description 1
- VKHQYTLHHOQKSC-UHFFFAOYSA-N sulfosulfamic acid Chemical compound OS(=O)(=O)NS(O)(=O)=O VKHQYTLHHOQKSC-UHFFFAOYSA-N 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 150000003568 thioethers Chemical class 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
- C09B47/00—Porphines; Azaporphines
- C09B47/04—Phthalocyanines abbreviation: Pc
- C09B47/06—Preparation from carboxylic acids or derivatives thereof, e.g. anhydrides, amides, mononitriles, phthalimide, o-cyanobenzamide
Definitions
- This invention relates to the manufacture of 5 coloring matters of the phthalocyanine series. More particularly this invention deals with the manufacture of magnetic metal-phthalocyanines, namely those of iron, nickel, and cobalt.
- organic initial material mentioned in these patents is phthalic anhydride, phthalmide, phthalic acid diamide and ortho-cyano-benzamide, the
- the initial material is relatively more expensive, and has to be specially synthesized from the initial material first mentioned.
- the present invention relates to a process for 50 the manufacture of the iron, nickel and cobalt phthalocyanines in good yield from starting materials difierent from those hitherto used and easily accessible, or in improved yield when known ate is heated with substancesyielding cobalt, nickel or iron (1. e. the metals themselves or salts,
- cobalt, iron or nickel phthalocyanines (as the case may be) 5 are formed.
- the metals are added to the reaction mixture in the form of salts, and the reaction then proceeds smoothly at 220 C. to 260 C. conveniently at 240 C. to 250 0.; when free metals 10 are used, they are to be in a state of fine division and a somewhat higher temperature is needed.
- aminosulphonic acid or a salt thereof is intended to include aminosulphonic acid (sulphaminic' acid) and iminodisulphonic acid and their saltsand the nitrilo-sulphonates (see Inorganic Chemistry, Ephraim, trans. Thorne, London and Edinburgh, 1926, page 540).
- phthalic acid or a salt thereof for instance ammonium phthalate or one of the compounds ob- 40 tainable, at least theoretically, in the successive dehydration and deamidation of ammonium phthalate, for instance phthalamic acid, ammonium phthalamate, phthalic anhydride, phthalic acid diamide (phthalamide), phthalimide, or ortho-cyano-benzamide.
- their nuclear substitution derivatives may be employed, for instance monoor di-halogen, monoor di-nitro compounds, sulfonic acid derivatives and others.
- naphthaleneor anthracene-orthodicarboxylic' acids in lieuof the mentioned compounds of the phthalic acid family, the corresponding derivatives from naphthaleneor anthracene-orthodicarboxylic' acids may be employed. More specifically, 4-chlorophthalic anhydride, and 3- and 4-nitrophthalic anhydrides or other corresponding derivatives of the respective acids may be mentioned.
- the sulphophthalic acids are likewise adapted to serve as starting materials, and give characteristic products, soluble in. water.
- the said initial material is mixed with a salt of one of the metals above mentioned, for instance ferrous or ferric chloride, nickel chloride, ferrous or ferric acetate or the corresponding amino-sulfonates.
- amino-sulfonic acid or a alt thereof for instance amino-sulfonic acid, im' ⁇ odisulfonic acid, salts thereof or salts or nitrilo-trisulfonic acid (N (SOaH)3). Since the presence of ammonium compounds is favorable to the reaction, it is preferable to select as salts of the said amino-sulfonic acids their corresponding ammonium compounds. Alternatively, one may select the amino-sulfonates in the form of an alkali-metal salt or in the form of a salt of that metal whose phthalocyanine it is desired to prepare, for instance nickel-amino-sulfonate, etc.
- Example 2 --7 parts of phthalamide (phthalic acid diamide), 5 parts of ammonium sulfamate and 2 parts of nickel chloride are well mixed and heated at 220 to 240 C. until no more coloring matter is formed. It is isolated as in Example 1 and appears to be the same compound.
- Example 3 The procedure is the same as in Example 2, except that 2 parts of ferric chloride are employed in lieu of nickel chloride.
- the product, iron phthalocyanine, is a dull green pigment.
- Example 4 66 parts of phthalimide, 90 parts of ammonium aminosulionate and 16 parts of anhydrous nickel chloride are mixed and heated for 2 hours at 220 C. The product is isolated as in Example 1. It is a green coloring matter.
- the corresponding cobalt phthalocyanine may be prepared. It is a blue pigment.
- amino-sulf0nic compounds which come into consideration for the purpose of this inven-- tion are amino-sulfonic acid itself, trisodiumnitrilo-sulfonic acid and sodium-dipotassium nitrilo-sulfonic acid. These may be used in lieu of ammonium sulfamate in those cases where the initial material selected has itself suflicient nitrogen to form the hypothetical, transient oarylene-dicyanide, as for instance in Examples 1, 2 and 3 above.
- solvents or suspension media may be employed to assist in the manipulation.
- Suitable media for this purpose are indifferent organic liquids of conveniently high boiling point, for instance naphthalene,
- beta-methyl-naphthalene or crude chloro-naphthalene are examples of beta-methyl-naphthalene or crude chloro-naphthalene.
- the magnetic-metal-phthalocyanines are usefulpigments, the iron and nickel compounds being greenish blue in shade.
- pigments must satisfy various demands in which particular physical properties (fineness of division, non-crystalline form, freedom from impurities) are of great importance.
- the products of the present invention in its preferred embodiments are obtained in such a form that they are excellently suited for use as pigments; the process being such that any excess of reagent is readily removed, and the shades of the pigments being very bright.
- Ammonia may be passed through the reaction mass if desired.
- the organic compounds of this series may all be considered as derived, at least in theory, from the corresponding diammonium-ortho-arylenedicarboxylate by dehydration and deammoniation; that is, elimination of H20 units and of NH3 units.
- the typical formula of a phthalocyanine that is [CcH4(CN) 2]4.M wherein M is a bivalent metal, it appears that the initial material jointly with the ammonia contained in itself or furnished by the reaction mass, probably forms an orthoarylene-dicyanide in transient state during the course of the reaction.
- the process of producing iron phthalocyanine which comprises fusing together ammonium sulfamate, a halide of iron and initial material selected from the group consisting of ammonium phthalate, phthalic acid and ammonia, phthalic anhydride and ammonia, phthalic acid diamide, phthalamide and ammonia, o-cyano-benzamide, phthalamic acid and ammonia, ammonium phthalamate and the ammonium salt of o-cyanobenzoic acid.
- the process of producing nickel phthalocyanine which comprises heating together at a temperature between 220 and 250 C., phthalimide, ammonium sulfamate and nickel chloride.
- the process of producing nickel phthalocyanine which comprises heating together at a temperature between 220 and 250 0., ammonium phthalate, ammonium sulfamate and nickel 10 chloride.
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Nitrogen Condensed Heterocyclic Rings (AREA)
Description
Patented Oct. 8, 1940 PATENT OFFICE MANUFACTURE OF COLORING MATTERS 'Max Wyler, Blackley, Manchester, England, as-
signor to Imperial Chemical Industries Limited, a corporation of Great Britain No Drawing. Application November 4, 1938, Serial No. 238,809
6 Claims.
\ This application is a continuation-in-part of my copending application Serial No. 82,147, filed May 2'7, 1936.
This invention relates to the manufacture of 5 coloring matters of the phthalocyanine series. More particularly this invention deals with the manufacture of magnetic metal-phthalocyanines, namely those of iron, nickel, and cobalt.
It is an object of this invention to provide an eillclent and economical process for producing these metal-phthalocyanines. Other and further objects of this invention will appear as the description proceeds.
In British Patents Nos. 322,169, 389,842 and 410,814, there are described a series of coloring matters obtainable for instance by reacting phthalonitrile and copper or copper compounds; ortho-cyano-benzamide with iron, nickel, chromium, lead or manganese in the form of free 80 metal or in the form of oxides, sulfides or carbonates; or by passing ammonia into a melt of phthalic anhydride, phthalamide or phthalimide in the presence of a metal or metal oxide or sulfide. 2b The coloring matters so obtained have been named generically metal-phthalocyanines, and
individually copper-phthalocyanine, iron-phthalocyanine, etc.,.according to the metal which they contain. A more detailed discussion of their 30 structure is contained in a series of articles by Linstead et al., in the Journal of the Chemical Society for 1934, pages 1016 to 1039.
The processes of the two earlier British patents above mentioned have the advantage of starting 86 with relatively inexpensive initial material. The
organic initial material mentioned in these patents is phthalic anhydride, phthalmide, phthalic acid diamide and ortho-cyano-benzamide, the
corresponding derivatives of naphthalene and 40 anthracene, or nuclear substitution derivatives of these compounds. These processes, however, do not give such good yields and such high quality products as that of the subsequent process of Br. Patent No. 410,814, wherein an orthoarylene-di- 45 cyanide is employed. The latter, however, has
the disadvantage that the initial material is relatively more expensive, and has to be specially synthesized from the initial material first mentioned.
The present invention relates to a process for 50 the manufacture of the iron, nickel and cobalt phthalocyanines in good yield from starting materials difierent from those hitherto used and easily accessible, or in improved yield when known ate is heated with substancesyielding cobalt, nickel or iron (1. e. the metals themselves or salts,
e. g., halides or acetates) and with an aminosulphonic acid or a salt thereof, then cobalt, iron or nickel phthalocyanines (as the case may be) 5 are formed.
Usually the metals are added to the reaction mixture in the form of salts, and the reaction then proceeds smoothly at 220 C. to 260 C. conveniently at 240 C. to 250 0.; when free metals 10 are used, they are to be in a state of fine division and a somewhat higher temperature is needed.
The process appears to involve a dehydration, and agreeably to this interpretation there may be used instead of an ammonium phthaiate anll other derivative of the corresponding phthalic acid. Thus the phthalic diamides, or the salts of the phthalamic acids or the o-cyanobenzoic acids, or the o-cyanobenzamides may be used. Also, as the ammonium phthalates may be formed in situ, it is possible to use a phthalimide or a phthalic anhydride or a free phthalic acid, sufficient ammonia being of course provided, as by use of another ammonium salt. In this respect the invention may be regarded as an improvement on that described in British specification No. 322,- 169, the improvement being that the process is technically more feasible and in particular that higher yields are obtained. The same may be said when cyanobenzamides are used (compare British specification No. 389,842).
The term an aminosulphonic acid or a salt thereof is intended to include aminosulphonic acid (sulphaminic' acid) and iminodisulphonic acid and their saltsand the nitrilo-sulphonates (see Inorganic Chemistry, Ephraim, trans. Thorne, London and Edinburgh, 1926, page 540).
More particularly, I select as initial material phthalic acid or a salt thereof, for instance ammonium phthalate or one of the compounds ob- 40 tainable, at least theoretically, in the successive dehydration and deamidation of ammonium phthalate, for instance phthalamic acid, ammonium phthalamate, phthalic anhydride, phthalic acid diamide (phthalamide), phthalimide, or ortho-cyano-benzamide. In lieu of the above particular compounds, their nuclear substitution derivatives may be employed, for instance monoor di-halogen, monoor di-nitro compounds, sulfonic acid derivatives and others. ,Also, in lieuof the mentioned compounds of the phthalic acid family, the corresponding derivatives from naphthaleneor anthracene-orthodicarboxylic' acids may be employed. More specifically, 4-chlorophthalic anhydride, and 3- and 4-nitrophthalic anhydrides or other corresponding derivatives of the respective acids may be mentioned. The sulphophthalic acids are likewise adapted to serve as starting materials, and give characteristic products, soluble in. water.
The said initial material is mixed with a salt of one of the metals above mentioned, for instance ferrous or ferric chloride, nickel chloride, ferrous or ferric acetate or the corresponding amino-sulfonates.
To these is added an amino-sulfonic acid or a alt thereof, for instance amino-sulfonic acid, im' \odisulfonic acid, salts thereof or salts or nitrilo-trisulfonic acid (N (SOaH)3). Since the presence of ammonium compounds is favorable to the reaction, it is preferable to select as salts of the said amino-sulfonic acids their corresponding ammonium compounds. Alternatively, one may select the amino-sulfonates in the form of an alkali-metal salt or in the form of a salt of that metal whose phthalocyanine it is desired to prepare, for instance nickel-amino-sulfonate, etc.
Without limiting my invention to any particular procedure, the following examples are given to illustrate my preferred mode of operation. Parts mentioned are by weight.
mp e 1.'7 parts of ammonium phthalate, CsH4(COONH4) 2, '7 parts of ammonium aminosulfonate and 2 parts of nickel chloride are well mixed and heated. The mixture becomes partly fluid at about 220 C. and blue at about 240 C. It is kept at 240 to 250 C. until formation of coloring matter is complete. The mixture is cooled, ground, boiled with water and filtered. The solid matter is dried, dissolved in 10 parts of 94% sulfuric acid, poured into 100 parts of water, filtered, washed free of acid and dried. Nickel phthalocyanine is thus obtained in good yield and constitutes a green pigment.
Example 2.--7 parts of phthalamide (phthalic acid diamide), 5 parts of ammonium sulfamate and 2 parts of nickel chloride are well mixed and heated at 220 to 240 C. until no more coloring matter is formed. It is isolated as in Example 1 and appears to be the same compound.
Example 3.-The procedure is the same as in Example 2, except that 2 parts of ferric chloride are employed in lieu of nickel chloride. The product, iron phthalocyanine, is a dull green pigment.
Example 4.-66 parts of phthalimide, 90 parts of ammonium aminosulionate and 16 parts of anhydrous nickel chloride are mixed and heated for 2 hours at 220 C. The product is isolated as in Example 1. It is a green coloring matter.
In a similar manner, by using cobaltous chloride, the corresponding cobalt phthalocyanine may be prepared. It is a blue pigment.
Other amino-sulf0nic compounds which come into consideration for the purpose of this inven-- tion are amino-sulfonic acid itself, trisodiumnitrilo-sulfonic acid and sodium-dipotassium nitrilo-sulfonic acid. These may be used in lieu of ammonium sulfamate in those cases where the initial material selected has itself suflicient nitrogen to form the hypothetical, transient oarylene-dicyanide, as for instance in Examples 1, 2 and 3 above.
In all the examples above, solvents or suspension media may be employed to assist in the manipulation. Suitable media for this purpose are indifferent organic liquids of conveniently high boiling point, for instance naphthalene,
beta-methyl-naphthalene or crude chloro-naphthalene.
The magnetic-metal-phthalocyanines are usefulpigments, the iron and nickel compounds being greenish blue in shade. For technical purposes pigments must satisfy various demands in which particular physical properties (fineness of division, non-crystalline form, freedom from impurities) are of great importance. The products of the present invention in its preferred embodiments are obtained in such a form that they are excellently suited for use as pigments; the process being such that any excess of reagent is readily removed, and the shades of the pigments being very bright.
Ammonia may be passed through the reaction mass if desired.
Other variations and modifications may be made, within the scope of the prior British patents above mentioned, as will be readily apparent to those skilled in the art.
It will be clear from the above discussion and examples that my invention is applicable to the manufacture of metal-phthalocyanines by starting out with the respective metalliferous reagent, that is the respective free metal or a salt thereof, and using any of the following organic or mixed initial materials:
Ammonium phthalate C|3H4(C00NH4)2 Phthalic acid ammonia e 4(C00H) 2NH Phtlialic anhydride ammonia CoH gCO)2O 2NH Phthalic acid dlamide (36H; CONHz 2 Phthallmide ammonia CH4(CO) NH NH also, nuclear substitution derivatives of the above compounds, as well as the corresponding derivatives of the naphthalene or anthracene series.
The organic compounds of this series may all be considered as derived, at least in theory, from the corresponding diammonium-ortho-arylenedicarboxylate by dehydration and deammoniation; that is, elimination of H20 units and of NH3 units. Furthermore, when the typical formula of a phthalocyanine is considered, that is [CcH4(CN) 2]4.M wherein M is a bivalent metal, it appears that the initial material jointly with the ammonia contained in itself or furnished by the reaction mass, probably forms an orthoarylene-dicyanide in transient state during the course of the reaction. These two factors tie the above diversified group of materials into a single family with readily determinable common characteristics.
I claim:
1. The process of producing a magnetic metal phthalocyanine which comprises heating initial material adapted to form an ortho-arylene-dicyanide by dehydration, with a reagent adapted to furnish a magnetic metal, in the presence of ammonium sulfamate.
2. The process of producing iron phthalocyanine which comprises fusing together ammonium sulfamate, a halide of iron and initial material selected from the group consisting of ammonium phthalate, phthalic acid and ammonia, phthalic anhydride and ammonia, phthalic acid diamide, phthalamide and ammonia, o-cyano-benzamide, phthalamic acid and ammonia, ammonium phthalamate and the ammonium salt of o-cyanobenzoic acid.
3. The process of producing nickel phthalophthalimide, a halide of a magnetic metal, and ammonium sulfamate.
5. The process of producing nickel phthalocyanine which comprises heating together at a temperature between 220 and 250 C., phthalimide, ammonium sulfamate and nickel chloride.
6. The process of producing nickel phthalocyanine which comprises heating together at a temperature between 220 and 250 0., ammonium phthalate, ammonium sulfamate and nickel 10 chloride.
MAX WYLER.
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US238809A US2216868A (en) | 1938-11-04 | 1938-11-04 | Manufacture of coloring matters |
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US238809A US2216868A (en) | 1938-11-04 | 1938-11-04 | Manufacture of coloring matters |
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Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2897039A (en) * | 1952-10-11 | 1959-07-28 | Bayer Ag | Intermediates for the production of cobalt phthalocyanines |
US3074958A (en) * | 1960-12-02 | 1963-01-22 | Allied Chem | Process for preparing metal phthalocyanines |
US3985767A (en) * | 1973-06-20 | 1976-10-12 | Produits Chimiques Ugine Kuhlmann | Process for the preparation of copper phthalocyanine |
-
1938
- 1938-11-04 US US238809A patent/US2216868A/en not_active Expired - Lifetime
Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2897039A (en) * | 1952-10-11 | 1959-07-28 | Bayer Ag | Intermediates for the production of cobalt phthalocyanines |
US3074958A (en) * | 1960-12-02 | 1963-01-22 | Allied Chem | Process for preparing metal phthalocyanines |
DE1192762B (en) * | 1960-12-02 | 1965-05-13 | Allied Chem | Process for the preparation of unsubstituted metal phthalocyanines |
US3985767A (en) * | 1973-06-20 | 1976-10-12 | Produits Chimiques Ugine Kuhlmann | Process for the preparation of copper phthalocyanine |
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