US3407098A - Colorant film for aluminum surfaces - Google Patents
Colorant film for aluminum surfaces Download PDFInfo
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- US3407098A US3407098A US482545A US48254565A US3407098A US 3407098 A US3407098 A US 3407098A US 482545 A US482545 A US 482545A US 48254565 A US48254565 A US 48254565A US 3407098 A US3407098 A US 3407098A
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- nickel
- aluminum
- isoindol
- imino
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- 229910052782 aluminium Inorganic materials 0.000 title claims description 33
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 title claims description 32
- 239000003086 colorant Substances 0.000 title description 8
- 238000000034 method Methods 0.000 claims description 19
- VEQPNABPJHWNSG-UHFFFAOYSA-N Nickel(2+) Chemical compound [Ni+2] VEQPNABPJHWNSG-UHFFFAOYSA-N 0.000 claims description 15
- 238000004040 coloring Methods 0.000 claims description 9
- 238000009835 boiling Methods 0.000 claims description 8
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 claims description 4
- 150000004945 aromatic hydrocarbons Chemical class 0.000 claims description 4
- 238000010438 heat treatment Methods 0.000 claims description 4
- 150000005826 halohydrocarbons Chemical class 0.000 claims description 3
- 101000740162 Homo sapiens Sodium- and chloride-dependent transporter XTRP3 Proteins 0.000 claims 1
- 102100037189 Sodium- and chloride-dependent transporter XTRP3 Human genes 0.000 claims 1
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 12
- 239000000243 solution Substances 0.000 description 12
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 11
- -1 Nujol Chemical compound 0.000 description 11
- RZVCEPSDYHAHLX-UHFFFAOYSA-N 3-iminoisoindol-1-amine Chemical compound C1=CC=C2C(N)=NC(=N)C2=C1 RZVCEPSDYHAHLX-UHFFFAOYSA-N 0.000 description 10
- 239000000203 mixture Substances 0.000 description 7
- 239000000047 product Substances 0.000 description 7
- PBKONEOXTCPAFI-UHFFFAOYSA-N 1,2,4-trichlorobenzene Chemical compound ClC1=CC=C(Cl)C(Cl)=C1 PBKONEOXTCPAFI-UHFFFAOYSA-N 0.000 description 6
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 6
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 6
- 125000003545 alkoxy group Chemical group 0.000 description 6
- 238000004043 dyeing Methods 0.000 description 6
- 125000001841 imino group Chemical group [H]N=* 0.000 description 6
- 150000002816 nickel compounds Chemical class 0.000 description 6
- LFHLEABTNIQIQO-UHFFFAOYSA-N 1H-isoindole Chemical compound C1=CC=C2CN=CC2=C1 LFHLEABTNIQIQO-UHFFFAOYSA-N 0.000 description 5
- VHMICKWLTGFITH-UHFFFAOYSA-N 2H-isoindole Chemical compound C1=CC=CC2=CNC=C21 VHMICKWLTGFITH-UHFFFAOYSA-N 0.000 description 5
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 description 5
- QKDLQFSLLCQTOH-UHFFFAOYSA-N Trichodonin Natural products C1C(O)C2C3(COC(=O)C)C(C=O)C(C)(C)CCC3OC(=O)C22C(=O)C(=C)C1C2 QKDLQFSLLCQTOH-UHFFFAOYSA-N 0.000 description 5
- 150000001875 compounds Chemical class 0.000 description 5
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 description 5
- 238000010992 reflux Methods 0.000 description 5
- RFFLAFLAYFXFSW-UHFFFAOYSA-N 1,2-dichlorobenzene Chemical compound ClC1=CC=CC=C1Cl RFFLAFLAYFXFSW-UHFFFAOYSA-N 0.000 description 4
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 4
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 4
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 4
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 4
- 230000001464 adherent effect Effects 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical class [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 description 4
- DNIAPMSPPWPWGF-GSVOUGTGSA-N (R)-(-)-Propylene glycol Chemical compound C[C@@H](O)CO DNIAPMSPPWPWGF-GSVOUGTGSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- AMQJEAYHLZJPGS-UHFFFAOYSA-N N-Pentanol Chemical compound CCCCCO AMQJEAYHLZJPGS-UHFFFAOYSA-N 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 239000011248 coating agent Substances 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- 239000000706 filtrate Substances 0.000 description 3
- 229910052759 nickel Inorganic materials 0.000 description 3
- 239000011541 reaction mixture Substances 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 2
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 2
- 235000019270 ammonium chloride Nutrition 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 239000000975 dye Substances 0.000 description 2
- 238000001704 evaporation Methods 0.000 description 2
- 150000002815 nickel Chemical class 0.000 description 2
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(II) nitrate Inorganic materials [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 2
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 description 2
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 2
- 239000003208 petroleum Substances 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 238000007738 vacuum evaporation Methods 0.000 description 2
- 239000008096 xylene Substances 0.000 description 2
- 229910000838 Al alloy Inorganic materials 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 238000007743 anodising Methods 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 238000005238 degreasing Methods 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- GWVMLCQWXVFZCN-UHFFFAOYSA-N isoindoline Chemical compound C1=CC=C2CNCC2=C1 GWVMLCQWXVFZCN-UHFFFAOYSA-N 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 239000003350 kerosene Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000005244 neohexyl group Chemical group [H]C([H])([H])C(C([H])([H])[H])(C([H])([H])[H])C([H])([H])C([H])([H])* 0.000 description 1
- AIYYMMQIMJOTBM-UHFFFAOYSA-L nickel(ii) acetate Chemical compound [Ni+2].CC([O-])=O.CC([O-])=O AIYYMMQIMJOTBM-UHFFFAOYSA-L 0.000 description 1
- 230000035515 penetration Effects 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D11/00—Electrolytic coating by surface reaction, i.e. forming conversion layers
- C25D11/02—Anodisation
- C25D11/04—Anodisation of aluminium or alloys based thereon
- C25D11/18—After-treatment, e.g. pore-sealing
- C25D11/24—Chemical after-treatment
- C25D11/243—Chemical after-treatment using organic dyestuffs
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F15/00—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table
- C07F15/04—Nickel compounds
- C07F15/045—Nickel compounds without a metal-carbon linkage
-
- 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
- C09B57/00—Other synthetic dyes of known constitution
- C09B57/04—Isoindoline dyes
-
- 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
- C09B57/00—Other synthetic dyes of known constitution
- C09B57/10—Metal complexes of organic compounds not being dyes in uncomplexed form
Definitions
- This invention relates to a novel class of coordination compounds, their synthesis and use.
- the novel compounds are useful for coloring aluminum.
- the vnovel compounds ofthis invention are-bis[ 3-(3-alkoxylH-isoindol-l-imino)-1H-isoindol-1-irninato] nickel II) having the formula shown in theaccompanying drawing where R is alkyl of 1 to 6 carbons, suitably methyl, ethyl, isopropyl, n-butyl, n-amyl, sec. amyl and neohexyl.
- I 'Dyeings possessing some acceptable'light-fastness are achieved on anodized aluminum when the aluminum is properly anodized and the surface sealed after dyeing by treating it with boiling water or steam.
- anodized aluminum has usually been dyed with various dyes in aqueous or non-aqueous solution.
- aqueous dyeing the depth of shade is often limited, and the colored alminum is not sufficiently light-fast to make it useful for exterior applications under weathering conditions.
- Aqueous dyeing procedures require extended periods of dyeing to obtain deep penetration into the oxide coating on the aluminum and it is generally necessary to follow the initial dyeing'by treatment at higher temperatures or otherwise to seal the coating and stop the dye absorption.
- Certain phthalocyanines have been applied to anodized aluminum to color it, but it is highly desirable to provide an improvedprocess for coloring aluminum to obtain permanently pigmented aluminum.
- One object of the present invention is to synthesize the novel nickel complexes defined above.
- Another object of the present invention is to provide an improved process for coloring anodized aluminum with a strongly adherent coatinghaving excellent fastness to light. Other objects appear hereinafter.
- the objects of this invention are accomplished by the 7 improved process of the present invention for coloring anodized -aluminum' which comprises synthesizing the novel nickel compounds and applying them to the aluminum to. be colored.
- the present invention it is now possible to color aluminum to form a colored surface on the metal which is remarkably adherent, stable and light fast.
- the. process of this invention is vastly superior.
- the aluminum coloring process of this invention is devoid of the numerous problems associated with the prior art procedures.
- the colored anodized aluminum displays a light fastness of at least 1000 Fade-O- Meter hours with no change in intensity. Previously, a light fastness of 500 Fade-O-Meter hours was considered satisfactory.
- the nickel compounds of this invention are also useful as colorants for paper, textiles and other metals, particularly aluminum alloys which are anodized by aluminum anodizing processes.
- novel compounds of this invention are prepared by the reaction of nickel (II) salts and 1,3-diiminoisoindoline, preferably in the stoichiometric ratio of about 4 grams moles of the diiminoisoindoline to 1 gram mole of nickel (II) salt. This ratio can vary considerably, for example, from 1:1 to 8:1. Excess reactant, however, remains to be separated from the desired product.
- the reaction is carried out in a large excess of an aliphatic alcohol having the formula ROH, where R has the same meaning as defined above, suitably at the reflux temperature of the alcohol.
- the molar ratio of alcohol to 1,3- diiminoisoindoline is appropriately from about 5:1 to
- the smaller ratios of alcohol advantageously permit cooling the reaction mixture and recovery of the precipitated product directly without evaporating excess alcohol.
- the reaction is rapid and is substantially completed usually in 10 minutes.
- the reaction time may vary from about 5 to 60 minutes or longer.
- the product is suitably recovered directly by cooling the reaction mixture or by evaporation of the excess alcohol and extraction of the residue to dissolve the nickel compound and to leave by-product ammonium chloride as an insoluble residue.
- Suitable extractants include heptane, octane, petroleum ether, chloroform, toluene, xylene, o-dichlorobenzene and 1,2,4-trichlorobenzene.
- the extractant is removed by vacuum evaporation and the nickel product is suitably recrystallized, for example, from acetone or alcohol.
- the nickel salt used in the preparation of the novel compounds of this invention is suitably introduced in the form of any of various salts, for example, nickel (II) chloride, oxide, nitrate, sulfate or acetate.
- the anhydrous salts are preferred.
- the novel nickel compounds of this invention are dissolved in a suitable solvent including aliphatic and aromatic hydrocarbons and hal'ohydrocarbons having boiling points at atmospheric pressure above about C.
- suitable solvent including aliphatic and aromatic hydrocarbons and hal'ohydrocarbons having boiling points at atmospheric pressure above about C. Examples include heptane, octane, petroleum ether, kerosene, Nujol, toluene, xylene, o-dichlorobenzene and 1,2,4- trichlorobenzene. Nujol is particularly advantageous and is preferred for its high flash point and boiling point.
- a concentration of the nickel compound of from 0.1 to 1.0% is suitable.
- the aluminum coloring process of the present invention is amenable to continuous operation by various modifications.
- Loose coils of anodized aluminum sheet are appropriately immersed in a container, for example, a degreasing tank containing the colorant mixture, continuously or intermittently replenished, until the metal is sufficiently coated.
- the finished coil is removed and replaced by a fresh coil of anodized aluminum.
- a solution of the colorant is sprayed on a moving strip of metal which passes through a suitably heated zone with a holding time therein suflicient to produce a coating of the desired depth of color.
- EXAMPLE II A 0.75% solution of the product of Example I in Nujol was heated to C. in contact with a piece of un- EXAMPLE III A mixture of 1.3 g. (0.1 mole) of anhydrous nickel (II) chloride and 300 ml. of n-amyl alcohol was refluxed and a solution of 5.8 g. (0.04 mole) of 1,3 diiminoisoindoline in 100 ml. of boiling amyl alcohol was added rapidly. The mixture was refluxed and stirred for minutes and the bis[3 (3 n amyloxy 1H isoindol- 1 imino) 1H isoindol 1 iminato] nickel (II) compound was isolated by the method described in Example I. Yield 6.1 g. or 85% of theoretical.
- Example IV The product of Example III was applied to anodized aluminum as described in Example II With essentially the same results.
- Example V The procedure of Example I was repeated using 5.4 g. (0.03 mole) of anhydrous nickel (II) acetate and 11.7 g. (0.08 mole) of 1,3-diiminoisoindoline to produce the same bis[3 (3 n butoxy 1H isoindol 1 imino)- 1H isoindol l iminato] nickel (II) compound in a yield of 60% based on the isoindoline.
- nickel (II) salt is nickel (II) chloride, oxide, nitrate, sulfate or acetate.
- Method of coloring aluminum which comprises heating unsealed anodized aluminum at to C. in contact with a solution of bis[3 (3 alkoxy- 1H isoindol 1 imino) 1H isoindol 1 iminato] nickel (II) in which said alkoxy contains 1 to 6 carbons in an aliphatic or aromatic hydrocarbon or halohydrocarbon having a boiling point above about 100 C. at atmospheric pressure.
- Aluminum having adherent on the surface thereof a colorant film produced by heating unsealed anodized aluminum at 100? to 150 C. in contact with a solution of bis[3 (3 alkoxy 1H isoindol 1 imino) 1H- isoindol 1 iminato] nickel (II) in which said alkoxy contains 1 to 6 carbons in an aliphatic or aromatic hydrocarbon or halohydrocarbon having a boiling point above about 100 C. at atmospheric pressure.
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
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- Electrochemistry (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
Description
Oct. 22, 1968 T. J. HURLEY ET AL 3,407,098
COLORANT FILM FOR ALUMINUM SURFACES Filed Aug. 25, 1965 INVENTORS. THOMAS J. HURLEY MART/IV A. ROBINSON JAMES A. SCRUGGS 62y A NT United States Patent f 3,407,098 COLORANT FILM FOR ALUMINUM SURFACES Thomas J Hurley, Madison, Martin A. Robinson, Orange, and James A. Scruggs, West Haven, Conn., assignors to Olin Mathieson Chemical Corporation, acorporation of Virginia r 1 Filed Aug. 25, 1965, Ser. No. 482,545 11 Claims. (Cl. 148-6.1)
This invention relates to a novel class of coordination compounds, their synthesis and use. The novel compounds are useful for coloring aluminum. More particularly the vnovel compounds ofthis invention are-bis[ 3-(3-alkoxylH-isoindol-l-imino)-1H-isoindol-1-irninato] nickel II) having the formula shown in theaccompanying drawing where R is alkyl of 1 to 6 carbons, suitably methyl, ethyl, isopropyl, n-butyl, n-amyl, sec. amyl and neohexyl.
I 'Dyeings possessing some acceptable'light-fastness are achieved on anodized aluminum when the aluminum is properly anodized and the surface sealed after dyeing by treating it with boiling water or steam. Heretofore, anodized aluminum has usually been dyed with various dyes in aqueous or non-aqueous solution. In aqueous dyeing, the depth of shade is often limited, and the colored alminum is not sufficiently light-fast to make it useful for exterior applications under weathering conditions. Aqueous dyeing procedures require extended periods of dyeing to obtain deep penetration into the oxide coating on the aluminum and it is generally necessary to follow the initial dyeing'by treatment at higher temperatures or otherwise to seal the coating and stop the dye absorption.
Certain phthalocyanines have been applied to anodized aluminum to color it, but it is highly desirable to provide an improvedprocess for coloring aluminum to obtain permanently pigmented aluminum.
One object of the present invention is to synthesize the novel nickel complexes defined above.
Another object of the present invention is to provide an improved process for coloring anodized aluminum with a strongly adherent coatinghaving excellent fastness to light. Other objects appear hereinafter.
The objects of this invention are accomplished by the 7 improved process of the present invention for coloring anodized -aluminum' which comprises synthesizing the novel nickel compounds and applying them to the aluminum to. be colored. By means of thepresent invention it is now possible to color aluminum to form a colored surface on the metal which is remarkably adherent, stable and light fast. Compared to the colored aluminum or prior art, processes, the. process of this invention is vastly superior. The aluminum coloring process of this invention is devoid of the numerous problems associated with the prior art procedures. The colored anodized aluminum displays a light fastness of at least 1000 Fade-O- Meter hours with no change in intensity. Previously, a light fastness of 500 Fade-O-Meter hours was considered satisfactory. The nickel compounds of this invention are also useful as colorants for paper, textiles and other metals, particularly aluminum alloys which are anodized by aluminum anodizing processes.
The novel compounds of this invention are prepared by the reaction of nickel (II) salts and 1,3-diiminoisoindoline, preferably in the stoichiometric ratio of about 4 grams moles of the diiminoisoindoline to 1 gram mole of nickel (II) salt. This ratio can vary considerably, for example, from 1:1 to 8:1. Excess reactant, however, remains to be separated from the desired product. The reaction is carried out in a large excess of an aliphatic alcohol having the formula ROH, where R has the same meaning as defined above, suitably at the reflux temperature of the alcohol. The molar ratio of alcohol to 1,3- diiminoisoindoline is appropriately from about 5:1 to
30:1. The smaller ratios of alcohol advantageously permit cooling the reaction mixture and recovery of the precipitated product directly without evaporating excess alcohol. The reaction is rapid and is substantially completed usually in 10 minutes. The reaction time may vary from about 5 to 60 minutes or longer. The product is suitably recovered directly by cooling the reaction mixture or by evaporation of the excess alcohol and extraction of the residue to dissolve the nickel compound and to leave by-product ammonium chloride as an insoluble residue. Suitable extractants include heptane, octane, petroleum ether, chloroform, toluene, xylene, o-dichlorobenzene and 1,2,4-trichlorobenzene. The extractant is removed by vacuum evaporation and the nickel product is suitably recrystallized, for example, from acetone or alcohol.
The nickel salt used in the preparation of the novel compounds of this invention is suitably introduced in the form of any of various salts, for example, nickel (II) chloride, oxide, nitrate, sulfate or acetate. The anhydrous salts are preferred.
For the aluminum-coloring process of this invention, the novel nickel compounds of this invention are dissolved in a suitable solvent including aliphatic and aromatic hydrocarbons and hal'ohydrocarbons having boiling points at atmospheric pressure above about C. Examples include heptane, octane, petroleum ether, kerosene, Nujol, toluene, xylene, o-dichlorobenzene and 1,2,4- trichlorobenzene. Nujol is particularly advantageous and is preferred for its high flash point and boiling point. A concentration of the nickel compound of from 0.1 to 1.0% is suitable. On heating the anodized aluminum to be colored in contact with the solution of the novel nickel compound at temperatures from 100 to 150 C., the aluminum gradually becomes colored. The color deepens with time but reaches a maximum intensity usually in about 10 minutes. Longer contact of the aluminum with the solution produces no deeper coloration.
The aluminum coloring process of the present invention is amenable to continuous operation by various modifications. Loose coils of anodized aluminum sheet are appropriately immersed in a container, for example, a degreasing tank containing the colorant mixture, continuously or intermittently replenished, until the metal is sufficiently coated. The finished coil is removed and replaced by a fresh coil of anodized aluminum. Alternatively a solution of the colorant is sprayed on a moving strip of metal which passes through a suitably heated zone with a holding time therein suflicient to produce a coating of the desired depth of color.
EXAMPLE I A mixture of 2.6 g. (0.02 mole) of anhydrous nickel (II) chloride and 625 ml. of n-butyl alcohol was heated to reflux temperature with stirring. To the suspension was added rapidly a solution of 11.7 g. (0.08 mole) of 1,3-diiminoisoindoline in 125 ml. of boiling butanol. The mixture was refluxed and stirred for 10 minutes. The dark red mixture was filtered hot and the filtrate was vacuum evaporated to remove the butanol. The red solid residue was extracted with hot toluene and filtered. Toluene was removed from the filtrate by vacuum evaporation and the red solid residue was crystallized from acetone. The yield of bis[3 (3 n butoxy 1H- isoindol 1 imino) 1H isoindol 1 iminato] nickel (II) was 9.6 g. or 67% of theoretical.
Analysis for C H N O Ni.-Calcd.: C, 66.95; H,-
4.74; N, 15.62. Found: C, 66.73; H, 5.17; N, 15.80.
EXAMPLE II A 0.75% solution of the product of Example I in Nujol was heated to C. in contact with a piece of un- EXAMPLE III A mixture of 1.3 g. (0.1 mole) of anhydrous nickel (II) chloride and 300 ml. of n-amyl alcohol was refluxed and a solution of 5.8 g. (0.04 mole) of 1,3 diiminoisoindoline in 100 ml. of boiling amyl alcohol was added rapidly. The mixture was refluxed and stirred for minutes and the bis[3 (3 n amyloxy 1H isoindol- 1 imino) 1H isoindol 1 iminato] nickel (II) compound was isolated by the method described in Example I. Yield 6.1 g. or 85% of theoretical.
Analysis for C H N O Ni.Calcd.: C, 67.65; H, 5.10; N, 15.03. Found: C, 67.45; H, 5.47; N, 15.27.
EXAMPLE IV The product of Example III was applied to anodized aluminum as described in Example II With essentially the same results.
EXAMPLE V The procedure of Example I was repeated using 5.4 g. (0.03 mole) of anhydrous nickel (II) acetate and 11.7 g. (0.08 mole) of 1,3-diiminoisoindoline to produce the same bis[3 (3 n butoxy 1H isoindol 1 imino)- 1H isoindol l iminato] nickel (II) compound in a yield of 60% based on the isoindoline.
EXAMPLE VI A slurry of 6 g. (0.46 mole) of anhydrous nickel (II) chloride in 1500 ml. of n-butanol was brought to reflux and a hot solution of 232 g. (1.60 moles) of 1,3-diiminoisoindoline in 2250 ml, of n-butanol was added quickly with stirring. The resulting red solution was held at reflux and stirred vigorously for 20 minutes. The solution was filtered hot and then cooled in a refrigerator. The bis[3 (3 n butoxy 1H isoindol 1 imino)- lH isoindol 1 iminato] nickel (II) which precipitated was removed by filtration and amounted to 143 g. or 50% of the theoretical yield. The remaining solution was evaporated to dryness and the red solid residue was dissolved in hot chloroform and filtered to remove ammonium chloride. The filtrate was evaporated to dryness. The residue was washed with cold methanol and recrystallized from acetone. An additional 60 grams of product was obtained. The total yield was 71% of theoretical.
What is claimed is:
1. Bis[3 (3 alkoxy 1H isoindol l imino)- lH isoindol 1 iminato] nickel (II) in which said alkoxy contains 1 to 6 carbons.
2. Bis[3 (3 l butoxy 1H isoindol l imino)- lI-I isoindol iminato] nickel (II).
3. Bis[3 (3 amyloxy 1H isoindol 1 imino)- lH isoindol l iminato] nickel (II).
4. Process for the preparation of bis[3 (3 alkoxy- 1H-- isoindol 1 imino) 1H isoindol -'1 --iminato] nickel (II) in which said alkoxy contains 1 to 6 carbons by refluxing a mixture of nickel (II) salt and 1,3-diiminoisoindoline in an aliphatic alcohol of 1 to 6 carbons and separating the resulting nickel complex from the reaction mixture. A, "I
5. The process of claim 4 in which the nickel (II) salt is nickel (II) chloride, oxide, nitrate, sulfate or acetate.
6. The process of claim 4 in which the molar ratio of 1,3-diiminoisoindoline to nickel (II) salt is from 1:1 to 8:1.
7. The process of claim 6 in which said molar ratio is substantially 4:1.
8. The process of claim 4 in which the molar ratio of said aliphatic alcohol to diiminoisoindoline is from 5:1 to 30: 1.
9. Method of coloring aluminum which comprises heating unsealed anodized aluminum at to C. in contact with a solution of bis[3 (3 alkoxy- 1H isoindol 1 imino) 1H isoindol 1 iminato] nickel (II) in which said alkoxy contains 1 to 6 carbons in an aliphatic or aromatic hydrocarbon or halohydrocarbon having a boiling point above about 100 C. at atmospheric pressure. w
10. Aluminum having adherent on the surface thereof a colorant film of bis[3 (3 alkoxy 1H isoindol- 1 imino) lH isoindol l iminato] nickel (II) in which said alkoxy contains 1 to 6 carbons.
11. Aluminum having adherent on the surface thereof a colorant film produced by heating unsealed anodized aluminum at 100? to 150 C. in contact with a solution of bis[3 (3 alkoxy 1H isoindol 1 imino) 1H- isoindol 1 iminato] nickel (II) in which said alkoxy contains 1 to 6 carbons in an aliphatic or aromatic hydrocarbon or halohydrocarbon having a boiling point above about 100 C. at atmospheric pressure.
References Cited UNITED sTATEs PATENTS 2,739,155 3/1956 Rosch et al. 260 326.1 3,023,164 2/1962 Lawton et a1 148-6.1 x 3,026,220 3/1962 Sowards 6t al. 148--6.1 3,114,660 12/1963 Cochran 1486.1 3,326,728 6/1967 Robinson 1486.1
FOREIGN PATENTS 297,833 4/1954 Switzerland.
RALPH S. KENDALL, Primary Examiner.
Claims (1)
- 9. METHOD OF COLORING ALUMINUM WHICH COMPRISES HEATING UNSEALED ANODIZED ALUMINUM AT 100* TO 150*C. IN CONTACT WITH A SOLUTION OF BIS(3 - (3 - ALKOXY - 1HISOINDOL - 1 - IMINO) - 1H - ISOINDOL - 1 - IMINATO) NICKEL (II) IN WHICH SAID ALKOXY CONTAINS 1 TO 6 CARBONS IN AN ALIPHATIC OR AROMATIC HYDROCARBON OR HALOHYDROCARBON HAVING A BOILING POINT ABOUT ABOUT 100*C. AT ATMOSPHERIC PRESSURE.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US482545A US3407098A (en) | 1965-08-25 | 1965-08-25 | Colorant film for aluminum surfaces |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US482545A US3407098A (en) | 1965-08-25 | 1965-08-25 | Colorant film for aluminum surfaces |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| US3407098A true US3407098A (en) | 1968-10-22 |
Family
ID=23916499
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| US482545A Expired - Lifetime US3407098A (en) | 1965-08-25 | 1965-08-25 | Colorant film for aluminum surfaces |
Country Status (1)
| Country | Link |
|---|---|
| US (1) | US3407098A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4091126A (en) * | 1976-03-05 | 1978-05-23 | Kabushiki Kaisha Hidan Seisakusho | Method of dyeing a pattern like the grain of wood on the surface of an aluminum |
| EP1306131A2 (en) * | 2001-10-23 | 2003-05-02 | Sumitomo Chemical Company, Limited | Cross-Coupling catalyst comprising a cyclic nitrogen ligand and process using the same |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CH297833A (en) * | 1949-08-25 | 1954-04-15 | Bayer Ag | Process for the preparation of a copper-containing polyiminoisoindolenine compound. |
| US2739155A (en) * | 1949-08-25 | 1956-03-20 | Bayer Ag | Process for the production of isoindolenine derivatives |
| US3023164A (en) * | 1958-05-21 | 1962-02-27 | Battelle Memorial Institute | Method of lubrication comprising the use of metal phthalocyanine |
| US3026220A (en) * | 1959-12-01 | 1962-03-20 | Du Pont | Aluminum pigments and fibers |
| US3114660A (en) * | 1959-04-16 | 1963-12-17 | Aluminum Co Of America | Anodized aluminum colored with water insoluble phthalocyanine and method |
| US3326728A (en) * | 1963-08-06 | 1967-06-20 | Olin Mathieson | Colored aluminum and process therefor |
-
1965
- 1965-08-25 US US482545A patent/US3407098A/en not_active Expired - Lifetime
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CH297833A (en) * | 1949-08-25 | 1954-04-15 | Bayer Ag | Process for the preparation of a copper-containing polyiminoisoindolenine compound. |
| US2739155A (en) * | 1949-08-25 | 1956-03-20 | Bayer Ag | Process for the production of isoindolenine derivatives |
| US3023164A (en) * | 1958-05-21 | 1962-02-27 | Battelle Memorial Institute | Method of lubrication comprising the use of metal phthalocyanine |
| US3114660A (en) * | 1959-04-16 | 1963-12-17 | Aluminum Co Of America | Anodized aluminum colored with water insoluble phthalocyanine and method |
| US3026220A (en) * | 1959-12-01 | 1962-03-20 | Du Pont | Aluminum pigments and fibers |
| US3326728A (en) * | 1963-08-06 | 1967-06-20 | Olin Mathieson | Colored aluminum and process therefor |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4091126A (en) * | 1976-03-05 | 1978-05-23 | Kabushiki Kaisha Hidan Seisakusho | Method of dyeing a pattern like the grain of wood on the surface of an aluminum |
| EP1306131A2 (en) * | 2001-10-23 | 2003-05-02 | Sumitomo Chemical Company, Limited | Cross-Coupling catalyst comprising a cyclic nitrogen ligand and process using the same |
| US20030162950A1 (en) * | 2001-10-23 | 2003-08-28 | Sumitomo Chemical Company, Limited | Coupling catalyst and process using the same |
| EP1306131A3 (en) * | 2001-10-23 | 2004-05-19 | Sumitomo Chemical Company, Limited | Cross-Coupling catalyst comprising a cyclic nitrogen ligand and process using the same |
| US7041856B2 (en) | 2001-10-23 | 2006-05-09 | Sumitomo Chemical Company, Limited | Coupling catalyst and process using the same |
| US20060111593A1 (en) * | 2001-10-23 | 2006-05-25 | Sumitomo Chemical Company, Limited | Coupling catalyst and process using the same |
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