CA1143724A - Azo compounds, their preparation and use - Google Patents
Azo compounds, their preparation and useInfo
- Publication number
- CA1143724A CA1143724A CA000365188A CA365188A CA1143724A CA 1143724 A CA1143724 A CA 1143724A CA 000365188 A CA000365188 A CA 000365188A CA 365188 A CA365188 A CA 365188A CA 1143724 A CA1143724 A CA 1143724A
- Authority
- CA
- Canada
- Prior art keywords
- methyl
- ethyl
- hydrogen
- formula
- acetoacetylamino
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10B—DESTRUCTIVE DISTILLATION OF CARBONACEOUS MATERIALS FOR PRODUCTION OF GAS, COKE, TAR, OR SIMILAR MATERIALS
- C10B21/00—Heating of coke ovens with combustible gases
- C10B21/20—Methods of heating ovens of the chamber oven type
Abstract
Azo compounds, their preparation and use Abstract of the disclosure:
Monoazo compounds of the formula I
Monoazo compounds of the formula I
Description
~ ~3'~
- 2 -The invention provides azo compounds of the formula I
N02 N ~ CH3 ROOC~
X Y
in which R is an alkyl radical having from 1 to 4 carbon atoms; X is hydrogen a chlorine or bromine atom, a methyl, ethyl, methoxy or ethoxy group; and Y is hydrogen, a methyl or ethyl group.
The invention provides furthermore a process for the preparation of the cited azo compounds, which comprises diazotizing compounds of the formula II
ROOC ~ NH2 (II) in which R is as defined above, and coupling the diazonium compound obtained with a compound of the formula III
; H
~ N~ O (III) X Y
in which X and Y are as defined sub formula I. ~-. .
N02 N ~ CH3 ROOC~
X Y
in which R is an alkyl radical having from 1 to 4 carbon atoms; X is hydrogen a chlorine or bromine atom, a methyl, ethyl, methoxy or ethoxy group; and Y is hydrogen, a methyl or ethyl group.
The invention provides furthermore a process for the preparation of the cited azo compounds, which comprises diazotizing compounds of the formula II
ROOC ~ NH2 (II) in which R is as defined above, and coupling the diazonium compound obtained with a compound of the formula III
; H
~ N~ O (III) X Y
in which X and Y are as defined sub formula I. ~-. .
3'7 'rhe invention rela-tes furthermore to the use of the azo compounds of the invention as coloring agents, especial-ly as pigments.
As amines of -the formula II, there may be used for example:
3-Nitro-4-aminoben%oic acid methyl ester, 3-Nitro-4-aminobenzoic acid ethyl ester, 3-Nitro-4-aminobenæoic acid-n-propyl-ester, 3-Nitro-4-aminobenzoic acid-isopropyl ester, 3-Nitro-4-aminobenzoic acid-n-butyl ester, 3-Nitro-4-aminobenzoic acid-isobutyl ester and 3-Nitro-4-aminobenzoic acid-1-methylpropyl ester.
lhe amine of the formula II can be diazotized for example with alkali metal nitrites or lower alkyl nitrites and sufficiently strong acids, especially a mineral acid, but also nitrosulfuric acid. ~y "lower" in connection with alkyl radicals, there are to be understood here and hereinafter groups having from 1 to 6, especially 1 to 4 carbon atoms. It may prove to be advantageous to add surfactants such as nonionic, anion-active or cation-active dispersing agents in this process step as well as in the subsequent coupling operation.
Examples of coupling components to be used are the following:
5-Acetoacetylaminobenzimidazolone-(2), 5-Acetoacetylamino-6-chlorobenzimidazolone-(2) 5-Acetoacetylamino-7-chlorobenzimidazolone-(2) 5-Acetoacetylamino-6-bromobenzimidazolone-(2) 5-Acetoacetylamino-7-bromobenzimidazolone-(2) 5-Acetoacetylamino-6-methylbenzimidazolone-(2) 5-Acetoacetylamino-7-methylbenzimidazolone-(2) 5-Acetoacetylamino-6-methoxybenzimidazolone-(2) 5-Acetoacetylamino-7-methoxybenzimidazolone-(2) 5-Acetoacetylamino-6-ethoxybenzimidazolone-(2) 5-Acetoacetylamino-7-ethoxybenzimidazolone-(2) 5-Acetoacetylamino-1-methylbenzimidazolone-(2) 5-Acetoacetylamino-1-ethylbenzimidazolone-(2) and 5-Acetoacetylamino-1-methyl-6-chlorobenzimidazolone-(2).
7'~
As amines of -the formula II, there may be used for example:
3-Nitro-4-aminoben%oic acid methyl ester, 3-Nitro-4-aminobenzoic acid ethyl ester, 3-Nitro-4-aminobenæoic acid-n-propyl-ester, 3-Nitro-4-aminobenzoic acid-isopropyl ester, 3-Nitro-4-aminobenzoic acid-n-butyl ester, 3-Nitro-4-aminobenzoic acid-isobutyl ester and 3-Nitro-4-aminobenzoic acid-1-methylpropyl ester.
lhe amine of the formula II can be diazotized for example with alkali metal nitrites or lower alkyl nitrites and sufficiently strong acids, especially a mineral acid, but also nitrosulfuric acid. ~y "lower" in connection with alkyl radicals, there are to be understood here and hereinafter groups having from 1 to 6, especially 1 to 4 carbon atoms. It may prove to be advantageous to add surfactants such as nonionic, anion-active or cation-active dispersing agents in this process step as well as in the subsequent coupling operation.
Examples of coupling components to be used are the following:
5-Acetoacetylaminobenzimidazolone-(2), 5-Acetoacetylamino-6-chlorobenzimidazolone-(2) 5-Acetoacetylamino-7-chlorobenzimidazolone-(2) 5-Acetoacetylamino-6-bromobenzimidazolone-(2) 5-Acetoacetylamino-7-bromobenzimidazolone-(2) 5-Acetoacetylamino-6-methylbenzimidazolone-(2) 5-Acetoacetylamino-7-methylbenzimidazolone-(2) 5-Acetoacetylamino-6-methoxybenzimidazolone-(2) 5-Acetoacetylamino-7-methoxybenzimidazolone-(2) 5-Acetoacetylamino-6-ethoxybenzimidazolone-(2) 5-Acetoacetylamino-7-ethoxybenzimidazolone-(2) 5-Acetoacetylamino-1-methylbenzimidazolone-(2) 5-Acetoacetylamino-1-ethylbenzimidazolone-(2) and 5-Acetoacetylamino-1-methyl-6-chlorobenzimidazolone-(2).
7'~
4 --Diazotization and coupling may alternatively be carried out in the presence of suitable organic solvents, for example glacial acetic acid, lower alkanols, dioxan, formamide, dimethyl formamide, dimethyl sulfoxide, pyridine or N-methylpyrrolidone.
In order to attain full tinctorial strength and an especially favorable crystal structure, it is advantageous in many cases to heat the coupling mixture for a certain time, for example to boil it or to maintain it at a temperature above 100C by applying pressure, optionally in the presence of` organic solvents such as lower a]kanols, for example ethanol, halogenated aromatic compounds such as chlorobenzene, or dichlorobenzenes such as o-dichloro-benzene, dimethyl formamide, or in the presence of resin soap. ~specially pure pigments of high tinctorial strength are obtained from the products of the invention when after coupling the moist press cakes or the dried powders are subjected to a thermal after-treatment with organic solv-vents such as alcohols, especially lower alkanols, pyridine, glacial acetic acid, dimethyl formamide, N-methylpyrroli done, dimethyl sulfoxide, halogenated aromatic compounds such as chlorobenzene, or dichlorobenzenes such as o-dichloroben-zene or nitrobenzene, or when the pigments are subsequently ground with addition of grinding auxiliaries.
The pigments may alternatively be prepared in the presence of a carrier material, for example barium sulfate.
The novel compounds are water-insoluble and insoluble in the usual organic solvents and they are suitable for pigmenting printing inks, color varnishes and dispersion paints, and for dyeing rubber, plastics and natural or synthetic resins. They are especially suitable for those varnishes and plastics which have to meet severe fastness requirements. They are furthermore suitable for pigment printing of substrates, especially textile fiber materials or other flat structures such as paper. The pigments can be applied also in other fields, for example, in a finely disperse form, for -the dyeing of the spinning mass for rayon made from viscose or cellulose ethers or esters,
In order to attain full tinctorial strength and an especially favorable crystal structure, it is advantageous in many cases to heat the coupling mixture for a certain time, for example to boil it or to maintain it at a temperature above 100C by applying pressure, optionally in the presence of` organic solvents such as lower a]kanols, for example ethanol, halogenated aromatic compounds such as chlorobenzene, or dichlorobenzenes such as o-dichloro-benzene, dimethyl formamide, or in the presence of resin soap. ~specially pure pigments of high tinctorial strength are obtained from the products of the invention when after coupling the moist press cakes or the dried powders are subjected to a thermal after-treatment with organic solv-vents such as alcohols, especially lower alkanols, pyridine, glacial acetic acid, dimethyl formamide, N-methylpyrroli done, dimethyl sulfoxide, halogenated aromatic compounds such as chlorobenzene, or dichlorobenzenes such as o-dichloroben-zene or nitrobenzene, or when the pigments are subsequently ground with addition of grinding auxiliaries.
The pigments may alternatively be prepared in the presence of a carrier material, for example barium sulfate.
The novel compounds are water-insoluble and insoluble in the usual organic solvents and they are suitable for pigmenting printing inks, color varnishes and dispersion paints, and for dyeing rubber, plastics and natural or synthetic resins. They are especially suitable for those varnishes and plastics which have to meet severe fastness requirements. They are furthermore suitable for pigment printing of substrates, especially textile fiber materials or other flat structures such as paper. The pigments can be applied also in other fields, for example, in a finely disperse form, for -the dyeing of the spinning mass for rayon made from viscose or cellulose ethers or esters,
5 _ polyamides, polyurethanes, polyglycol terephthala-tes or polyacrylonitri]es; or for the dyeing of paper.
The pi~ments can be easily processed in the cited media. The dyeings have a very good fastness to light and weathering, and they are stable to influences of chemicals, especially solven-ts. In varnishes, the pigments of -the invention are furthermore fast to overvarnishin~, and in plastics, they are fast to bleeding.
The following examples illustrate the invention; per-centages being by weight.
~ X A M P L ~ 1:
_ _ _ 10.5 g of 3-nitro-4-aminobenzoic acid ethyl ester are suspended in 80 ml of glacial acetic acid, and stirred for 1 hour with 15 ml of 31 ~ hydrochloric acid. The bath is then cooled to 8-10C, 10 ml of a 5 N sodium nitrite solution are added dropwise, and stirring is continued for a further 30 minutes.
12 g of 5-acetoacetylaminobenzimidazolone-(2) are dissolved in 150 ml of water and 9 ml of 33 % sodium hydroxide solution, and filtered after addition of 5 g of kieselguhr. 1 g of a condensation product of stearyl alcohol with 25 equivalents of ethylene oxide is added to the filtered solution, and the coupling component is precipitated by adding 6 ml of glacial acid in 50 ml of water all at once. Subseqquently, 25 ml of a 4 N sodium acetate solution are added.
The diazonium salt solution so prepared is added dropwise at 25C within 1 hour to the suspension of the coupling component. After coupling, the batch is heated for 30 mintes to 95C, the product is suction-filtered, washed with water until it is free from salt, and dried at 60-70C. The dry crude pigment is heated to 115C in 250 ml of glacial acetic acid, and maintained at this temperature for 15 minutes. The orange colored pigment is then filtered off, washed with methanol and water, and dried. Yield: 20.2 g of pigment having the formula 3~7
The pi~ments can be easily processed in the cited media. The dyeings have a very good fastness to light and weathering, and they are stable to influences of chemicals, especially solven-ts. In varnishes, the pigments of -the invention are furthermore fast to overvarnishin~, and in plastics, they are fast to bleeding.
The following examples illustrate the invention; per-centages being by weight.
~ X A M P L ~ 1:
_ _ _ 10.5 g of 3-nitro-4-aminobenzoic acid ethyl ester are suspended in 80 ml of glacial acetic acid, and stirred for 1 hour with 15 ml of 31 ~ hydrochloric acid. The bath is then cooled to 8-10C, 10 ml of a 5 N sodium nitrite solution are added dropwise, and stirring is continued for a further 30 minutes.
12 g of 5-acetoacetylaminobenzimidazolone-(2) are dissolved in 150 ml of water and 9 ml of 33 % sodium hydroxide solution, and filtered after addition of 5 g of kieselguhr. 1 g of a condensation product of stearyl alcohol with 25 equivalents of ethylene oxide is added to the filtered solution, and the coupling component is precipitated by adding 6 ml of glacial acid in 50 ml of water all at once. Subseqquently, 25 ml of a 4 N sodium acetate solution are added.
The diazonium salt solution so prepared is added dropwise at 25C within 1 hour to the suspension of the coupling component. After coupling, the batch is heated for 30 mintes to 95C, the product is suction-filtered, washed with water until it is free from salt, and dried at 60-70C. The dry crude pigment is heated to 115C in 250 ml of glacial acetic acid, and maintained at this temperature for 15 minutes. The orange colored pigment is then filtered off, washed with methanol and water, and dried. Yield: 20.2 g of pigment having the formula 3~7
- 6 -N2 ~ CH~
C2H500C ~ ~ ~H> o lI
X A M P IJ ~ 2 ___ _ 31.8 g of 40 % nitrosylsulfuric acid are added within 45 minutes to 19.6 g of 3-nitro-4-aminobenzoic acid methyl ester dissolved in 200 ml of glacial acetic acid. 23.3 g ` of 5-acetoacetylaminobenzimidazolone-(2) are dissolved in 200 ml of water and 18 ml of 33 % sodium hydroxide solu-tion. This solution and the diazonium salt solution are added dropwise and simultaneously to a solution of 200 ml of water, 12 ml of glacial acetic acid, 20 ml of a 10 %
aqueous solution of the condensation product of stearyl alcohol with 25 equivalents of ethylene oxide, and 25 ml of a 4 N sodium acetate solution. Coupling is complete after 45 minutes. The mixture os heated to 95C, maintained at this temperature for 30 minutes, and cooled to 70C. The product is suction-filtered, washed free from salt; the moist pressure cake is stirred with 600 ml of 50 % isobutanol, and heated for 1 hour to 120C.
After having distilled off the isobutanol by means of steam, the product os filtered and dried. Yield: 42.3 g of a reddish-yellow pigment having the formula ~_ O~
H
X A It~ P ~
10.5 g of 3-nitro-4-aminobenzoic acld ethyl es-ter are stirred for 1 hour in 160 ml of glacial acetic acid and 30 ml of 30 7~ hydrochloric acid. The batch is cooled to 10C, and 10 ml of a 5 N sodium nitrite solution is added below the surface. The diazonillm salt solution is stirred for a further 30 mintes, and clarified by adding a small amount of kieselguhr and filtering.
14 g of 5-ace-toacetylamino-7-chlorobenzimidazolone-(2) are dissolved in 150 ml of water and 10 ml of 33 ~ sodium hydroxide solution. The two solutions so prepared are added dropwise and simultaneously at 10C to a solution prepared frorn -the following components: 200 ml of ice-water, 6 ml of glacial acetic acid, 10 ml of a 10 aqueous solution of the addition product of stearyl alcohol with 25 equivalents of ethylene oxide, and 25 ml of a 4 N sodium acetate solution. Dropwise addition takes 1 hour. After coupling, stirring is continued for 1 hour at room temperature, the product os suction-filtered, washed with water until it is free from salt, and dried.
The crude pigment is heated to 120C in 250 ml of chlorobenzene, and maintained for 15 minutes at this temperature. Subsequently, it is suction-filtered, washed with chlorobenzene, methanol and water, and dried. Yield:
21 g of a reddish-yellow pigment having the formula C2H500C ~ ~ N
Cl H
In the following table, there are listed further examples of azo compounds obtained by coupling the diazoti-zed aromatic amines (diazo components) of the formula II
with the coupling components of the formula III:
3'7~
_ ._ ~ . No. formula Il formula III Sh~de X Y
, _ _ _ ____ 4 CH3 6-Cl H yellowish oran~e CH3 7-Cl .H yel:lowish orange 6 CH3 6-~Br H yellow
C2H500C ~ ~ ~H> o lI
X A M P IJ ~ 2 ___ _ 31.8 g of 40 % nitrosylsulfuric acid are added within 45 minutes to 19.6 g of 3-nitro-4-aminobenzoic acid methyl ester dissolved in 200 ml of glacial acetic acid. 23.3 g ` of 5-acetoacetylaminobenzimidazolone-(2) are dissolved in 200 ml of water and 18 ml of 33 % sodium hydroxide solu-tion. This solution and the diazonium salt solution are added dropwise and simultaneously to a solution of 200 ml of water, 12 ml of glacial acetic acid, 20 ml of a 10 %
aqueous solution of the condensation product of stearyl alcohol with 25 equivalents of ethylene oxide, and 25 ml of a 4 N sodium acetate solution. Coupling is complete after 45 minutes. The mixture os heated to 95C, maintained at this temperature for 30 minutes, and cooled to 70C. The product is suction-filtered, washed free from salt; the moist pressure cake is stirred with 600 ml of 50 % isobutanol, and heated for 1 hour to 120C.
After having distilled off the isobutanol by means of steam, the product os filtered and dried. Yield: 42.3 g of a reddish-yellow pigment having the formula ~_ O~
H
X A It~ P ~
10.5 g of 3-nitro-4-aminobenzoic acld ethyl es-ter are stirred for 1 hour in 160 ml of glacial acetic acid and 30 ml of 30 7~ hydrochloric acid. The batch is cooled to 10C, and 10 ml of a 5 N sodium nitrite solution is added below the surface. The diazonillm salt solution is stirred for a further 30 mintes, and clarified by adding a small amount of kieselguhr and filtering.
14 g of 5-ace-toacetylamino-7-chlorobenzimidazolone-(2) are dissolved in 150 ml of water and 10 ml of 33 ~ sodium hydroxide solution. The two solutions so prepared are added dropwise and simultaneously at 10C to a solution prepared frorn -the following components: 200 ml of ice-water, 6 ml of glacial acetic acid, 10 ml of a 10 aqueous solution of the addition product of stearyl alcohol with 25 equivalents of ethylene oxide, and 25 ml of a 4 N sodium acetate solution. Dropwise addition takes 1 hour. After coupling, stirring is continued for 1 hour at room temperature, the product os suction-filtered, washed with water until it is free from salt, and dried.
The crude pigment is heated to 120C in 250 ml of chlorobenzene, and maintained for 15 minutes at this temperature. Subsequently, it is suction-filtered, washed with chlorobenzene, methanol and water, and dried. Yield:
21 g of a reddish-yellow pigment having the formula C2H500C ~ ~ N
Cl H
In the following table, there are listed further examples of azo compounds obtained by coupling the diazoti-zed aromatic amines (diazo components) of the formula II
with the coupling components of the formula III:
3'7~
_ ._ ~ . No. formula Il formula III Sh~de X Y
, _ _ _ ____ 4 CH3 6-Cl H yellowish oran~e CH3 7-Cl .H yel:lowish orange 6 CH3 6-~Br H yellow
7 CH3 7-:E3r H reddish yellow
8 CH3 6-CH ~ II brown
9 CH3 7-CH3 H reddish yellow CH3 6-OCH3 H yellowish brown 11 CH3 7-OCH3 H orange 12 CE-I3 6-OC2H5 H yellowish brown 13 CH3 7-OC2H5 H orange 14 CH3 H CH3 yellowish brown C2H5 6-Cl H reddish yellow 16 C2H5 6-Br H orange 17 C2H5 7-33r H yellowish brown 18 C2H5 6-CH3 H brown 19 C2H5 7-CH3 H orange C2H5 6-OCH3 H brown 21 C2H5 7-OCH3 H orange 22 C2H5 6-OC2H5 H brown 23 C2H5 H CH3 orange 24 C2H5 6-Cl CH3 brown n-C3H7 H H reddish yellow 26 iso-C3H7 H H yellow 27 n-C4Hg H H reddish yellow 28 iso-C4Hg H H reddish yellow 29 ,CEI CH2 CH3 H H yellow C~I3 n~C3~I7 7-Cl H reddish yellow 31 . _ rCl H reddish yellow
Claims (8)
1) A compound of the formula 1 (I) wherein R is alkyl of 1 to 4 carbon atoms, X is hydrogen, chlorine, bromine, methyl, ethyl, methoxy or ethoxy and Y is hydrogen, methyl or ethyl.
2) A compound as claimed in claim 1, wherein R is methyl or ethyl, X is hydrogen, chlorine, methyl or methoxy and Y is hydrogen.
3) A compound as claimed in claim 2, wherein X is in 7-position and stands for hydrogen, chlorine or methyl.
4) The compound as claimed in claim 3, wherein R is ethyl and X is hydrogen.
5) The compound as claimed in claim 3, wherein R is methyl and X is hydrogen.
6) The compound as claimed in claim 3, wherein R is ethyl and X is chlorine.
7) The compound as claimed in claim 3, wherein R is methyl and X is chlorine.
8) The compound as claimed in claim 3, wherein R and X are methyl.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DEP294744L.7 | 1979-11-24 | ||
| DE2947447A DE2947447C2 (en) | 1979-11-24 | 1979-11-24 | Method of heating coking ovens |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1143724A true CA1143724A (en) | 1983-03-29 |
Family
ID=6086811
Family Applications (2)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000353976A Expired CA1171021A (en) | 1979-11-24 | 1980-06-13 | Method of heating coke ovens |
| CA000365188A Expired CA1143724A (en) | 1979-11-24 | 1980-11-21 | Azo compounds, their preparation and use |
Family Applications Before (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000353976A Expired CA1171021A (en) | 1979-11-24 | 1980-06-13 | Method of heating coke ovens |
Country Status (13)
| Country | Link |
|---|---|
| JP (1) | JPS5676484A (en) |
| AR (1) | AR223532A1 (en) |
| AU (1) | AU530601B2 (en) |
| BE (1) | BE884942A (en) |
| BR (1) | BR8005493A (en) |
| CA (2) | CA1171021A (en) |
| DE (1) | DE2947447C2 (en) |
| FR (1) | FR2470150B1 (en) |
| GB (1) | GB2064081B (en) |
| IN (1) | IN152657B (en) |
| IT (1) | IT1128120B (en) |
| NL (1) | NL8004129A (en) |
| ZA (1) | ZA805191B (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR2530259B1 (en) * | 1982-07-16 | 1986-09-26 | Solmer | METHOD AND INSTALLATION FOR AUTOMATICALLY CONDUCTING THE HEATING OF COKE OVENS |
| DE3347244A1 (en) * | 1983-12-28 | 1985-07-11 | Dr. C. Otto & Co Gmbh, 4630 Bochum | Process for operating a coke oven battery |
Family Cites Families (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE2255500B1 (en) * | 1972-11-13 | 1973-08-02 | Hoogovens Ijmuiden B V , Ijmuiden (Niederlande) | PROCEDURE FOR OPERATING A COOK OVEN BATTERY |
| JPS5271501A (en) * | 1975-12-11 | 1977-06-15 | Otto & Co Gmbh Dr C | Method of regeneratively operating coke oven battery by swiching flue |
| DE2555692B2 (en) * | 1975-12-11 | 1979-08-09 | Dr. C. Otto & Comp. Gmbh, 4630 Bochum | Method for operating a battery of coking ovens in regenerative puff change |
| US4039391A (en) * | 1976-05-19 | 1977-08-02 | Bethlehem Steel Corporation | Coke oven battery and method for operation on a slow-down basis |
| DE2933069C2 (en) * | 1979-08-16 | 1984-07-05 | Dr. C. Otto & Co Gmbh, 4630 Bochum | Method for operating a battery of coking ovens |
| JPS5653179A (en) * | 1979-10-06 | 1981-05-12 | Nippon Steel Corp | Method for controlling combustion temperature of heating chamber in coke oven |
-
1979
- 1979-11-24 DE DE2947447A patent/DE2947447C2/en not_active Expired
-
1980
- 1980-03-29 JP JP3967780A patent/JPS5676484A/en active Pending
- 1980-06-13 CA CA000353976A patent/CA1171021A/en not_active Expired
- 1980-06-27 IT IT49089/80A patent/IT1128120B/en active
- 1980-06-30 IN IN750/CAL/80A patent/IN152657B/en unknown
- 1980-06-30 AR AR281585A patent/AR223532A1/en active
- 1980-07-07 AU AU60155/80A patent/AU530601B2/en not_active Ceased
- 1980-07-09 FR FR8015289A patent/FR2470150B1/fr not_active Expired
- 1980-07-17 NL NL8004129A patent/NL8004129A/en not_active Application Discontinuation
- 1980-08-15 GB GB8026701A patent/GB2064081B/en not_active Expired
- 1980-08-22 ZA ZA00805191A patent/ZA805191B/en unknown
- 1980-08-27 BE BE0/201880A patent/BE884942A/en not_active IP Right Cessation
- 1980-08-29 BR BR8005493A patent/BR8005493A/en unknown
- 1980-11-21 CA CA000365188A patent/CA1143724A/en not_active Expired
Also Published As
| Publication number | Publication date |
|---|---|
| GB2064081A (en) | 1981-06-10 |
| NL8004129A (en) | 1981-06-16 |
| DE2947447A1 (en) | 1981-06-04 |
| BR8005493A (en) | 1981-06-09 |
| JPS5676484A (en) | 1981-06-24 |
| CA1171021A (en) | 1984-07-17 |
| DE2947447C2 (en) | 1984-06-28 |
| IT1128120B (en) | 1986-05-28 |
| FR2470150A1 (en) | 1981-05-29 |
| ZA805191B (en) | 1981-09-30 |
| IT8049089A0 (en) | 1980-06-27 |
| BE884942A (en) | 1980-12-16 |
| AU530601B2 (en) | 1983-07-21 |
| GB2064081B (en) | 1983-06-02 |
| AU6015580A (en) | 1981-05-05 |
| AR223532A1 (en) | 1981-08-31 |
| IN152657B (en) | 1984-03-03 |
| FR2470150B1 (en) | 1986-04-25 |
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