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AU594760B2 - Process for making azo pigments - Google Patents
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AU594760B2 - Process for making azo pigments - Google Patents

Process for making azo pigments Download PDF

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Publication number
AU594760B2
AU594760B2 AU72407/87A AU7240787A AU594760B2 AU 594760 B2 AU594760 B2 AU 594760B2 AU 72407/87 A AU72407/87 A AU 72407/87A AU 7240787 A AU7240787 A AU 7240787A AU 594760 B2 AU594760 B2 AU 594760B2
Authority
AU
Australia
Prior art keywords
acid
reaction
coupling component
coupling
reaction step
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.)
Ceased
Application number
AU72407/87A
Other versions
AU7240787A (en
Inventor
Hartmut Behringer
Heinrich Rehberg
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Hoechst AG
Original Assignee
Hoechst AG
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Hoechst AG filed Critical Hoechst AG
Publication of AU7240787A publication Critical patent/AU7240787A/en
Application granted granted Critical
Publication of AU594760B2 publication Critical patent/AU594760B2/en
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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Classifications

    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09BORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B67/00Influencing the physical, e.g. the dyeing or printing properties of dyestuffs without chemical reactions, e.g. by treating with solvents grinding or grinding assistants, coating of pigments or dyes; Process features in the making of dyestuff preparations; Dyestuff preparations of a special physical nature, e.g. tablets, films
    • C09B67/006Preparation of organic pigments
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09BORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B41/00Special methods of performing the coupling reaction
    • C09B41/006Special methods of performing the coupling reaction characterised by process features

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Chemistry (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Paints Or Removers (AREA)
  • Pigments, Carbon Blacks, Or Wood Stains (AREA)
  • Inks, Pencil-Leads, Or Crayons (AREA)
  • Photoreceptors In Electrophotography (AREA)

Description

Pr- COMMONWEALTH OF AUSTRALIA PATENTS ACT 1952-69 5947f300 COMPLETE SPECIFICATION
(ORIGINAL)
Class I t. Class Application Number: Lodged: 7 qo 7 IF7 ACCcmplete Specification Lodged: D riority: Accepted: Published: 1bTh o.wisc)LLnS r~ amntskexts Made und.r Sect~on 49.
and 4e 4 hr z~b I I Related Art 04 Name of Applicant: Address of Applicant: HOECHST AKTIENGESELLSCHAFT 45 Bruningstrasse, D-6230 Frankfurt/Main Federal Republic of Germany HEINRICH REHBERG and H-ARTMUT BEHRINGER EDWD. WATERS SONS, 50 QUEEN STREET, MELBOURNE, AUSTRALIA, 3000.
Actual Inventor: Address for Service:
I
Complete Specification for the invention entitled: PROCESS FOR MAKING AZO PIGMENTS The following statement is a full description of this invention, including the best method of performing it known toI.
HOE 86/H 011 Azo pigments are made, preferably by subjecting a diazonium compound to an azo coupling reaction with a coupling component, such as an aromatic amine, acetoacetic acid arylide, naphthol, phenol or pyrazolone. This is commonly done by mixing the feed materials in aqueous phase. Reactions of this kind have long been known and described in textbooks of organic chemistry (cf. e.g. Louis and Mary Fieser, Organische Chemie, Verlag Chemie, Weinheim/Bergstrasse, 1965, pages 890 et seq., 1431, 1766 et seq.).
The coupling of components difficultly soluble in an aqueous system raises special problems. To undergo reaction, it is necessary for such coupling components to be distributed as finely as possible. This is done by adding a dispersant, emulsifier or solvent, e.g. an alcohol, or by to t15 grinding or precipitating the coupling components which are soluble in strongly alkaline media and can be precipitated by the addition of an acid. The difficult solubility of the coupling component often leads to occlusions in the pigment; as is known, the difficulty of producing pure pigments increases with a decreasing solubility of the pigment in the reaction system.
Normally, the diazonium salt solution stabler in the Sacid pH-range is allowed to run into the solution or suspension of the coupling component; the acid set free during the azo coupling reaction and -the excess acid present in the diazonium salt solution are neutralized by adding a base so as to maintain a predetermined pH. At the feed 1 G 8 40 0 S0 00 0 0 0 I6 inlet for the acid diazonium salt solution, there is always a pH-value different from that which establishes after mixing, and agitator kind and agitation velocity also influence the formation of by-products and ultimately the coloristic propertie's of the pigment to be made. In order to avoid side reactions, care is always taken to ensure that the reaction mixture remains free from diazonium compound in excess.
We have now unexpectedly found that pure azo pigmentsk free from occlusions of unreacted coupling component can be reproducibly obtained by very rapidly mixing, under certain reaction conditions, equivalent quantities of an aqueous/ acid-diazonium salt solution with an aqueous reactive suspension of a coupling component difficultly soluble in the aqueous/neutral to aqueous/acid pH-range. A difficultly soluble coupling component is one having a solubility of less than 0.1 wgt at pH 7.
The present invention provides more particularly a process for making azo pigments by subjecting a diazo component to an azo coupling reaction with the equivalent quantity of a coupling component difficultly soluble at less than 65 0 °C in the aqueous/acid and aqueous/neutral pHranges, which comprises: continuously mixing in a first reaction step, an aqueous/alkaline solution of the coupling component with an aqueous solution of an acid selected from the group consisting of acetic acid, boric acid, phosphoric acid, hydrochloric acid or sulfuric acid at a temperature lower than 65°C and within a period of less than 1 minute,
I~
1 during which the coupling component ,eo ene- precipitating at least partially as reactive matter; continuously mixing, in a second reaction step immediately following the first reaction step, the suspension obtained with an aqueous/acid solution of the diazo component at a temperature of less than 65°C within a period of less than 1 minute, and establishing a predetermined pH between 2 and 9 by controlling the flow of the mass streams of the diazo component and coupling component and thereby causing a portion of the coupling component to undergo immediate reaction to the azo pigment to be made; and reacting the balance portion of the coupling component in a post-reaction phase with unreacted diazo component to the azo pigment to be made.
Further preferred and optional features of the process s 15 of this invention provide: a) for the continuous mixing to be effected over a period of less than 6 seconed, in the second reaction step; b) for a buffering substance contributing to establishing the predetermined pH to be added during the second reaction step; c) for 60 to 98 of the coupling component to undergo immediate reaction to the azo pigment to be made, in the second reaction step; d) for the temperature during the azo coupling reaction including the post-reaction phase to be 10 to 55 0
C
during the second reaction step; 3
S-
11'
J
S.
e) for the reactive coupling component precipitated during the first reaction step, depending on its chemical composition, to have an enolate, phenolate or naphtholate group fixed to the surface of its particles.
The first processing step of this invention comprises mixing an aqueous/alkaline-solution of the difficultly soluble coupling component within a period of less than 1 minute with an aqueous, optionally buffering acid solution at temperatures of less than 65 0 C, the resulting pH-value being within the weakly acid to alkaline range (pH 4-11).
During that operation, at least a portion of the difficultly soluble coupling component is precipitated as reactive matter which is more reactive than the particles of the pure coupling component. Depending on the chemical -i r- of the coupling component, the regular finely crystalline particles have a phenolate, enolate or naphtholate group, fixed to their surface, which acts upon the electron density within the crystalline particles and renders them especially reactive.
Immediately after the mixing operation during which coupling component is precipitated, the resulting aqueous suspension is mixed with the equivalent quantity of an aqueous/acid-diazonium salt solution at a temperature of less than 65°C and within a period of less than 1 minute, the resulting pH-value varying between 2 and 9. Establishing an even narrower range depends on the diazo component and coupling component selected and the particular product to be made. It is however allowable or even obligatory for the pH 4 t:C.~hr? selected to be the higher within the limits specified the stabler the diazo component and the lower the solubility of the coupling component in the neutral range.
A portion of the azo pigment to be made is formed immediately on mixing the feed materials, and another portion is formed in a post reaction phase, depending on the specific properties of the feed materials, from diazo compound still present and coupling component precipitated as reactive matter. Although an excess of diazo component has long been held highly undesirable, we have unexpectedly found that within the pH- and temperature ranges specifically selected in this invention for the less than 1 minute rapid mixing of the feed components, the diazonium component is substantially not liable to undergo decomposition during a 0.01 1 15 hour period which is sufficiently long for the precipitated o a| reactive matter portion of the coupling component to become completely coupled in a post-reaction phase, which varies between 0.01 and 1 hour, depending on the product to be made. It is often advantageous for a portion of the product coming from the mixer to be recycled, through an intermet S diate container, if desired, in order to promote the mixing and regulate the residence time of the material in the mixer.
S k r feed materials for making the diazo component are e.g. 2,5-dichloroaniline; 2-chloro-4-nitroaniline; ~5-nitro-2-aminoanisole or 3-nitro-4-aminotoluene. The useful i coupling components should preferably be selected e.g. from 0 2-hydroxy-3-naphthoic acid anilide; 3-naphthol or aceto acetic acid-o-aniside.
Example 1 (cf. accompanying drawing) Preparation of 2-(2-methoxy-4-nitrophenylazo)-N-(2methoxy-phenyl)-3-oxobutane imide of the formula
CH
0 0 0 II II NH C CH C CH 3
N
OCH
3
NO
2 2 0'0 0. 00 0 00 .000 00 0 00 0 0 0 00 0$.
0 08D Sa 0s 00 8 ).c 134 g 0.80 mol) 5-nitro-2-aminoanisole formula of the
NH
2
OCH
3
NO
2 was suspended in 250 ml water and 210 ml hydrochloric acid (31 wgt %),the suspension was cooled by adding 400 g ice and diazotized at 5 10 0 C with 113 ml sodium nitrite solution wgt 5 g filter aid and clarifying agent (kieselguhr and active carbon) were added,.the solution was filtered and made up with ice water to 2 liters in container Next, the nitrite in excess was practically completely decomposed by adding amidosulfuric acid (aminosulfonic acid H 2
N-SO
2 0H).
172 g 0.83 mol) acetoacetic acid-o-anisidide of the formula 0 0 N
CH
3
-C-CH
2
-C-N-
OCH
3 was suspended in 530 ml water and dissolved by adding 200 ml sodium hydroxide solution (25 wgt The solution was cooled to 10°C and made up with water to 1000 ml. Within 2 hours, this solution from container (11) was introduced jointly with a mixture (coming from line 12) of 152 ml aceo tic acid (60 wgt and 400 ml water into mixer Dilute acetic acid was added as a buffering substance in quantities I° 15 monitored by means of pH-probe near the outlet of mixer (13) 0000 o°a so as to have a pH of 5.5. A portion of the coupling compo- So nent precipitated as reactive matter.
The material coming from mixer (13) was introduced into oo mixer (14) and mixed therein within 2 hours at 10 0 C with the 20 diazonium solution coming from container The product 0 leaving mixer (14) was introduced through line (15) into collecting tank The residence time in each of mixers (13) and (14) was 1 second.
The mixing operation in mixer (14) was promoted by means of a stream of auxiliary material recycled from collecting tank (16) through recycle line into mixer (14); the auxiliary material was used in a quantity (by volume) ten times larger than the quantity (by volume) of the diazonium salt used per hour. The pH in collecting tank (16) was 3.6 and the temperature was maintained at 10 0 C by adding ice.
After all materials from containers (10) and (11) and line (12) had been added, the batch in collecting tank (16) was allowed to undergo post-reaction for 20 minutes at 20 0
C
until diazo compound was no longer detectable.
The azo pigment taken from collecting tank (16) through line (18) by filtration, and dried at 100 0 C (302 g 0.78 mol) was free from occluded coupling component and had a coloring strength 10 stronger than that obtainable by conventional methods.
;e Example 2 (cf. accompanying drawing) Preparation of 1-(2-nitro-4-methylphenylazo)-2-hydroxy- 15 naphthalene of the formula
NO
«t °N
OH
0.526 mol) 3-nitro-4-aminotoluene of the formula
CH
3 3 S NO 2 NH 2 was suspended in 500 ml water and 126 ml hydrochloric acid (31 wgt and the suspension was diazotized at 5 0 C with 69 S-d "a o on 0900 0 n *00* 00 Cae C CC
CC
0ra ml sodium nitrite solution (40 wgt 5 g filter aid and clarifying agent (kieselguhr, active carbon) were added, the diazonium salt solution was filtered and made up with water to 2000 ml. The nitrite in excess was practically completely decomposed by means of amidosulfuric acid (H 2 N-SO2OH), and the diazonium salt solution was stored at 5 0 C in container g B-naphthol (0.521 mol) was dissolved in container (11) in 500 ml water and 186 ml sodium hydroxide solution (25 wgt the solution was cooled to 10 0 C and made up to 1500 ml. This solution from container (11) was introduced within 2 hours jointly with a solution (coming from line 12) of 24 g phosphoric acid (85 wgt as a buffering substance in 500 ml water into mixer a portion of the coupling 15 component precipitated as reactive matter.
The material coming from mixer (13) was introduced into mixer (14) and mixed at 10-15 0 C with the diazonium salt solution from container The product was taken from mixer (14) through line (15) and collected in collecting tank The residence time was 6 seconds in mixer (13) and 2 seconds in mixer (14).
The mixing operation in mixer (14) was promoted by means of a stream of auxiliary material recycled from collecting tank (16) through recycle line (17) into mixer (14); the auxiliary material was used in a quantity (by volume) ten times larger than the quantity (by volume) of the diazonium salt used per hour. Collecting tank (16) had initially o
I
3 Ii
LL
been charged with 250 ml water diluting the auxiliary material recycled on starting the reaction.
A pH of 8.5 8.8 was metered in collecting tank (16) which was maintained by fine control of the mass streams of acid diazonium salt solution and alkaline coupling solution.
The conversion rate of diazonium component to desirable azo pigment was about 98 at the outlet of mixer it became quantitative during a 0.6 minute post-reaction period.
The suspension was taken from collecting tank (16) through line filtered and dried at 110 0 C; the azo pigment so made was of high brillancy and obtained in a yield of 156 g (0.51 mol).

Claims (8)

1. Process for making pure azo pigments substantially free from occlusions of unreacted coupling components by subjecting a diazo component to an azo coupling reaction with the equivalent quantity of a coupling component difficulty soluble, that is, a coupling component having a solubility of less than 0.1 wgt at pH7 at temperatures less than 65°C in the aqueous/acid and aqueous/neutral pH-ranges, which comprises: continuously mixing, in a first reaction step, an aqueous/alkaline solution of the coupling component with an aqueous solution of an acid selected from the group consisting of acetic acid, boric acid, phosphoric acid, hydrochloric acid or sulfuric acid at a temperature lower than 65°C and within a period of less than 1 minute, the resulting pH value being within the weakly acid to alkaline range, during which the coupling component commences precipitating at least partially as reactive matter; continuously mixing, in a second reaction step immediately following the first reaction step, the suspension obtained with an aqueous/acid solution of the diazo component at a temperature of less than 65°C within a period of less than 1 minute, and establishing a predetermined pH between 2 and 9 by controlling the flow of the mass streams of the diazo component and coupling component and thereby causing a portion of the coupling component to undergo immediate reaction to the azo pigment to be made; and reacting the balance portion of the coupling component in a post-reaction phase with unreacted diazo component to the azo pigment to be made.
2. Process as claimed in claim 1, wherein the continuous mixing is effected over a period of less than 6 seconds, in the second reaction step. .1
3. Process as claimed in claim 1 or 2, wherein a buffering substance contributing to establishing the predetermined pH is added during the second reaction step.
4. Process as claimed in at least one of the preceding claims, wherein 60 to 98 of the coupling component un- dergoes immediate reaction to the azo pigment to be ma- de, in the second reaction step.
Process as claimed in at least one of the' preceding claims, wherein the temperature during the azo coupling reaction including the post-reaction phase is 10 to during the second reaction step.
6. Process as claimed in at least one of the preceding claims, wherein, depending on its chemical composition, the reactive coupling component precipitated during the first reaction step has an enolate, phenolate or naphtholate group fixed to the surface of its particles.
7. Process as claimed in at least one of the preceding claims conducted substantially as described in Example 1 or 2 herein.
8. Azo pigments whenever obtained by a process as claimed Ii j' in at least one of the preceding claims. DATED this 30th day of April 1987. SIHOECHST AKTIENGESELLSCHAFT SEDWD. WATERS SONS PATENT ATTORNEYS QUEEN STREET MELBOURNE. VIC. 3000.
AU72407/87A 1986-05-03 1987-05-01 Process for making azo pigments Ceased AU594760B2 (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE3615100 1986-05-03
DE3615100 1986-05-03

Publications (2)

Publication Number Publication Date
AU7240787A AU7240787A (en) 1987-11-05
AU594760B2 true AU594760B2 (en) 1990-03-15

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ID=6300159

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AU72407/87A Ceased AU594760B2 (en) 1986-05-03 1987-05-01 Process for making azo pigments

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EP (1) EP0244687B1 (en)
JP (1) JPH0784566B2 (en)
KR (1) KR960008248B1 (en)
AU (1) AU594760B2 (en)
DE (1) DE3782966D1 (en)
DK (1) DK168394B1 (en)
ES (1) ES2037023T3 (en)
IN (1) IN169308B (en)

Families Citing this family (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
IN169307B (en) * 1986-05-03 1991-09-28 Hoechst Ag
DE3932829C1 (en) * 1989-09-30 1991-05-02 Ciba-Geigy Ag, Basel, Ch
DE4447593C2 (en) * 1994-10-05 2000-12-07 Clariant Gmbh Toner for electrophotographic developers containing an azo yellow pigment
US6099635A (en) * 1999-04-09 2000-08-08 Lonza Ag Acetoacetylated suspensions in pigment applications
JP2006028341A (en) * 2004-07-16 2006-02-02 Toyo Ink Mfg Co Ltd Disazo pigment production method and disazo pigment
GB0416256D0 (en) * 2004-07-20 2004-08-25 Avecia Ltd Manufacturing process
DE602005025919D1 (en) * 2004-12-03 2011-02-24 Canon Kk PREPARATION FOR AZOPIGMENT DISPERSION
JP4533303B2 (en) * 2004-12-03 2010-09-01 キヤノン株式会社 Method for producing azo pigment dispersion

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
AU7240687A (en) * 1986-05-03 1987-11-05 Hoechst Aktiengesellschaft Process for making azo pigments

Family Cites Families (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2174954A (en) * 1937-03-22 1939-10-03 Harmon Color Works Inc Azo pigment and method of preparing
DE1085278B (en) * 1958-03-08 1960-07-14 Hoechst Ag Process for the continuous production of azo pigments
DE2629076B2 (en) * 1976-06-29 1978-04-27 Basf Farben + Fasern Ag, 2000 Hamburg Process for the production of a disazo pigment with improved application properties
US4395264A (en) * 1981-11-06 1983-07-26 Basf Wyandotte Corporation Azo coupling process
GB2129434B (en) * 1982-10-08 1986-04-16 Ciba Geigy Ag Production of azo compounds

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
AU7240687A (en) * 1986-05-03 1987-11-05 Hoechst Aktiengesellschaft Process for making azo pigments

Also Published As

Publication number Publication date
DK223487D0 (en) 1987-05-01
DK223487A (en) 1987-11-04
EP0244687A2 (en) 1987-11-11
EP0244687A3 (en) 1990-11-14
ES2037023T3 (en) 1993-06-16
JPS62263261A (en) 1987-11-16
EP0244687B1 (en) 1992-12-09
KR960008248B1 (en) 1996-06-21
DK168394B1 (en) 1994-03-21
IN169308B (en) 1991-09-28
KR870011207A (en) 1987-12-21
JPH0784566B2 (en) 1995-09-13
DE3782966D1 (en) 1993-01-21
AU7240787A (en) 1987-11-05

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