CN1563202A - Method for preparing organic pigment of red benzimidazolones - Google Patents
Method for preparing organic pigment of red benzimidazolones Download PDFInfo
- Publication number
- CN1563202A CN1563202A CN 200410017720 CN200410017720A CN1563202A CN 1563202 A CN1563202 A CN 1563202A CN 200410017720 CN200410017720 CN 200410017720 CN 200410017720 A CN200410017720 A CN 200410017720A CN 1563202 A CN1563202 A CN 1563202A
- Authority
- CN
- China
- Prior art keywords
- acid
- methyl
- amino
- hydroxyl
- naphthoyl
- 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.)
- Granted
Links
Landscapes
- Inks, Pencil-Leads, Or Crayons (AREA)
Abstract
A method for preparing red benzimidazolone organic dyestuff includes applying diazotization process to carry out diazotization for substituted aromatic amine and aminobenzenesulfonic acid separately for obtaining relevant diazoles solutions, mixing the two diazols, using mixed diazols to couple with coupling composition for obtaining coupled material in mixed crystal form and producing final dyestuff product through pigmenting.
Description
Technical field
The present invention relates to a kind of preparation method of benzoglyoxaline ketone pigment dyestuff, relate in particular to a kind of preparation method of red benzoglyoxaline ketone pigment dyestuff.
Background technology
Benzoglyoxaline ketone pigment dyestuff is to be the azo pigment of coupling component with the amino benzimidazolone or derivatives thereof of 2 '-hydroxyl-3 '-naphthoyl-5-, its structure as the formula (1):
This pigment is a class high-performance pigment dyestuff, and their color and luster is very strong, can satisfy the application demand of most of industrial sectors, is mainly used in high-grade occasion, as senior plastics and high-grade printing ink goods etc.
At present, the preparation method of red benzoglyoxaline ketone pigment dyestuff generally is divided into three steps, one is for replacing the diazotization of aryl primary amine, and it two be the coupling of diazonium salt and 2 '-hydroxyl-3 '-naphthoyl-5-amino benzimidazolone or derivatives thereof, and it three is the pigmenting processing of conjugates.The diazotization reaction that wherein replaces aryl primary amine realizes industrial being easy to, but these diazonium salts are when carrying out coupling with the amino benzimidazolone or derivatives thereof of 2 '-hydroxyl-3 '-naphthoyl-5-, if the condition of reaction and the aftertreatment of product are not controlled well, although then can obtain red azo product, but they can not use as pigment, because their color is not bright-coloured, tinting strength is low and their solid particulate is very hard, easily disperse is bad, can not satisfy the application requiring of derived product.Therefore, the product that obtains of coupled reaction also will just can make it to become pigment through special pigmenting processing.For this reason, the reaction conditions in control coupling stage and to the key that special aftertreatment is the red benzoglyoxaline ketone azo organic pigment of preparation of carrying out of product, the document of relevant this respect is seldom.
English Patent (GB978094) discloses a kind of method for preparing red benzoglyoxaline ketone pigment dyestuff, according to the method, coupling product (crude pigment product) must be carried out aftertreatment in pyridine, but peculiar stink beastly of pyridines solvent and toxicity are very disadvantageous to operator's physical and mental health.English Patent (GB996075) also discloses a kind of method for preparing red benzoglyoxaline ketone pigment dyestuff, according to their this method, must coupling product (crude pigment product) is dry later at N, carry out aftertreatment in the dinethylformamide (DMF), dispose, also must add the water of 2 times of DMF volumes, could obtain pigment.Well imagine that DMF is the organic solvent that can dissolve each other with water, added water therein and will reclaim just very difficultly later on again that production cost will be very high just like this.
Summary of the invention
The objective of the invention is to, provide a kind of new method for preparing red benzoglyoxaline ketone pigment dyestuff, to overcome the defective of prior art.
Technical scheme:
The preparation method of the said red benzoglyoxaline ketone pigment dyestuff of the present invention, it comprises: the diazotization that 1. replaces aryl primary amine, 2. the amino benzimidazolone or derivatives thereof of diazonium salt and 2 '-hydroxyl-3 '-naphthoyl-5-makes conjugates through coupled reaction, 3. the pigmenting of conjugates is handled three steps, it is characterized in that, step 2. in said diazonium salt be: replace the mixture that diazonium salt that the diazotization of aryl primary amine makes and compound (a) are formed in 1. by step, wherein replace diazonium salt that the diazotization of aryl primary amine makes in 1. and the mol ratio of compound (a) is 7～9.9: 3～0.1 by step
In the formula: X is Cl
-Or HSO
4 -, n is 1～5 a integer.
The present invention at first adopts existing diazotisation methods to carry out diazotization respectively to replacing aryl primary amine and aniline sulfonic acid, obtain corresponding diazonium salt solution (or suspension), then two kinds of diazonium salts are mixed, with mixing diazonium salt and coupling component (the amino benzimidazolone or derivatives thereof of 2 '-hydroxyl-3 '-naphthoyl-5-) coupling, the conjugates (crude product pigment) that obtains the mixed crystal form is carried out obtaining pigment product after pigmenting is handled again.Facts have proved that the pigment that adopts the method for the invention to make is more far better than existing pigment (one-component pigment) aspect application performance.
Embodiment
The preparation method of the said red benzoglyoxaline ketone pigment dyestuff of the present invention, it comprises the steps:
(1) diazotization reaction of replacement aryl primary amine and aniline sulfonic acid:
This is a prior art, does not repeat them here, and its reaction formula is as follows:
Wherein: X is Cl
-Or HSO
4 -[compound (b)] is optional for described replacement aryl primary amine: adjacent fluoroaniline, Ortho-Chloro aniline, p-Chlorobenzoic acid amide, m-bromoaniline, between Iodoaniline, Ortho Toluidine, para-totuidine, ORTHO ANISIDINE, o-Nitraniline, m-nitraniline, p-Nitroaniline, methyl o-aminobenzoate, the positive butyl ester of anthranilic acid, 2,4-xylidine, adjacent methyl p-Chlorobenzoic acid amide, 2-methyl-5-chloro aniline, 2-methyl-4-N-methyl-p-nitroaniline, 2-methyl-4-amino-5-methoxyl group-benzene sulfonyl methylamine, 2-methoxyl group-4-chloroaniline, 2-methoxyl group-5-chloroaniline, 2-methoxyl group-4-N-methyl-p-nitroaniline, 2-nitro-4-methyl-aniline, 2-nitro-4-anisidine, 2-nitro-4-acetylaminoaniline, 2,5-dichlorphenamide bulk powder, 2-amino-4,4 '-DCBP ether, 2, the 3-aminobenzamide, 3-amino-4-methoxy benzamide, 3-aminobenzoyl methylamine, 3-aminobenzoic anilide, 4-amino-3-methoxybenzoyl aniline, 3-amino-4-methoxybenzoyl-2 '-methyl-3 '-chloroaniline, 4-aminobenzoyl methylamine, a kind of in 4-aminobenzamide or the 4-aminobenzoyl methylamine etc.; Described aniline sulfonic acid is optional: m-sulfanilic acid, Sulphanilic Acid or aniline-2, a kind of in the 5-disulfonic acid etc.
(2) coupled reaction of mixing diazonium salt and 2 '-hydroxyl-3 '-naphthoyl-amino benzimidazolone or derivatives thereof of 5-:
The diazonium salt of the replacement aryl primary amine that will be made by step (1) and the diazonium salt of Phenylsulfonic acid are that 7～9.9: 3～0.1 mixed is formed and mixed diazonium salt in molar ratio;
The amino benzimidazolone or derivatives thereof of 2 '-hydroxyl-3 '-naphthoyl-5-is suspended in water, add sodium hydroxide solution, stir and make it dissolving, add proper amount of active carbon then, restir 30 minutes removes by filter insolubles,
Filtrate is coupling solution;
In the process of carrying out coupled reaction, coupling solution can be added to and contain in the damping fluid that mixes diazonium liquid, also can be added in the damping fluid that contains coupling solution mixing diazonium liquid, or both are added in the damping fluid simultaneously, also contain dispersion agent, emulsifying agent and rosin soap lye in damping fluid except buffer reagent.The coupled reaction temperature is 10 ℃～50 ℃, is preferably 15 ℃～25 ℃, and reaction is no diazonium liquid existence to this system.Whether exist the method for diazonium salt referring to ZL 00111495.6 in the check reaction system.After finishing, reaction after filtration, promptly get the crude pigment product that wets after washing and pressing dry, or it is promptly being got the crude pigment product of doing after pulverizing again after 50～100 ℃ of dryings; The reaction formula of main coupled reaction is as follows:
In the formula: R=H, Cl, Br, CH
3, OCH
3Or OC
2H
5
The amino benzimidazolone derivatives of described 2 '-hydroxyl-3 '-naphthoyl-5-is optional: 5-(2 ', 3 '-hydroxyl naphthoamide)-the amino benzimidazolone of 6-chloro-, 2 '-hydroxyl-3 '-naphthoyl-5-amino-7 chloro benzimidazole ketone, 2 '-hydroxyl-3 '-naphthoyl-5-amino-6 methyl benzimidazolone, a kind of in 2 '-hydroxyl-3 '-naphthoyl-5-amino-6-oxyethyl group benzo imidazolone or 2 '-hydroxyl-3 '-naphthoyl-5-amino-7-bromobenzene and the imidazolone.
Said dispersion agent comprises: the condenses of lipid acid and taurine; the condenses of lipid acid and N methyl taurine; the condenses of lipid acid and hydroxyethylsulfonic acid; alkyl benzene sulphonate (ABS); alkyl naphthalene sulfonic acid; the sulfuric ester of alkylphenol polyoxyethylene; the sulfuric ester of fatty alcohol-polyoxyethylene ether; the sulfuric ester of fatty amide Soxylat A 25-7, dialkyl succinylsuccinate monoamide, alkenyl succinic acid monoesters; fatty alcohol-polyoxyethylene ether sulfuric acid succinate monoester; alkylsulphonic acid, lipid acid L-glutamic acid condenses, alkylsurfuric acid succinate monoester.Described lipid acid refers to: palmitinic acid, stearic acid, oleic acid, aliphatic amide alcoxyl hydrochlorate, alcoxyl acid polyamines, aliphatic amine polyoxyethylene ether, aliphatic amide, binary aliphatic amide and derive and the polyamine that comes by aliphatic amide and Fatty Alcohol(C12-C14 and C12-C18), amine oxide, fatty alcohol-polyoxyethylene ether, aliphatic alcohol polyethenoxy ester, trimethyl-glycine, as fatty acid amide-N-CAB, fatty alcohol phosphate or fatty alcohol-polyoxyethylene ether, fatty amide ethoxy hydrochlorate, the oxidation of fat enol adds and thing and polyoxyethylene alkylphenol ether, poly N-vinyl pyrrolidone (PVP), alkyl sulfonamide (length of alkane chain corresponding to their boiling range at 180～210 ℃), 2,4, the condenses of 6-tributyl phenol and oxyethane, oleylamide acetate, two-octadecyl-alkyl dimethyl ammonium chloride, the condenses of oil enol and oxyethane, fatty alcohol-polyoxyethylene ether silane, fatty alcohol-polyoxyethylene ether etc. or their mixture.
Said emulsifying agent is one or more in alkyl phenol ethylene oxide condensate, Span60 or the sorbitan monooleate Soxylat A 25-7.
Said rosin soap lye is the light yellow transparent liquid of being made up of rosin and sodium hydroxide solution.
Said buffer reagent has: ammonium chloride and ammoniacal liquor or phosphoric acid and sodium phosphate, their content in damping fluid are 20%～40% (weight); Dispersion agent, emulsifying agent and the total content of rosin soap lye in buffered soln are 0.1%～2% (weight) of crude pigment product weight.
Above-mentioned dispersion agent and emulsifying agent are commercially available product.
After coupled reaction finishes, except main body pigment, also generated the product of aniline sulfonic acid diazonium salt as the formula (2) like this with 2 '-hydroxyl-3 '-naphthoyl-5-amino benzimidazolone or derivatives thereof coupling:
(3) pigmenting of crude pigment product is handled:
The crude pigment product that step (2) is obtained joins in the organic solvent, is heated to suitable temperature, for example: 50～180 ℃, preferably 80～150 ℃, stirred preferably 1～3 hour 0.5～8 hour.Cool off, filter, mother liquor reclaims reusable through distillation, washes filter cake with water to wherein not containing organic solvent, can obtain said red benzoglyoxaline ketone pigment dyestuff after filter cake drying, the pulverizing;
Said machine solvent can adopt the organic solvent that dissolves each other with water, as: methyl ethyl ketone, isopropyl acetone, acetone, isobutyl ketone, methyl alcohol, ethanol, propyl alcohol, N-Methyl pyrrolidone, N, dinethylformamide, formic acid, acetate and/or propionic acid etc., or employing and the immiscible organic solvent of water, as: isopropylcarbinol, propyl carbinol, chlorobenzene and/or dichlorobenzene etc., its add-on with 10 times～20 times of crude pigment product weight for well; As adopting and the immiscible organic solvent of water, preferably add 0.5%～2% tensio-active agent of crude pigment product gross weight, live to be made of said dispersion agent of preamble and emulsifying agent agent in the available surface.
The red benzoglyoxaline ketone pigment dyestuff that aforesaid method is prepared, coloured light is gorgeous and easily disperse good, can be used for the production of high-grade plastics and high-grade printing ink goods etc.
Below will the present invention is further illustrated by embodiment, the cited case does not limit protection scope of the present invention:
Embodiment 1
The preparation of adjacent n-buty formate phenylazo-5-(2 ', 3 '-hydroxyl naphthoamide)-amino benzimidazolone (C.I. Pigment red 208)
The main reaction formula is as follows:
The preparation of diazonium liquid
1) diazotization of aniline sulfonic acid
Sulphanilic Acid (1.73g, 10mmol) water-soluble (25ml includes 10mmolNaOH) stirs 15min under the room temperature, filters, and discards insolubles, and ice bath is cooled to 0-5 ℃, adds NOHSO
4(1.59g, 12.5mmol are made up of the vitriol oil and Sodium Nitrite), finish, continue to stir 10min, get gray suspension, be diluted to cumulative volume 50ml with 1N hydrochloric acid, refrigerate standby.
2) diazotization of the positive butyl ester of anthranilic acid
(35g, 0.18mol), water (800ml), 30% hydrochloric acid (30ml) mix the back and are cooled to 0-5 ℃ with ice bath the positive butyl ester of anthranilic acid, add small amounts of emulsifiers OP-10, stir 5 minutes, slowly drip NaNO in 30-40 minute
2Solution is (by 12.7gNaNO
2Form with 30ml water), controlled temperature is at 0-5 ℃ when reinforced, sampling analysis, be little blueness on the starch-kalium iodide test paper and show that then reaction finishes when reaction solution drops in, add a little activated carbon insulated and stirred 10-30min, filter, remove insolubles, gained filtrate is the diazonium liquid of the positive butyl ester of anthranilic acid.
3) preparation of mixing diazonium liquid
9: 1 in molar ratio, get the diazonium liquid of the positive butyl ester of anthranilic acid and the diazonium liquid of Sulphanilic Acid respectively, under ice bath cooling, both are mixed promptly to get mix diazonium liquid.
The preparation of coupling solution
Under the room temperature, with 5-(2 ', 3 '-hydroxyl naphthoamide)-amino benzimidazolone (60g 0.188mol) mixes with 5%NaOH (1000ml) and makes it dissolving, adds a small amount of activated carbon, stirs 10min, filter coupling solution.Coupling
In the time of 5～10 ℃, the damping fluid (600ml) for preparing is in advance joined in the coupling reactor, stir and add paucidisperse agent and polyoxyethylene nonylphenol ether and rosined soap down again, controlled temperature is at 10～15 ℃, and PH=8.5～9.0 are with coupling solution and diazonium liquid, add in the reactor in the mode that also flows, maintain the temperature at 10～15 ℃ during this time, by dripping PH=8.5～9.0 that 10%NaOH solution keeps system, whether completely consumed is fallen with H acid test diazonium liquid.If, then keep 10～15 ℃ of temperature, continue to stir 1 hour, be warming up to 90～95 ℃ subsequently, be incubated 2 hours, filtered while hot is 50～55 ℃ a water thorough washing with temperature, the crude pigment product that press dry wetly.
The pigmenting processing of crude pigment product
Under the room temperature, and the mixed solvent that will form by DMF/ ethanol (DMF: ethanol=9.5: 0.5 (volume ratio), 1700ml) join in the reactor, stir and add above-mentioned wet crude pigment product down, finish, be warming up to 85 ℃, insulated and stirred 1～1.5 hour.Subsequently, be cooled to 15～20 ℃ of filtrations, mother liquor reuses after reclaiming, after the filter cake filter is done, again join and add water making beating in the reactor, be warmed up to 70～80 ℃, stirred 0.5～1 hour, filter, filter cake is washed with deionized water, pulverizes after the drying again and promptly gets pigment elaboration 80g.
Embodiment 2
The preparation of adjacent n-buty formate phenylazo-5-(2 ', 3 '-hydroxyl naphthoamide)-amino benzimidazolone (C.I. Pigment red 208)
Synthesizing of crude pigment product with embodiment 1.
The pigmenting processing of crude pigment product
By crude pigment product weight (g): DMF (ml)=1: 20 crude pigment product and the solvent of doing joined in the reactor, finish, be warming up to 80～90 ℃, insulated and stirred 0.5～1 hour under stirring.Subsequently, be cooled to 15～20 ℃ of filtrations, the DMF mother liquor reuses after reclaiming, and filter cake promptly gets pigment elaboration 65g through washing after the drying and crushing.
Embodiment 3
The preparation of 2-methoxyl group-5-methyl-4-sulphonyl methylamine-phenyl-azo-5-(2 ', 3 '-hydroxyl naphthoamide)-amino benzimidazolone (C.I. Pigment red 185)
The main reaction formula is:
The preparation of diazonium liquid
1) aniline-2, the diazotization of 5-disulfonic acid
Method is with the diazotization of Sulphanilic Acid
2) diazotization of 2-methoxyl group-5-methyl-4-sulphonyl methylamino aniline
Under the room temperature, with 2-methoxyl group-5-methyl-4-sulphonyl methylamino aniline (46g, 0.19mol), water (500ml), 30% hydrochloric acid (25ml) joins in the reactor, it is molten entirely to be stirred to material, ice bath is cooled to 0～5 ℃, drips NaNO in 25～30 minutes
2Solution is (by 14g NaNO
2Form with 35ml water), during temperature be controlled at 0～5 ℃, check reaction end with the starch-kalium iodide test paper, reaction finishes the back and adds a small amount of activated carbon, continue to stir 5～10 minutes, remove by filter insolubles, filtrate is the diazonium liquid of 2-methoxyl group-5-methyl-4-sulphonyl methylamino aniline.
3) preparation of mixing diazonium liquid
9: 1 in molar ratio, get the diazonium liquid and the aniline-2 of 2-methoxyl group-5-methyl-4-sulphonyl methylamino aniline respectively, the diazonium liquid of 5-disulfonic acid under the ice bath cooling, mixes both promptly to get and mixes diazonium liquid.
The preparation of coupling solution
Under the room temperature, with 5-(2 ', 3 '-hydroxyl naphthoamide)-amino benzimidazolone (64g 0.2mol) mixes with 5%NaOH (1000ml) and makes it dissolving, adds a small amount of activated carbon, stirs 10min, filter coupling solution.
Coupling
In the time of 5～10 ℃, the damping fluid (600ml) for preparing is in advance joined in the coupling reactor, stir and add paucidisperse agent and polyoxyethylene nonylphenol ether and rosined soap down again, controlled temperature is at 10～15 ℃, and PH=8.5～9.0 are with coupling solution and diazonium liquid, add in the reactor in the mode that also flows, maintain the temperature at 10～15 ℃ during this time, drip 10%NaOH and keep PH=8.5～9.0, whether completely consumed is fallen with H acid test diazonium liquid.If, then keep 10～15 ℃ of temperature, continue to stir 1 hour, be warming up to 90～95 ℃ subsequently, be incubated 2 hours, filtered while hot is 60～65 ℃ a water thorough washing with temperature, the crude pigment product that press dry wetly.
The pigmenting processing of crude pigment product
Under the room temperature, and the mixed solvent that will form by the DMF/ isobutyl ketone (DMF: isobutyl ketone=9: 1 (volume ratio), 2000ml) join in the reactor, stir and add above-mentioned wet crude pigment product down, finish, be warming up to 85 ℃, insulated and stirred 1～1.5 hour.Subsequently, be cooled to 15～20 ℃ of filtrations, join again after filter cake takes out and add the water making beating in the reactor, be warmed up to 70～80 ℃, stirred 0.5～1 hour, filtration, filter cake is washed with deionized water, promptly gets pigment elaboration 95g after the drying.
Embodiment 4
The preparation of 2-methoxyl group-5-methyl-4-sulphonyl methylamine-phenyl-azo-5-(2 ', 3 '-hydroxyl naphthoamide)-amino benzimidazolone (C.I. Pigment red 185)
Synthesizing of crude pigment product with example 3
The pigmenting processing of crude pigment product
Crude pigment product and solvent by crude pigment product weight (g): DMF (ml)=adding in 1: 20 is done finish, and are warming up to 70～80 ℃, insulated and stirred 0.5～1 hour.Subsequently, be cooled to 15～20 ℃ of filtrations, filtrate is in order to reclaim DMF, and filter cake promptly gets pigment elaboration 75g through washing after drying, the pulverizing.
Embodiment 5
The preparation of 2-methoxyl group-4-formylaniline phenyl-azo-5-(2 ', 3 '-hydroxyl naphthoamide)-amino benzimidazolone (C.I. Pigment red 176)
The main reaction formula is as follows:
The preparation of diazonium liquid
1) diazotization of m-sulfanilic acid
Method is with the diazotization of Sulphanilic Acid.
2) diazotization of 2-methoxyl group-4-formylaniline base aniline
Under the room temperature, with 2-methoxyl group-4-formylaniline base aniline (44g, 0.18mol), water (500ml), 30% hydrochloric acid (30ml) joins in the reactor, it is molten entirely to be stirred to material, ice bath is cooled to 0～5 ℃, drips NaNO in 25～30 minutes
2Solution is (by 12.7g NaNO
2Form with 35mL water), during temperature be controlled at 0～5 ℃, check reaction end with the starch-kalium iodide test paper, reaction finishes the back and adds a small amount of activated carbon, continue to stir 5～10 minutes, remove by filter insolubles, filtrate is the diazonium liquid of 2-methoxyl group-4-formylaniline base aniline.
3) preparation of mixing diazonium liquid
9: 1 in molar ratio, get the 2-methoxyl group-diazonium liquid of 4-formylaniline base aniline and the diazonium liquid of m-sulfanilic acid respectively, under ice bath cooling, both are mixed promptly to get mix diazonium liquid.
The preparation of coupling solution
Under the room temperature, with 5-(2 ', 3 '-hydroxyl naphthoamide)-amino benzimidazolone (60g 0.188mol) mixes with 5%NaOH (1000ml) and makes it dissolving, adds a small amount of activated carbon, stirs 10min, filter coupling solution.
Coupling
Under the room temperature, the damping fluid for preparing in advance (is made up of phosphoric acid and sodium phosphate, 600ml) join in the coupling reactor with diazonium liquid, stir and add paucidisperse agent and polyoxyethylene nonylphenol ether and rosined soap down again, in 2 hours, be added drop-wise to coupling solution in the above-mentioned component equably then, control PH=5～6,5～10 ℃ of temperature.Whether completely consumed is fallen with H acid test diazonium liquid.If, then keep 5～10 ℃ of temperature, continue to stir 0.5～1 hour, be warming up to 90～95 ℃ subsequently, be incubated 2 hours, filtered while hot, filter cake temperature are 60～70 ℃ water thorough washing, the crude pigment product that press dry wetly.
The pigmenting processing of crude pigment product
Under the room temperature, will by the DMF/ Virahol (DMF: Virahol=9.5: 0.5 (volume ratio), 2000ml) join in the reactor, stir and to add above-mentioned wet crude pigment product down, finish, be warming up to 85 ℃, insulated and stirred 1～1.5 hour.Subsequently, be cooled to 15-20 ℃ of filtration, filtrate is in order to reclaim solvent, joins again after filter cake takes out to add the water making beating in the reactor, is warmed up to 70～80 ℃, stirs 0.5～1 hour, and filtration is washed with deionized water, promptly gets pigment elaboration 95g behind the filtration cakes torrefaction.
Embodiment 6
The preparation of 2-methoxyl group-4-formylaniline phenyl-azo-5-(2 ', 3 '-hydroxyl naphthoamide)-amino benzimidazolone (C.I. Pigment red 176)
Synthesizing of crude pigment product with embodiment 5
The pigmenting processing of crude pigment product
Crude pigment product and solvent by crude pigment product weight (g): DMF (ml)=adding in 1: 20 is done finish, and are warming up to 70～80 ℃, insulated and stirred 0.5-1 hour.Subsequently, be cooled to 15～20 ℃ of filtrations, filtrate is in order to reclaim DMF, and filter cake promptly gets pigment elaboration 75g through washing after drying, the pulverizing.
Claims (4)
1, a kind of preparation method of red benzoglyoxaline ketone pigment dyestuff, it comprises: the diazotization that 1. replaces aryl primary amine, 2. the amino benzimidazolone or derivatives thereof of diazonium salt and 2 '-hydroxyl-3 '-naphthoyl-5-makes conjugates through coupled reaction, 3. the pigmenting of conjugates is handled three steps, it is characterized in that, step 2. in said diazonium salt be: replace the mixture that diazonium salt that the diazotization of aryl primary amine makes and compound (a) are formed in 1. by step, wherein replace diazonium salt that the diazotization of aryl primary amine makes in 1. and the mol ratio of compound (a) is 7～9.9: 3～0 by step
In the formula: X is Cl
-Or HSO
4 -, n is 1～5 a integer.
2, preparation method as claimed in claim 1 is characterized in that, wherein said compound (a) is one of following compounds:
In the formula: X is Cl
-Or HSO
4 -
3, preparation method as claimed in claim 1 or 2 is characterized in that, said preparation method comprises the steps:
1. aryl primary amine and aniline sulfonic acid diazotization will be replaced respectively, then the diazonium salt of diazotization gained mixedly diazonium salt must be mixed in molar ratio at 7～9.9: 3～0.1;
2. the coupling solution that will form by amino benzimidazolone or derivatives thereof of 2 '-hydroxyl-3 '-naphthoyl-5-and water, in the ammonium chloride that contains dispersion agent, emulsifying agent and rosin soap lye and ammoniacal liquor or phosphoric acid and sodium phosphate buffer, mix diazonium salt and carry out coupled reaction with 1. making by step, the coupled reaction temperature is 10 ℃～50 ℃, react that no diazonium liquid exists to the system, reaction product after filtration, promptly get the crude pigment product that wets after washing and pressing dry or is promptly getting the crude pigment product of doing with reaction product after pulverizing again after 50～100 ℃ of dryings;
Wherein: the content of buffer reagent monochlor(in)ate ammonium and ammoniacal liquor or phosphoric acid and sodium phosphate is 20～40 (weight) % in the said damping fluid; The total content of dispersion agent, emulsifying agent and rosin soap lye is 0.1～2 (weight) % of crude pigment product weight; Said dispersion agent is: the condenses of lipid acid and taurine, the condenses of lipid acid and N methyl taurine, the condenses of lipid acid and hydroxyethylsulfonic acid, alkyl benzene sulphonate (ABS), alkyl naphthalene sulfonic acid, the sulfuric ester of alkylphenol polyoxyethylene, the sulfuric ester of fatty alcohol-polyoxyethylene ether, the sulfuric ester of fatty amide Soxylat A 25-7, the dialkyl succinylsuccinate monoamide, the alkenyl succinic acid monoesters, fatty alcohol-polyoxyethylene ether sulfuric acid succinate monoester, alkylsulphonic acid, lipid acid L-glutamic acid condenses, alkylsurfuric acid succinate monoester, described lipid acid refers to: palmitinic acid, stearic acid, oleic acid, aliphatic amide alcoxyl hydrochlorate, alcoxyl acid polyamines, aliphatic amine polyoxyethylene ether, aliphatic amide, binary aliphatic amide and derive and the polyamine that comes by aliphatic amide and Fatty Alcohol(C12-C14 and C12-C18), amine oxide, fatty alcohol-polyoxyethylene ether, aliphatic alcohol polyethenoxy ester, trimethyl-glycine, fat alcohol phosphate or fatty alcohol-polyoxyethylene ether, fatty amide ethoxy hydrochlorate, fatty enol oxidation adds and thing and polyoxyethylene alkylphenol ether, poly N-vinyl pyrrolidone, alkyl sulfonamide, 2,4, the condenses of 6-tributyl phenol and oxyethane, oleylamide acetate, two-octadecyl-alkyl dimethyl ammonium chloride, the condenses of oily enol and oxyethane, fatty alcohol-polyoxyethylene ether silane, fatty alcohol-polyoxyethylene ether etc. or their mixture;
Said emulsifying agent is one or more in alkyl phenol ethylene oxide condensate, Span60 or the sorbitan monooleate Soxylat A 25-7;
Said rosin soap lye is the light yellow transparent liquid of being made up of rosin and sodium hydroxide solution;
3. will be joined by the crude pigment product that 2. step is obtained in the organic solvent, and be heated to 50～180 ℃, stir 0.5～8 hour, cooling is filtered, and washes filter cake with water to wherein not containing organic solvent, can obtain target product after filter cake drying, the pulverizing;
Wherein: the consumption of organic solvent is 10 times～20 times of crude pigment product weight.
4, preparation method as claimed in claim 3 is characterized in that, step 1. in said replacement aryl primary amine be adjacent fluoroaniline, Ortho-Chloro aniline, p-Chlorobenzoic acid amide, m-bromoaniline, between Iodoaniline, Ortho Toluidine, para-totuidine, ORTHO ANISIDINE, o-Nitraniline, m-nitraniline, p-Nitroaniline, methyl o-aminobenzoate, the positive butyl ester of anthranilic acid, 2,4-xylidine, adjacent methyl p-Chlorobenzoic acid amide, 2-methyl-5-chloro aniline, 2-methyl-4-N-methyl-p-nitroaniline, 2-methyl-4-amino-5-methoxyl group-benzene sulfonyl methylamine, 2-methoxyl group-4-chloroaniline, 2-methoxyl group-5-chloroaniline, 2-methoxyl group-4-N-methyl-p-nitroaniline, 2-nitro-4-methyl-aniline, 2-nitro-4-anisidine, 2-nitro-4-acetylaminoaniline, 2,5-dichlorphenamide bulk powder, 2-amino-4,4 '-DCBP ether, 2, the 3-aminobenzamide, 3-amino-4-methoxy benzamide, 3-aminobenzoyl methylamine, 3-aminobenzoic anilide, 4-amino-3-methoxybenzoyl aniline, 3-amino-4-methoxybenzoyl-2 '-methyl-3 '-chloroaniline, 4-aminobenzoyl methylamine, 4-aminobenzamide or 4-aminobenzoyl methylamine;
Step 2. in the derivative of the amino benzimidazolone of said 2 '-hydroxyl-3 '-naphthoyl-5-be 5-(2 ', 3 '-hydroxyl naphthoamide)-the amino benzimidazolone of 6-chloro-, 2 '-hydroxyl-3 '-naphthoyl-5-amino-7 chloro benzimidazole ketone, 2 '-hydroxyl-3 '-naphthoyl-5-amino-6 methyl benzimidazolone, 2 '-hydroxyl-3 '-naphthoyl-5-amino-6-oxyethyl group benzo imidazolone or 2 '-hydroxyl-3 '-naphthoyl-5-amino-7-bromobenzene and imidazolone;
Step 3. in said organic solvent be methyl ethyl ketone, isopropyl acetone, acetone, isobutyl ketone, methyl alcohol, ethanol, propyl alcohol, N-Methyl pyrrolidone, N, dinethylformamide, formic acid, acetate, propionic acid, isopropylcarbinol, propyl carbinol, chlorobenzene and/or dichlorobenzene.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2004100177205A CN100339442C (en) | 2004-04-16 | 2004-04-16 | Method for preparing organic pigment of red benzimidazolones |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2004100177205A CN100339442C (en) | 2004-04-16 | 2004-04-16 | Method for preparing organic pigment of red benzimidazolones |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1563202A true CN1563202A (en) | 2005-01-12 |
| CN100339442C CN100339442C (en) | 2007-09-26 |
Family
ID=34479123
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB2004100177205A Expired - Fee Related CN100339442C (en) | 2004-04-16 | 2004-04-16 | Method for preparing organic pigment of red benzimidazolones |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN100339442C (en) |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102391663A (en) * | 2011-09-06 | 2012-03-28 | 鞍山七彩化学股份有限公司 | Preparation method of C.I. pigment yellow 151 |
| CN103923480A (en) * | 2014-04-21 | 2014-07-16 | 南通市争妍颜料化工有限公司 | Preparation method of orange benzimidazolone azo pigment |
| CN104592787A (en) * | 2014-12-25 | 2015-05-06 | 上虞舜联化工有限公司 | Preparation method of C.I. pigment yellow 181 |
| CN105524484A (en) * | 2016-01-14 | 2016-04-27 | 上虞市新利化工有限公司 | Preparation method for C.I. pigment red 176 |
| CN106833005A (en) * | 2017-01-23 | 2017-06-13 | 浙江浩川科技有限公司 | A kind of method for preparing permeability azo organic pigment high |
| CN110591409A (en) * | 2019-09-21 | 2019-12-20 | 龙口佳源颜料有限公司 | Preparation method of pigment orange 16 |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3124565A (en) * | 1964-03-10 | Water-insoluble benzimidazolone mono- | ||
| CH395388A (en) * | 1960-03-05 | 1965-12-31 | Hoechst Ag | Process for the production of water-insoluble azo dyes on cellulosic textile materials |
| DE1217008B (en) * | 1961-02-18 | 1966-05-18 | Hoechst Ag | Process for the preparation of water-insoluble monoazo dyes |
| DE1216460B (en) * | 1961-04-01 | 1966-05-12 | Hoechst Ag | Process for the preparation of water-insoluble monoazo dyes |
| CN1089100C (en) * | 2000-01-25 | 2002-08-14 | 华东理工大学 | Process for preparing organic yellow benzimidazoleone pigments |
-
2004
- 2004-04-16 CN CNB2004100177205A patent/CN100339442C/en not_active Expired - Fee Related
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102391663A (en) * | 2011-09-06 | 2012-03-28 | 鞍山七彩化学股份有限公司 | Preparation method of C.I. pigment yellow 151 |
| CN103923480A (en) * | 2014-04-21 | 2014-07-16 | 南通市争妍颜料化工有限公司 | Preparation method of orange benzimidazolone azo pigment |
| CN104592787A (en) * | 2014-12-25 | 2015-05-06 | 上虞舜联化工有限公司 | Preparation method of C.I. pigment yellow 181 |
| CN105524484A (en) * | 2016-01-14 | 2016-04-27 | 上虞市新利化工有限公司 | Preparation method for C.I. pigment red 176 |
| CN105524484B (en) * | 2016-01-14 | 2018-04-10 | 上虞市新利化工有限公司 | A kind of preparation method of C.I. paratoneres 176 |
| CN106833005A (en) * | 2017-01-23 | 2017-06-13 | 浙江浩川科技有限公司 | A kind of method for preparing permeability azo organic pigment high |
| CN110591409A (en) * | 2019-09-21 | 2019-12-20 | 龙口佳源颜料有限公司 | Preparation method of pigment orange 16 |
| CN110591409B (en) * | 2019-09-21 | 2021-05-28 | 龙口佳源颜料有限公司 | Preparation method of pigment orange 16 |
Also Published As
| Publication number | Publication date |
|---|---|
| CN100339442C (en) | 2007-09-26 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| TWI507486B (en) | Disperse azo dyes, disperse dye composition, dyed material and process for preparing disperse azo dyes | |
| CN1268689C (en) | Yellow, orange benzimidazolone like azo dye making method | |
| CN1886466A (en) | Disperse dyes | |
| CN1685023A (en) | Pigment compositions for oil-based lithographic printing inks | |
| CN1288212C (en) | Azodyes, preparing method thereof and use in dyeing or printing of hydrophobic fiber materials | |
| CN100339442C (en) | Method for preparing organic pigment of red benzimidazolones | |
| CN1111664A (en) | Phthalimidylazo dyes, process for their preparation and the use thereof | |
| CN1182120C (en) | Hydroxypyridone methide azo dyes | |
| CN1101840C (en) | Dye additive containing diazo compounds and dyeing compositions | |
| CN1183437A (en) | Polyazo dyes | |
| EP3063228B1 (en) | Disperse dyes, their preparation and their use | |
| CN1890329A (en) | Storagestable concentrated aqueous solutions of anionic dis- or tetrazo dyestuffs | |
| CN1289607C (en) | Phthalimidyl azo dyes, process for preparation thereof and the use thereof | |
| CN1125240A (en) | Monoazo type pyridone series compound dye | |
| CN1294212C (en) | Composition of high washing fastness reactive black compound dyestuff | |
| CN1197916C (en) | Olive green cationic dye and its preparing method | |
| CN1076706A (en) | Composition and compound | |
| CN1890331A (en) | Inkjet inks and methods of preparing the same | |
| CN1282717C (en) | Light-resistant clouring agent and composition containing same | |
| JPS60184569A (en) | Mixture comprising monoazo dye | |
| WO2020067063A1 (en) | Compound, colored composition, ink, toner, colored resin composition, and fiber-dyeing composition | |
| CN1729253A (en) | Phthalimidylazo dyes, processes for the preparation thereof and the use thereof | |
| CN101955682A (en) | Method for preparing high-performance organic pigment PR176 | |
| CN1230469C (en) | Process for preparing red benzimidazoleone pigments | |
| CN1102654A (en) | Cationic diazacyanine dye stuffs |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| C17 | Cessation of patent right | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20070926 Termination date: 20110416 |