CN104497619A - Preparation method of C.I. pigment brown 25 - Google Patents
Preparation method of C.I. pigment brown 25 Download PDFInfo
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Abstract
The invention discloses a preparation method of C.I. pigment brown 25. The preparation method comprises the following steps: (1) preparing a diazo salt liquid of 2,5-dichloroaniline; (2) dissolving 5-(2'-hydroxy-3'-naphthalene-carbamoyl)-2-benzimidazolone in an alkaline water liquid, and adding an acid water liquid to acidify, so as to prepare a suspended coupling liquid; (3) adding the diazo salt liquid into the coupling liquid to carry out a coupling reaction, controlling the pH value of the reacted mixed liquid at 5.5-6.5 by virtue of an alkaline additive in a coupling process, and processing after the coupling so as to obtain a rough pigment; and (4) carrying out pigmentation on the rough pigment to obtain the finished C.I. pigment brown 25. According to the preparation method, coupled components are separated out in a particle manner in an acidification process and are coupled with added diazo components, so that the uniformity of the coupling reaction is guaranteed, and the obtained C.I. pigment brown 25 has the beneficial effects that the particle sizes are uniform, particles are floppy, the dispersibility is excellent, the color is bright, and the coloring strength is high.
Description
Technical field
The present invention relates to pigment preparing technical field, specifically relate to a kind of preparation method of C.I. pigment brown 25.
Background technology
C.I. (Chinese is by name: 4-[2-(2 for pigment brown 25,5-dichlorophenyl) azo]-N-(2,3-dihydro-2-oxo--1H-benzoglyoxaline-5-base)-3-hydroxyl-2-naphthoamide) belong to benzoglyoxaline ketone, be the brown high-grade pigment dyestuff of a kind of pure ruddiness, there is following molecular structure:
This pigment variety rarely provides by single molecular structure the pigment that pure, fancy brown adjusts, identical with yellow, orange, red benzoglyoxaline ketone pigment, due to containing cyclic amide substituted radical (-NHCONH-) in molecular structure, make the imido grpup (-NH-) in its molecule and form hydrogen bond between pigment molecule between carbonyl (=O):
What the formation of intermolecular hydrogen bonding obviously affected its pigment molecule crystal piles up mode, and the introducing of four chlorine atoms, changes the polarity of its pigment molecule, tone, makes pigment have higher fusing point.Compared with non-benzoglyoxaline ketone azoic coupling component pigment (as: C.I. Pigment red 2, Pigment Red 112, pigment red 146, the Pigment red 170 etc.) performance that molecular structure is approximate, there is more excellent multiple application performance; As light fastness, fastness to weathering, solvent resistance, resistance to migration and heat-resistant stability, be widely used in printing-ink (polyurethane ink) painted; Pigment coloration, pigment light fastness in the alkyd Melamine of reduced tint (1:300 TiO2) reaches 7-8 level; Be particularly useful for coloring plastic, in polyvinyl chloride (PVC) heat-resisting 200 DEG C, light fastness is 8 grades, heat-resisting 290 DEG C of high density polyethylene(HDPE) (HDPE), not obvious lower than 220 DEG C of size distortions.Some application performances of commercial pigments C.I. pigment brown 25 (Hostaperm Brown HFR) are as row in table-1:
The some application performances of table-1 commercial pigments Hostaperm Brown HFR
| Hue angle, degree (1/3 standard depth) | 43.5 |
| Light fastness, level | 8 |
| Fastness to weathering, level | 4-5 |
| Resistance toheat, DEG C | 200 |
| Resistance to cover paint performance, level | 5 |
| Solvent resistance: BuOH/ Cellosolve, level | 4-5/2 |
| N-BUTYL ACETATE/methylethylketone, level | 4/3-4 |
| Dimethylbenzene/petroleum solvent, level | 4-5/4-5 |
C.I. pigment brown 25 is by 2,5-dichlorphenamide bulk powder diazotization reaction, the diazonium salt generated and coupling component 5-(2 '-hydroxyl-3 '-naphthoyl amido)-2-benzimidazolone (hereinafter referred to as azoic coupling component AS-BI) carry out coupled reaction, then prepare commercial pigments C.I. pigment brown 25 by specific pigmenting process.
Existing document has been reported for work the method for synthesis C.I. pigment brown 25:
Earlier German Hirst (Hoechst) house journal (US 3,124,565,1964) in, what describe multiple benzoglyoxaline ketone pigment contains into method, by Ou He Productivity thing in aqueous medium and the common heat treated of oil emulsifier, or with pyridine solvent process crude product pigmenting techniques; Wherein adopt and add oil base amine acetate as auxiliary agent (Oleylamino acetate) in coupling component. synthesis C.I. pigment brown 25.
Report is separately had to adopt water medium to carry out diazotization reaction, coupled reaction, product carries out the process of pigmenting process pigmenting by organic solvent (DMF): by 24g crude product pigment and 240ml dimethyl formamide (DMF), 140 DEG C are heated under fully stirring, keep 2h, be cooled to 100 DEG C, filter, washing, obtains the C.I. pigment brown 25 product of 22g.(University Of Tianjin, Tianjin Ran Hualiu factory, dyestuffs industries (1979), No.6:30).
Simultaneously synthesis in water another kind method is joined in damping fluid by the azoic coupling component AS-BI of diazonium salt solution and dissolving, controls the pH value of reacted mixed solution with sodium carbonate; Coupling terminates to carry out pigmenting process can obtain pigment brown 25 finished product (synthetic dyestuff palm fibre 25 research in aqueous media, Lv Feng, Pei Wen, research and development, the 15th volume the 2nd phase in 2008,10-12 page).
Hirst (Hoechst) company other two sections of patents (US 5,243,032,1993; US 5,086,168,1992) report the C.I. pigment brown 25 technique preparing low levels polychlorobiphenyl (PCBs).Example 10:16.3 part 2,5-dichlorphenamide bulk powder is according to US in patent 5,086, and 168 (1992) example 1 methods carry out diazotization reaction: 33 parts of 5-(2 '-hydroxyl-3 '-naphthoyl amino)-benzimidazolone-2, azoic coupling component AS-BI, be scattered in 300 parts of water, 70 DEG C, add 23 parts of (33%) sodium hydroxide solutions, be diluted with water to 400 parts of volumes, two kinds of solution prepared are in 1 hour, and by pump recycle stock, coupling pH value is 5.1-5.8; Reacting by heating thing to 95 DEG C, 1 hour, filters, washing except desalting, obtaining the content 20 μ g/g of polychlorobiphenyl (PCBs) in C.I. pigment brown 25.But and the concrete grammar of undeclared pigmenting process.
Aforesaid method is when coupled reaction, that the solution of diazonium salt solution and coupling component acutely mixes post-reacted, along with the generation of precipitation in building-up process, the solid particulate formed is harder, such crude pigment product only in the strong solvent that toxicity is large pigmenting just can obtain bright-colored, that good dispersity, tinting strength are high product, the product obtained at Weak solvent or Pigment in Water Medium is lackluster, bad dispersibility, tinting strength are low.And crude pigment product just can carry out pigmenting process after wanting drying in literature procedures, activity time is long, and energy consumption is high, not energy-conserving and environment-protective.
Summary of the invention
The invention provides a kind of preparation method of C.I. pigment brown 25, the method adopts and is separated out in granular form by 5-(2'-hydroxyl-3'-naphthoyl amido)-benzimidazolone-2, and then react with the diazonium salt added, prepare crude product filter cake and require no drying and processing, directly add Weak solvent pigment process, the C.I. pigment brown 25 uniform particle sizes finally prepared, particle are soft, and dispersiveness is excellent, bright-colored, tinctorial strength is high.
A preparation method for C.I. pigment brown 25, comprises the steps:
(1) by the dissolving with hydrochloric acid of 2,5-dichlorphenamide bulk powder by mass concentration 30%, cooling to-2-5 DEG C, is the quick diazotization of sodium nitrite solution of 40% by mass concentration, obtained diazonium salt solution; 2,5-dichlorphenamide bulk powder: hydrochloric acid (hydrogenchloride): Sodium Nitrite mol ratio is 1:2.1-3.0:0.99-1.05;
(2) 5-(2'-hydroxyl-3'-naphthoyl amido)-2-benzimidazolone is called for short azoic coupling component AS-BI, dissolve with alkali aqueous solution, the acid solution adding mass concentration 10% carries out acid out, azoic coupling component AS-BI separates out, until acid out terminates, pH value is 7, the obtained coupling solution suspended; Adjustment temperature is 0-10 DEG C; 2,5-dichlorphenamide bulk powder: azoic coupling component AS-BI mol ratio is 1:0.98-1.05.Azoic coupling component AS-BI: sodium hydroxide: acetic acid quality is than being 1:0.17:0.26;
(3) joined in coupling solution by diazonium salt solution and carry out coupled reaction, the pH value controlling the mixed solution of reaction in coupled processes with the alkaline additive of mass concentration 30% is 5.5-7.5, and coupling terminates, and aftertreatment obtains C.I. pigment brown 25 crude pigment product;
(4) join in organic solvent by C.I. pigment brown 25 crude pigment product, making beating, is warmed up to 70-120 DEG C, and insulation 1-5 hour, namely suction filtration, washing, oven dry obtain C.I. pigment brown 25 finished product.
In described step (1), 2,5-dichlorphenamide bulk powder: hydrochloric acid (hydrogenchloride): Sodium Nitrite mol ratio is preferably 1:2.45:0.99; Diazotization temperature is 5-10 DEG C, and the sodium nitrite solution joining day is no more than 5 minutes.
In described step (2), 2,5-dichlorphenamide bulk powder: azoic coupling component AS-BI mol ratio is preferably 1:0.98.
Being core procedure of the present invention in step (2), is emphasis improvements of the present invention.Adopt acid out process, follow-up coupled reaction is reacted at solid-liquid two-phase interface, and speed of response is applicable to, and ensures that the crude product filter cake for preparing also can pigmenting process without strong solvent, obtains uniform particle sizes, the soft pigment brown 25 of particle.
In step (2), described alkali aqueous solution is generally the aqueous solution of highly basic, such as, can select the aqueous solution of sodium hydroxide, potassium hydroxide, as preferably, can select the aqueous solution of sodium hydroxide.The mass percent concentration of alkali aqueous solution is preferably 1-5%, solid alkali and water can be selected to configure and form, and concentrated alkali solution and water also can be selected to dilute and form.Described aqueous acid is generally one or more in formic acid, acetic acid, hydrochloric acid, is preferably acetic acid.The mass percent concentration of aqueous acid is generally 5-25%.The speed adding aqueous acid should not be too fast, and avoid local reaction too fast, the solid particulate granularity of precipitation is uneven, and hardness is comparatively large, as preferably, generally in 30-180 minute, adds aqueous acid.
In the acid out process of step (2), the too high excessive velocities easily causing separating out of the mass percentage content of 5-(2'-hydroxyl-3'-naphthoyl amido)-2-benzimidazolone in reacted mixed solution, the grain graininess of separating out is comparatively large, is unfavorable for follow-up reaction once in a while; Concentration is too low, then be unfavorable for the precipitation of solid particulate, cannot ensure that follow-up coupling component all participates in reaction in solid-liquid two-phase, as preferred scheme, in acid out process, the mass percentage content of 5-(2'-hydroxyl-3'-naphthoyl the amido)-benzimidazolone-2 described in reacted mixed solution is 5-10%.
After the acid out end of processing of step (2), the control of pH value is also a crucial factor, because coupling medium pH value not only affects coupling position, also affects speed of response significantly simultaneously.As preferably, after described acid out terminates, the pH value of reacted mixed solution is 5.5-7.0, is preferably 6.5-7.0.
In the acid out process of step (2), stirring velocity also can affect the grain graininess of acid out, and stirring velocity is too fast, and the particle of the coupling component of precipitation is too small, and the particle that coupling generates is also very little, and in last handling process, difficulty in filtration is larger; Stirring velocity is too slow, and the particle of the coupling component of precipitation is comparatively large, and the granules of pigments that last coupling generates can be comparatively hard, and coloring effect is bad.As preferably, in described acid out process, stirring velocity is 40-90 rev/min.
In the acid out process of step (2), described acid out temperature can be carried out at normal temperatures, even for ensureing the grain graininess of separating out, and as preferably, described acid out temperature is 5-20 DEG C.
In step (3), described alkaline additive is general mineral alkali, for ease of regulating, generally selects weak base.Described alkaline additive is one or more in sodium-acetate, SODIUM PHOSPHATE, MONOBASIC, sodium carbonate, sodium bicarbonate, salt of wormwood, sodium hydroxide, is preferably sodium bicarbonate.In this step, after coupling terminates, the treating processes of the available routine of described last handling process, for improving the granular mass of crude pigment product.Described last handling process is: coupling terminates to be warming up to 80-120 DEG C, is preferably 90 DEG C, and is incubated 2-3 hour, cools to 60-70 DEG C of filtration, washing, obtains crude product pigment filter cake.
In step (3), described coupled reaction can be carried out at normal temperatures, and the time of described coupled reaction is generally 1-3 hour.
Step (4) is pigmenting process, component too small for particle is removed, by component excessive for particle under the effect of organic solvent, changes to applicable particle, is conducive to improving the color of pigment finished product and tinctorial strength etc.Organic solvent treating processes utilizes pigment in specific solvent, have oligodynamical degree, occur to dissolve and recrystallization in treating processes, the wider grain diameter of original size distribution is narrowed, rely on the solvability remove portion soluble impurity of solvent simultaneously, by the perviousness of solvent, make particle soft.Described organic solvent is one or more in ethanol, Virahol, isopropylcarbinol, propyl carbinol, is preferably Virahol.During pigmenting, the mass percent concentration of described pigment brown 25 crude product pigment is 3-10%.The mass ratio of described crude product pigment and organic solvent can affect quality product and product yield, and when the amount of organic solvent is too much, the pigment brown 25 that particle is applicable to also can be partly dissolved loss; When the amount of organic solvent is very few, the granules of pigments that particle is less on the one hand can not fully be removed; On the other hand, the particle that particle is larger is difficult to be converted into the applicable pigment product of particle, affects the quality of pigment product.In step (4), described pigment brown 25 and the mass percent of organic solvent are 3-10%.The pigmenting time is generally 5-10 hour.Pigmenting temperature is general relevant with the kind of organic solvent, can determine according to actual needs.
Wherein diazo component is 2,5-dichlorphenamide bulk powder, its structural formula:
Wherein coupling component is 5-(2'-hydroxyl-3'-naphthoyl amido)-2-benzimidazolone (being called for short azoic coupling component AS-BI), its structural formula:
Its reaction equation is:
(1) diazotization reaction
(2) coupled reaction
Compared with prior art, beneficial effect of the present invention is embodied in:
(1), in diazo process of the present invention, adopt quick heavy nitrogen, control Sodium Nitrite feed rate, to prevent in diazo process diazo component from even, improve diazotization yield and reduce the generation of by product.
(2), coupling component of the present invention first dissolves with buck, acid out is carried out again with acid, controlled by Optimization Technology, coupling component is separated out with small soft particle form, granular size is suitable, then carry out coupled reaction with the diazo component added, speed of response is applicable to, and ensure that the homogeneity of coupled reaction.
(3) crude pigment product, obtained through coupling of the present invention can in Weak solvent pigment process, avoid the strong solvent that toxicity is large, be conducive to improving the color of pigment finished product and tinctorial strength etc., the C.I. pigment brown 25 uniform particle sizes prepared, particle are soft, and dispersiveness is excellent, bright-colored, tinctorial strength is high.
(4), the C.I. pigment brown 25 yield for preparing of the present invention is higher, and production cost is low.
Embodiment
Most preferred embodiment 1
By 32.6g 2,5-dichlorphenamide bulk powder, 54ml mass percent concentration are that the hydrochloric acid of 30% and the water stirring of 250ml are cooled to 5 DEG C, add the quick diazotization of sodium nitrite solution of 35g mass percent concentration 40% in 2 minutes, diazonium terminates to eliminate unnecessary Sodium Nitrite, obtains diazonium salt solution.
65g azoic coupling component AS-BI (5-(2'-hydroxyl-3'-naphthoyl amido)-2-benzimidazolone), be dissolved in 40ml mass percent concentration be 30% aqueous sodium hydroxide solution and 600ml water in, adjustment temperature is 5 DEG C, thread adds the dilute hydrochloric acid of 72ml mass concentration 10%, adding stirring velocity in dilute hydrochloric acid process is 50 revs/min, until acid out terminates, pH value is 6, obtains Coupling Solution.Aqueous sodium hydroxide solution also can select potassium hydroxide solution to replace.
Slowly joined in Coupling Solution in 3 hours by diazonium salt solution and react, be 5.5 by the pH value that the sodium hydroxide of 31ml mass concentration 30% controls reacted mixed solution in coupled processes, coupling terminates, be warming up to 90 DEG C, be incubated 2 hours, filter, obtain crude pigment product filter cake.
Get the crude pigment product filter cake that 262g synthesizes, add in 2800g ethanol and pull an oar, be heated to backflow under good agitation, be incubated 10 hours, filter, washing, oven dry at 85-90 DEG C, pulverizing obtain about 96g pigment brown 25.
Embodiment 2
By 32.6g 2,5-dichlorphenamide bulk powder, 54ml mass percent concentration are that the hydrochloric acid of 30% and the water stirring of 250ml are cooled to 5 DEG C, add the Sodium Nitrite diazotization of 35g mass percent concentration 40% in 3 minutes fast, diazonium terminates to eliminate unnecessary Sodium Nitrite, obtains diazonium salt solution.
65g azoic coupling component AS-BI, be dissolved in 40ml mass percent concentration be 30% aqueous sodium hydroxide solution and 600ml water in, adjustment temperature is 15 DEG C, thread adds the dilute formic acid of 92ml mass concentration 10%, adding stirring velocity in dilute hydrochloric acid process is 70 revs/min, until acid out terminates, pH value is 6.5, obtains Coupling Solution.
Joined in Coupling Solution in 2.5 hours by diazonium salt solution and react, be 6.0 by the pH value that the sodium hydroxide of 31ml mass concentration 30% controls reacted mixed solution in coupled processes, coupling terminates, be warming up to 90 DEG C, be incubated 2 hours, filter, obtain crude pigment product filter cake.
Get 260g synthesis crude product pigment filter cake, add in 2800g Virahol and pull an oar, be heated under good agitation backflow, be incubated 8 hours, washing, at 85-90 DEG C dry, pulverizing obtain 95g product.
Embodiment 3
By 32.6g 2,5-dichlorphenamide bulk powder, 54ml mass percent concentration are that the hydrochloric acid of 30% and the water stirring of 250ml are cooled to 5 DEG C, add the Sodium Nitrite diazotization of 35g mass percent concentration 40% in 1 minute fast, diazonium terminates to eliminate unnecessary Sodium Nitrite, obtains diazonium salt solution.
65g azoic coupling component AS-BI, be dissolved in 40ml mass percent concentration be 40% aqueous sodium hydroxide solution and 600ml water in, adjustment temperature is 10 DEG C, thread adds the dilute acetic acid of 120ml mass concentration 10%, adding stirring velocity in dilute acetic acid process is 90 revs/min, until acid out terminates, pH value is 6, obtains Coupling Solution.
Joined in Coupling Solution in 3 hours by diazonium salt solution and react, be 6.5 by the pH value that 26.5g sodium bicarbonate controls reacted mixed solution in coupled processes, coupling terminates, and is warming up to 90 DEG C, is incubated 2 hours, filters, obtains crude pigment product filter cake.
Get 270g synthesis crude product pigment filter cake, add in 2600g Virahol and pull an oar, be heated under good agitation backflow, be incubated 8 hours, washing, at 85-90 DEG C dry, pulverizing obtain 98g product.
Embodiment 4
By 32.6g 2,5-dichlorphenamide bulk powder, 54ml mass percent concentration are that the hydrochloric acid of 30% and the water stirring of 250ml are cooled to 5 DEG C, add the Sodium Nitrite diazotization of 35g mass percent concentration 40% in 3 minutes fast, diazonium terminates to eliminate unnecessary Sodium Nitrite, obtains diazonium salt solution.
65g azoic coupling component AS-BI, be dissolved in 40ml mass percent concentration be 30% aqueous sodium hydroxide solution and 600ml water in, adjustment temperature is 15 DEG C, thread adds the dilute hydrochloric acid of 72ml mass concentration 10%, adding stirring velocity in dilute hydrochloric acid process is 60 revs/min, until acid out terminates, pH value is 6, obtains Coupling Solution.
Joined in Coupling Solution in 1.5 hours by diazonium salt solution and react, be 6.0 by the pH value that the salt of wormwood of 30.7g controls reacted mixed solution in coupled processes, coupling terminates, and is warming up to 90 DEG C, is incubated 2 hours, filters, obtains crude pigment product filter cake.
Get 262g synthesis crude pigment product filter cake, add in 2080g propyl carbinol and pull an oar, be heated under good agitation backflow, be incubated 5 hours, washing, at 85-90 DEG C dry, pulverizing obtain 96g product.
Embodiment 5
By 32.6g 2,5-dichlorphenamide bulk powder, 54ml mass percent concentration are that the hydrochloric acid of 30% and the water stirring of 250ml are cooled to 5 DEG C, add the Sodium Nitrite diazotization of 35g mass percent concentration 40% in 2 minutes fast, diazonium terminates to eliminate unnecessary Sodium Nitrite, obtains diazonium salt solution.
65g azoic coupling component AS-BI, be dissolved in 40ml mass percent concentration be 30% aqueous sodium hydroxide solution and 600ml water in, adjustment temperature is 10 DEG C, thread adds the dilute acetic acid of 120ml mass concentration 15%, adding stirring velocity in dilute acetic acid process is 75 revs/min, until acid out terminates, pH value is 6.5, obtains Coupling Solution.
Joined in Coupling Solution in 2 hours by diazonium salt solution and react, be 6.5 by the pH value that the sodium hydroxide of 31ml mass concentration 30% controls reacted mixed solution in coupled processes, coupling terminates, be warming up to 90 DEG C, be incubated 2 hours, filter, obtain crude pigment product filter cake.
Get 258g synthesis crude pigment product filter cake, add in 2080g isopropylcarbinol and pull an oar, be heated under good agitation backflow, be incubated 8 hours, washing, at 85-90 DEG C dry, pulverizing obtain 94g product.
Comparative example 1
By 32.6g 2,5-dichlorphenamide bulk powder, 54ml mass percent concentration are that the hydrochloric acid of 30% and the water stirring of 250ml are cooled to 5 DEG C, add the Sodium Nitrite diazotization of 35g mass percent concentration 40%, diazonium terminates to eliminate unnecessary Sodium Nitrite, obtains diazonium salt solution.
65g azoic coupling component AS-BI (5-(2'-hydroxyl-3'-naphthoyl amido)-2-benzimidazolone), be dissolved in 40ml mass percent concentration be 30% aqueous sodium hydroxide solution and 600ml water in, obtain Coupling Solution.
40g sodium-acetate is joined in the water of 400ml, adds 2.4g allylamine, configuration buffered soln; Diazonium salt solution and Coupling Solution are joined in buffered soln, controlling reacted pH of mixed with sodium carbonate is 5.5, and coupling terminates, and is warming up to 90 DEG C simultaneously, is incubated 2 hours, filters, dries to obtain crude pigment product.
Get the crude pigment product that 260g synthesizes, add in 2800g ethanol and pull an oar, be heated to backflow under good agitation, be incubated 3 hours, filter, washing, oven dry at 85-90 DEG C, pulverizing obtain about 92g C.I. pigment brown 25.
Comparative example 2
By 32.6g 2,5-dichlorphenamide bulk powder, 54ml mass percent concentration are that the hydrochloric acid of 30% and the water stirring of 250ml are cooled to 5 DEG C, add the Sodium Nitrite diazotization of 35g mass percent concentration 40%, diazonium terminates to eliminate unnecessary Sodium Nitrite, obtains diazonium salt solution.
65g azoic coupling component AS-BI (5-(2'-hydroxyl-3'-naphthoyl amido)-2-benzimidazolone), be dissolved in 40ml mass percent concentration be 30% aqueous sodium hydroxide solution and 600ml water in, obtain Coupling Solution.
Slowly joined in coupling solution by diazo liquid, controlling reacted pH of mixed with sodium carbonate is 5.5, and coupling terminates, and is warming up to 90 DEG C, is incubated 2 hours, filters, dries to obtain crude pigment product.
By 250g crude product pigment and 2400ml dimethyl formamide (DMF), be heated to 140 DEG C, keep 2h, be cooled to 100 DEG C, filter, washing under abundant stirring, oven dry at 85-90 DEG C, pulverizing obtain about 85g C.I. pigment brown 25.
The performance comparison of embodiment 1-5 and comparative example 1-2 is as shown in table 1:
Table 1
| Numbering | Outward appearance | Coloured light | Tinting strength % | Must (g) be measured |
| Embodiment 1 | Uniform particles, soft | Bright-coloured | 105 | 96 |
| Embodiment 2 | Uniform particles, soft | Bright-coloured | 106 | 95 |
| Embodiment 3 | Uniform particles, soft | Bright-coloured | 108 | 98 |
| Embodiment 4 | Uniform particles, soft | Bright-coloured | 105 | 96 |
| Embodiment 5 | Uniform particles, soft | Bright-coloured | 104 | 94 |
| Comparative example 1 | Uniform particles, soft | Bright-coloured | 100 | 92 |
| Comparative example 2 | Particle is soft | Darker | 95 | 85 |
As can be seen from upper contrast, the C.I. pigment brown 25 uniform particle sizes that the present invention obtains, particle are soft, and dispersiveness is excellent, bright-colored, tinctorial strength is high.Yield also obviously increases.
Claims (10)
1. a preparation method for C.I. pigment brown 25, comprises the steps: it is characterized in that,
(1) by the dissolving with hydrochloric acid of 2,5-dichlorphenamide bulk powder by mass concentration 30%, cooling to-2-5 DEG C, is the quick diazotization of sodium nitrite solution of 40% by mass concentration, obtained diazonium salt solution; 2,5-dichlorphenamide bulk powder: hydrochloric acid (hydrogenchloride): Sodium Nitrite mol ratio is 1:2.1-3.0:0.99-1.05;
(2) 5-(2'-hydroxyl-3'-naphthoyl amido)-2-benzimidazolone is called for short azoic coupling component AS-BI, dissolve with alkali aqueous solution, the acid solution adding mass concentration 10% carries out acid out, azoic coupling component AS-BI separates out, until acid out terminates, pH value is 7, the obtained coupling solution suspended; Adjustment temperature is 0-10 DEG C; 2,5-dichlorphenamide bulk powder: azoic coupling component AS-BI mol ratio is 1:0.98-1.05.Azoic coupling component AS-BI: sodium hydroxide: acetic acid quality is than being 1:0.17:0.26;
(3) joined in coupling solution by diazonium salt solution and carry out coupled reaction, the pH value controlling the mixed solution of reaction in coupled processes with the alkaline additive of mass concentration 30% is 5.5-7.5, and coupling terminates, and aftertreatment obtains C.I. pigment brown 25 crude pigment product;
(4) join in organic solvent by C.I. pigment brown 25 crude pigment product, making beating, is warmed up to 70-120 DEG C, and insulation 1-5 hour, namely suction filtration, washing, oven dry obtain C.I. pigment brown 25 finished product.
2. the preparation method of a kind of C.I. pigment brown 25 according to claim 1, is characterized in that, in described step (1), and 2,5-dichlorphenamide bulk powder: hydrochloric acid (hydrogenchloride): Sodium Nitrite mol ratio is preferably 1:2.45:0.99; Diazotization temperature is 5-10 DEG C, and the sodium nitrite solution joining day is no more than 5 minutes.
3. the preparation method of a kind of C.I. pigment brown 25 according to claim 1, is characterized in that, in described step (2), and 2,5-dichlorphenamide bulk powder: azoic coupling component AS-BI mol ratio is preferably 1:0.98; Sodium hydroxide or the potassium hydroxide aqueous solution of described alkali aqueous solution to be mass percent concentration be 1-5%; Described acid is one or more in formic acid, acetic acid, hydrochloric acid, and the mass percent concentration of described aqueous acid is 5-25%.
4. the preparation method of a kind of C.I. pigment brown 25 according to claim 1, is characterized in that, in described step (2), in described acid out process, in the mixed solution of reaction, the mass percentage content of azoic coupling component AS-BI is 5-10%.
5. the preparation method of a kind of C.I. pigment brown 25 according to claim 1, is characterized in that, in described step (2), after described acid out terminates, the mixed solution of reaction pH value control as 6.5-7.0.
6. the preparation method of a kind of C.I. pigment brown 25 according to claim 1, is characterized in that, in the acid out process of described step (2), stirring velocity is 40-90 rev/min.
7. the preparation method of a kind of C.I. pigment brown 25 according to claim 1, is characterized in that, in described step (2), described acid out temperature is 5-20 DEG C.
8. the preparation method of a kind of C.I. pigment brown 25 according to claim 1, it is characterized in that, in described step (3), described alkaline additive is one or more in sodium-acetate, SODIUM PHOSPHATE, MONOBASIC, sodium carbonate, sodium bicarbonate, salt of wormwood, sodium hydroxide; Described last handling process is: coupling terminates to be warming up to 80-120 DEG C, and is incubated 2-3 hour, cools to 60-70 DEG C of filtration, washing, obtains crude product pigment filter cake; Described coupled reaction is carried out at normal temperatures, and the time of described coupled reaction is generally 1-3 hour.
9. the preparation method of a kind of C.I. pigment brown 25 according to claim 1, is characterized in that, in described step (4), described organic solvent is one or more in ethanol, Virahol, isopropylcarbinol, propyl carbinol.
10. the preparation method of a kind of C.I. pigment brown 25 according to claim 1, it is characterized in that, in described step (4), described C.I. pigment brown 25 crude pigment product and the mass percent of organic solvent are 3-10%, and the pigmenting time is 5-10 hour; Intensification and holding temperature are 90 DEG C.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107383991A (en) * | 2017-07-17 | 2017-11-24 | 安徽省宏宝莱机车科技有限公司 | A kind of compound electric automobile electrophoresis finish paint and its preparation technology |
| CN110041725A (en) * | 2019-04-30 | 2019-07-23 | 江苏彩瑞实业有限公司 | A kind of technical process producing high light-fast fastness, high durable fastness pigment red 146 |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107383991A (en) * | 2017-07-17 | 2017-11-24 | 安徽省宏宝莱机车科技有限公司 | A kind of compound electric automobile electrophoresis finish paint and its preparation technology |
| CN110041725A (en) * | 2019-04-30 | 2019-07-23 | 江苏彩瑞实业有限公司 | A kind of technical process producing high light-fast fastness, high durable fastness pigment red 146 |
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