CN102532035B - Method for synthesizing azoic coupling component AS-BI - Google Patents
Method for synthesizing azoic coupling component AS-BI Download PDFInfo
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Abstract
The invention discloses a method for synthesizing an azoic coupling component AS-BI. The method comprises the following steps of: adding N-methyl pyrrolidone serving a solvent into a reaction kettle; adding pretreated and purified 5-amino benzimidazolone and 2,3-acid at the vacuum degree of 0.06-0.098 MPa under the condition of stirring; heating to 60-90 DEG C within 50-70 minutes; slowly sucking phosphorus trichloride from the bottom of the reaction kettle; after sucking, continually reacting at the temperature of 40-65 DEG C for 10-30 minutes; sucking ethylene diamine from the bottom of the reaction kettle at one time; slowly sucking purified triphenyl phosphite from the bottom; after sucking, continually reacting at the temperature of 40-60 DEG C for 100-150 minutes; undergoing a condensation reaction, performing filter pressing and separating the solvent out to obtain a crude azoic coupling component AS-BI; washing the crude azoic coupling component AS-BI with alkali and water; and drying to obtain an azoic coupling component AS-BI product of which the content is over 99.5 percent by weight.
Description
Technical field
The present invention relates to technical field of organic synthesis, relate in particular to the synthetic method of a kind of azoic coupling component AS-BI.
Background technology
Azoic coupling component AS-BI, chemical name is 5-(2 '-hydroxyl-3 '-naphthoyl amido)-2-benzimidazolone, to produce to contain benzoglyoxaline ketone group azo pigment, as organic Pigment red P.R.171, P.R.175, P.R.176, P.R.183, P.R.185, P.R.208, the important intermediate of pigment violet P.V.32 and pigment brown P.Br.25 etc., take that it contains benzimidazolyl ketone groups in the pigment dyestuff molecular structure that starting raw material is produced, make pigment there is excellent fast light, fastness to weathering, good resistance to solvent, resistance to migration and heat-resistant stability energy; And the decomposition temperature of most kinds is more than 330 ℃, can bear the treatment temp of plastic hot machine-shaping, harmless to the physical property of coloured plastics; There is the performances such as acid and alkali-resistance, resistance to soap and washing composition.In above-mentioned kind, especially even more important with Pigment red P.R.176 and Pigment red P.R.185, on its diazo component, there are benzamido and sulphonyl methylamino-that polarity is strong, make pigment applications performance more excellent, can be applicable to pigment, pigment coloration, also can be used for high-grade printing in China ink.Because benzimidazolone pigment is introduced imide group, existence-NHCONH-cyclic substituents in dye molecule, can cause the formation of intermolecular hydrogen bond, the pigment aggregate banded with formation has direct relation, therefore be different from general azo pigment, its every fastness is very excellent, has high chemical resistant properties, good acid resistance, alkali resistance, for polyolefine, have quite high thermotolerance, wherein some kind is current the most heat-resisting known pigment dyestuff kind.Because such pigment dyestuff class is high, quality good, integrated application excellent property, in a plurality of industries such as ink, plastics, coating, be widely used.If pigment brown P.Br.25 is PV fast brown HFR, fastness to weathering is excellent, is the brown kind of excellent property.Brown and purple spectrum pigment dyestuff is three important colors outside basic colors spectrum, although can make material painted by the rational colorant match mode of basic chromatogram in actual applications, the needs that meet application, Dan specific occasion, as high-grade coating and coloring plastic, still needs to select weather resistance and application fastness brown, violet pigment kind good, single structure.Brown, violet pigment kind is applied in a plurality of fields, and that in same chromatogram pigment, can contend with it only has pigment brown P.Br.23, in the original liquid coloring of PVC, polyolefine, acrylic fiber, paint industry, senior ink goods, is widely used.
Nearest for some time, it is also everybody interested scientific research project that application pigment dyestuff carries out ink-jet printed.In numerous kinds, Pigment red P.R.185 and Pigment red P.R.208 firmly get user's favorable comment and have the trend being widely used with its good light fastness, by dyeing, are approved.Pigment dyestuff is with its irreplaceable high tinctorial strength, bright colors, and the feature such as chromatogram is complete, and toxicity is low and being applied even more extensively in coatings industry, the most representative with the building coating of the highest car paint of state of the art and consumption maximum.Abroad, Pigment red P.R.171 etc. are used for many years at coating industry, and the coating of external many good weatherability includes the compositions such as the red P.R.171 of pigment dyestuff mostly.The type pigment, is particularly useful for the painted of plastics, resin, and not only light fastness is excellent, and resistance to solvent, resistance to migration, resistance toheat are also very outstanding.
The existing production technique of azoic coupling component AS-BI mainly contains following several:
(1) one step condensation method
By 2-hydroxyl-3-naphthoic acid and 5-Amino-2-benzimidazolinone direct reaction, made.According to the difference of solvent, reaction conditions is each has something to recommend him.But because the essence of this condensation reaction is-NH
2group is sloughed a part water with-COOH group and is formed amide group, thus the selection of dewatering agent, reaction conditions determine, how to remove to greatest extent the focus that moisture has just become research.
The advantage of this technique is: (1) production operation is easy, and process is easy to control, and process parameters range is wide, dangerous little; (2) use raw material variety few; (3) with short production cycle; (4) condensation reaction is complete, and material aftertreatment is simple; (5) solvent can recycle, apply mechanically repeatedly.But this technique has the following disadvantages again simultaneously: (1) solvent consumption that once feeds intake is large; (2) solvent needs to add in recycling process, although the amount of adding is each time different, but generally all need to append 20% left and right of a front quantity of solvent, otherwise follow-up condensation reaction reaction system viscosity is large especially, even there will be the consequence that reaction can not be carried out or product yield is very low; (3) solvent aftertreatment problem.After solvent Reusability, in solvent, can be dissolved with a large amount of impurity, the one, the carrying out of impact reaction, the 2nd, soluble a certain amount of finished product AS-BI in solvent, more has the impurity such as phenol of a great deal of, at solvent, can not continue to apply mechanically while needing distilation, the impurity phenol approaching with solvent boiling point can together with steam, even in negative pressure, use under efficient wire packing condition and to be also difficult to solvent separated with phenol completely, recovered solvent purity is low, affects next batch condensation reaction effect; (4) product purity is lower than 95wt%, and the comprehensive yield of finished product is no more than 90%, is generally 85～88%, has affected the economic benefit of product.
(2) 2-hydroxyl-3-naphthoyl chloride method
First prepare 2-hydroxyl-3-naphthoyl chloride, then under the existence of catalyzer, solvent etc., react with 5-Amino-2-benzimidazolinone and prepare azoic coupling component AS-BI.In theory, acyl chlorides structure and-NH
2radical reaction is easier, but due to 2-hydroxyl-3-naphthoyl chloride and 5-Amino-2-benzimidazolinone molecule space steric hindrance larger, reaction have certain difficulty, must just can complete by the effect of the auxiliary agents such as catalyzer.
The advantage of this technique is: (1) product yield is higher than a step condensation method of 2-hydroxyl 3-naphthoic acid and 5-Amino-2-benzimidazolinone, and yield surpasses 90%; (2) temperature of reaction is low, and operational condition is gentle; (3) solvent for use price is relatively low; (4) solvent recovering rate is high.But this technique still has the following disadvantages: (1) is used SOCl
2with become-COCl of make-COOH of 2,3-acid-respons group, increased operation sequence, the production cycle extends; (2) prepare 2-hydroxyl-3-naphthoyl chloride, prepare two kinds of different solvents of azoic coupling component AS-BI use, using various ingredients is catalyzer and acid binding agent, and operation easier is large, and synergy is poor; (3) product purity is low, and melting range is wide, appearance poor, storage of finished products poor stability; (4) although product yield is high, comprehensive benefit is poor, and quantity of three wastes is larger, and processing costs is high, has the problems such as recovery of HCl; (5) identical construction scale, investment is larger than a step condensation method.
Compare with state's azoic coupling component AS-BI production technique such as Japan, Germany, India, the deficiency of domestic existing technique is fairly obvious, mainly concentrates on the following aspects, and the one, product cost is high, deficiency in economic performance; The 2nd, the comprehensive yield of product is low, and raw material consumption is high; The 3rd, product quality problem, is mainly that content is low, analyzes (HPLC) purity only 99%, and product appearance is poor in addition, melts journey wide; The 4th, the final pigment dyestuff product of preparation, product tinting strength during application, light fastness are poor.
In recent years, for adapting to the demand of some Application Areas to high performance pigment, production has excellent endurance quality (as fast light, fastness to weathering), heat-resistant stability, resistance to migration etc. and high tinctorial strength, and the pigment dyestuff of good application performance is very urgent.Concealed pigment is owing to having following features: make insoluble pigment molecule have the potential pigment of certain temporary dissolubility; The potential pigment generating distributes with molecularity in organic solvent, polymer; By heating or chemical reaction, can prepare the even fine pigment dispersion of nano level (as being less than 20nm); Can be used for preparing sosoloid (sosoloid) and mixed crystal product; There is high transparency, good heat-resisting, light fastness and solvent resistance, progressively paid attention to and applied, to take the high-grade pigment of benzoglyoxaline ketone that azoic coupling component AS-BI is raw material production, have higher requirement, also to each quality index of basic raw material azoic coupling component AS-BI, require more strict simultaneously.
Problem for existing technique and the existence of azoic coupling component AS-BI product, in an existing step condensation method, 2-hydroxyl-3-naphthoyl chloride reacts on the basis of preparing azoic coupling component AS-BI technique with 5-Amino-2-benzimidazolinone, according to 5-Amino-2-benzimidazolinone and 2, 3-acid, the mechanism of reacting with 2-hydroxyl-3-naphthoyl chloride, considering solvent selects, catalyzer, the selection of acid binding agent etc., production cost, quality product, domestic raw materials quality index and supply, the factors such as application performance of final sintetics, theoretical in conjunction with relevant catalytic theory and organic synthesis, work out a kind of new azoic coupling component AS-BI production technique, meet the domestic production to azoic coupling component AS-BI at present, quality requirement, have important practical significance.
Summary of the invention
Technical problem to be solved by this invention is: for the deficiency of prior art existence, provide the synthetic method of the azoic coupling component AS-BI that a kind of product purity is high, yield is high, solvent recuperation rate of utilization is high, production cost is low.
For solving the problems of the technologies described above, technical scheme of the present invention is:
The synthetic method of a kind of azoic coupling component AS-BI, comprise the following steps: solvent N-Methyl pyrrolidone is joined in reactor, in vacuum tightness, be 0.06～0.098MPa, under agitation condition, add the 5-Amino-2-benzimidazolinone and 2 after pre-treatment removal of impurities, 3-acid, in 50～70 minutes, be warming up to 60～90 ℃, the suction phosphorus trichloride slowly from the bottom of reactor, in temperature, it is 30～50 ℃, in 30～60 minutes, suction is complete, at 40～65 ℃, continue reaction 10～30 minutes again, then from the disposable suction quadrol in bottom of reactor, again by the triphenyl phosphite of purifying slowly suction from bottom, in temperature, it is 35～55 ℃, in 20～40 minutes, suction is complete, and then continue reaction 100～150 minutes at 40～60 ℃, solvent is isolated in the complete press filtration of condensation reaction, obtain crude product azoic coupling component AS-BI, by described crude product azoic coupling component AS-BI through alkali cleaning and washing after, it is azoic coupling component AS-BI product more than 99.5wt% that oven dry obtains content.
As a kind of improvement, the complete press filtration of described condensation reaction is isolated after solvent, joins in methanol solution agitator treating 30～60 minutes, and then methanol solution is isolated in press filtration, obtains crude product azoic coupling component AS-BI.
As a kind of preferred, described N-Methyl pyrrolidone, 5-Amino-2-benzimidazolinone, 2, the weight ratio of 3-acid, triphenyl phosphite, phosphorus trichloride, quadrol, methyl alcohol is 100: 8.5～9.5: 12～14: 17～28: 2～10: 1.4～7.2: 40～50.
As a kind of improvement, the isolated methanol solution of described press filtration reclaims the methanol wash for next batch material.
As another kind, improve, the isolated solvent recuperation of the complete press filtration of described condensation reaction is for the condensation reaction solvent of next batch material.
As another kind, improve, during described alkali cleaning, in described crude product azoic coupling component AS-BI, adding weight is the softening water of 1.05～1.5 times of solvent N-Methyl pyrrolidone, at 60～95 ℃, dissolves 50～80 minutes, is cooled to 40～55 ℃, and spray adds Na
2cO
3content is 3～5% Na of 2,3-acid weight
2cO
3solution, stirs alkali cleaning 30～50 minutes, is then warming up to 90～98 ℃ and continues alkali cleaning 10～20 minutes, and alkaline solution is isolated in press filtration.
As further improving, described washing comprises following water-washing step at least in triplicate: in the crude product azoic coupling component AS-BI after alkali cleaning, adding weight is the softening water of 1.05～1.5 times of solvent N-Methyl pyrrolidone, in temperature, be that 60～95 ℃, pressure are 0.08～0.2MPa, stir washing 50～80 minutes, drying and obtaining content is azoic coupling component AS-BI product more than 99.5wt%.
Described oven dry is carried out in the time of 100～110 ℃.
The pre-treatment removal of impurities of described raw material 5-Amino-2-benzimidazolinone, that 5-Amino-2-benzimidazolinone is joined in ethanolic soln according to 1: 1.2～1.5 weight ratio, 20～40 ℃ of stirring reactions 20～40 minutes, then in vacuum tightness 0.02～0.08MPa, 40～60 ℃ of oven dry of temperature, and after the deironing of iron ion trap, then participate in condensation reaction.
The purification of described triphenyl phosphite is that triphenyl phosphite is heated to 60～80 ℃, by vacuum, sucks still kettle distillation, the phlegma that the distillation vacuum tightness 0.098～0.10MPa of intercepting, top gas phase temperature are 178～190 ℃.
Owing to having adopted technique scheme, the invention has the beneficial effects as follows:
1, the present invention adopts dual-component catalyst when condensation reaction, and add in the different steps of condensation reaction, use phosphorus trichloride catalyzer early stage and add from condensation kettle bottom, avoided the phenomenon of catalyzer phosphorus trichloride because of other product of hydrolysis generation, given full play to its catalytic activity, later stage is used triphenyl phosphite and adds quadrol as coordination catalyst, quadrol reacts with macromole acidic cpd, meeting accelerated reaction process, reaction is carried out to target product direction, promote condensation reaction to carry out, and use the pyridine series product of the alternative traditional technology of quadrol as coordination catalyst, not only make operational condition improve, and production cost reduces.Condensation reaction of the present invention is carried out under vacuum condition, temperature of reaction is low, reaction times shortens, side reaction reduces, especially add the phosphorus trichloride stage, the HCl of generation removes in time from reaction system, has reduced the impact of HCl on reaction, significantly reduce the generation of by product 5-Amino-2-benzimidazolinone hydrochloride, improved product yield and purity.Condensation reaction time of the present invention shortens nearly 2 hours than an existing step condensation method production technique.
2, owing to often containing the impurity such as two amido things, benzimidazolone, 5-Nitro-2-benzimidazolinone in industrial goods 5-Amino-2-benzimidazolinone, if do not remove, to have a negative impact to condensation reaction, affect to a certain extent the stable of ketone group, likely cause variation and the migration of ketone group in finished product AS-BI molecular structure.Industrial goods triphenyl phosphite is in fact also the mixture of multiple phenoxy group substituent, a lot of side reactions can occur when condensation reaction and affect product purity.The present invention is to raw material 5-Amino-2-benzimidazolinone, triphenyl phosphite adopts respectively washing with alcohol, the mode of distilation is carried out pre-treatment, purity and the reactive behavior of raw material have been significantly improved, reduced the generation of side reaction, outward appearance and the inner quality of the finished product have been improved, improved product stability, product purity prepared by the present invention is up to more than 99.5% (HPLC), outward appearance near-white, insolubles≤0.05wt% in alkali lye, the downstream pigment dyestuff quality product synthetic with the prepared azoic coupling component AS-BI of the present invention obviously improves, for example synthetic Pigment red P.R.176 is blue streak redness, there is high tinting strength, solarization fastness is better, thermostability at high density polyethylene(HDPE) can reach 290 ℃/5min, do not affect the warping property of these plastics.And the transformation efficiency of raw material 5-Amino-2-benzimidazolinone obviously improves, the comprehensive yield of product (in 5-Amino-2-benzimidazolinone) is in the situation that solvent is applied mechanically 8 times still >=92%.
3, the present invention isolates after solvent in the complete press filtration of condensation reaction, again through methanol solution agitator treating, displace remaining solvent, reduced the loss of solvent, first alcohol and solvent can continue to use after Distillation recovery respectively, and the present invention is because side reaction is few, the impurity generating is few, solvent purity is high, solvent recuperation access times and result of use have been increased, condensation reaction is from second batch feeds intake, and the quantity of solvent of adding is only good for the 10wt% condensation reaction of first quantity of solvent that feeds intake, and does not occur the special thickness of material, reacts inadequate unusual phenomenon.
4, the present invention adopts the reinforced mode of spray when alkali cleaning, and alkali lye contact with material evenly, and removal acidic substance are thorough, during alkali cleaning once gets final product with system in acidic substance; During washing, adopt pressurization washing, only wash the water-soluble substances that can remove in material for three times, improve product purity, product tape reddish tone after the oven dry of having avoided thoroughly not occurring because of washing, presented the situations such as reddish-brown, product appearance near-white prepared by the present invention.Compared to existing technology, reduce washing times, shortened the production time, reduced energy consumption.
5, the present invention has the advantages such as facility investment is few, material cost is low, energy consumption is low, quality product is high, yield is high, basic non-environmental-pollution, and product has very strong competitive capacity.Along with the development of Domestic Automotive Industry, the expansion of plastics industry scale, the rapid emergence of printing-ink industry, high-grade pigment comprises azoic coupling component AS-BI deep processed product, and consumption will be increasing at home; AS-BI has exported a plurality of countries and regions such as Japan, France, the U.S., Germany, and its deep processed product, as a plurality of kinds such as Pigment red P.R.171, P.R.176 have exported, will advantageously promote production and the demand of this intermediate.Application of the present invention, will produce actively and far-reaching influence the development of industry and even whole benzoglyoxaline ketone pigment dyestuff.
Embodiment
Below in conjunction with specific embodiment, further set forth the present invention.
Embodiment 1
Weight ratio by raw material 5-Amino-2-benzimidazolinone according to 1: 1.2 joins in ethanolic soln, and 20 ℃ of stirring reactions 20 minutes, proceed to after filtration in vacuum drier, then at vacuum tightness 0.04MPa, temperature 50 C, dries, then passes through the deironing of iron ion trap.Triphenyl phosphite is heated to 60 ℃, by vacuum, sucks still kettle distillation, heating, opens vacuum unit, and the phlegma that the distillation vacuum tightness 0.099MPa of intercepting, top gas phase temperature are 180～190 ℃ is as qualified catalyzer.
By solvent N-Methyl pyrrolidone, 5-Amino-2-benzimidazolinone, 2, 3-acid, triphenyl phosphite, phosphorus trichloride, quadrol, methyl alcohol was according to 100: 8.5: 12: 17: 2: 1.4: 40 weight ratio is got the raw materials ready, solvent N-Methyl pyrrolidone is joined in the reactor that processed crosses, open vacuum pump and stirring, in vacuum tightness, be 0.06MPa, under agitation condition, add the 5-Amino-2-benzimidazolinone and 2 after pre-treatment removal of impurities, 3-acid, in 50 minutes, be warming up to 60 ℃, the suction phosphorus trichloride slowly from the bottom of reactor, in temperature, it is 30 ℃, in 30 minutes, suction is complete, at 40 ℃, continue reaction 10 minutes again, then from the disposable suction quadrol in bottom of reactor, again by the triphenyl phosphite of purifying slowly suction from bottom, in temperature, it is 35 ℃, in 20 minutes, suction is complete, and then continue reaction 100 minutes at 40 ℃, condensation reaction is complete is pressed into tank filter by material, with pressurized air press filtration, isolate after solvent, join in methanol solution agitator treating 30 minutes, then methanol solution is isolated in press filtration, obtain crude product azoic coupling component AS-BI, the isolated methanol solution of press filtration reclaims the methanol wash for next batch material, the isolated solvent recuperation of press filtration is for the condensation reaction solvent of next batch material.
In alkali cleaning still, adding weight is the softening water of 1.05 times of solvent N-Methyl pyrrolidone, will in crude product azoic coupling component AS-BI, add in batches, is heated to 60 ℃ and dissolves 50 minutes, is cooled to 40 ℃, and spray adds Na
2cO
3content is 3% Na of 2,3-acid weight
2cO
3solution, is made into and approaches saturated solution, stirs alkali cleaning 30 minutes, is then warming up to 90 ℃ and continues alkali cleaning 10 minutes, and alkaline solution is isolated in press filtration.
In alkali cleaning still, adding weight is the softening water of 1.05 times of solvent N-Methyl pyrrolidone, crude product azoic coupling component AS-BI after alkali cleaning is added, be heated to 60 ℃, to alkali cleaning still, passing into pressurized air adjusting pressure is 0.08MPa, stir washing 50 minutes, above water-washing step in triplicate, in the time of 100 ℃, dry obtain quality in Table 1 azoic coupling component AS-BI product.
Embodiment 2
Weight ratio by raw material 5-Amino-2-benzimidazolinone according to 1: 1.5 joins in ethanolic soln, and 40 ℃ of stirring reactions 40 minutes, proceed to after filtration in vacuum drier, then at vacuum tightness 0.08MPa, temperature 60 C, dries, then passes through the deironing of iron ion trap.Triphenyl phosphite is heated to 80 ℃, by vacuum, sucks still kettle distillation, heating, opens vacuum unit, and the phlegma that the distillation vacuum tightness 0.10MPa of intercepting, top gas phase temperature are 178～190 ℃ is as qualified catalyzer.
By solvent N-Methyl pyrrolidone, 5-Amino-2-benzimidazolinone, 2, 3-acid, triphenyl phosphite, phosphorus trichloride, quadrol, methyl alcohol was according to 100: 9.5: 14: 28: 10: 7.2: 50 weight ratio is got the raw materials ready, the solvent N-Methyl pyrrolidone of recovery is for the second time joined in reactor, open vacuum pump and stirring, in vacuum tightness, be 0.098MPa, under agitation condition, add the 5-Amino-2-benzimidazolinone and 2 after pre-treatment removal of impurities, 3-acid, in 70 minutes, be warming up to 90 ℃, the suction phosphorus trichloride slowly from the bottom of reactor, in temperature, it is 50 ℃, in 60 minutes, suction is complete, at 65 ℃, continue reaction 30 minutes again, then from the disposable suction quadrol in bottom of reactor, again by the triphenyl phosphite of purifying slowly suction from bottom, in temperature, it is 55 ℃, in 40 minutes, suction is complete, and then continue reaction 150 minutes at 60 ℃, condensation reaction is complete is pressed into tank filter by material, with pressurized air press filtration, isolate after solvent, join in methanol solution agitator treating 60 minutes, then methanol solution is isolated in press filtration, obtain crude product azoic coupling component AS-BI, the isolated methanol solution of press filtration reclaims the methanol wash for next batch material, the isolated solvent recuperation of press filtration is for the condensation reaction solvent of next batch material.
In alkali cleaning still, adding weight is the softening water of 1.5 times of solvent N-Methyl pyrrolidone, will in crude product azoic coupling component AS-BI, add in batches, is heated to 95 ℃ and dissolves 80 minutes, is cooled to 55 ℃, and spray adds Na
2cO
3content is 5% Na of 2,3-acid weight
2cO
3solution, is made into and approaches saturated solution, stirs alkali cleaning 50 minutes, is then warming up to 98 ℃ and continues alkali cleaning 20 minutes, and alkaline solution is isolated in press filtration.
In alkali cleaning still, adding weight is the softening water of 1.5 times of solvent N-Methyl pyrrolidone, crude product azoic coupling component AS-BI after alkali cleaning is added, be heated to 95 ℃, to alkali cleaning still, passing into pressurized air adjusting pressure is 0.2MPa, stir washing 80 minutes, above water-washing step in triplicate, in the time of 110 ℃, carry out dries quantity in Table 1 azoic coupling component AS-BI product.
Embodiment 3
Weight ratio by raw material 5-Amino-2-benzimidazolinone according to 1: 1.35 joins in ethanolic soln, and 30 ℃ of stirring reactions 30 minutes, proceed to after filtration in vacuum drier, then at vacuum tightness 0.05MPa, temperature 50 C, dries, then passes through the deironing of iron ion trap.Triphenyl phosphite is heated to 70 ℃, by vacuum, sucks still kettle distillation, heating, opens vacuum unit, and the phlegma that the distillation vacuum tightness 0.098MPa of intercepting, top gas phase temperature are 178～190 ℃ is as qualified catalyzer.
By solvent N-Methyl pyrrolidone, 5-Amino-2-benzimidazolinone, 2, 3-acid, triphenyl phosphite, phosphorus trichloride, quadrol, methyl alcohol was according to 100: 9: 13: 22: 6: 4: 45 weight ratio is got the raw materials ready, the solvent N-Methyl pyrrolidone of the 4th recovery is joined in reactor, open vacuum pump and stirring, in vacuum tightness, be 0.08MPa, under agitation condition, add the 5-Amino-2-benzimidazolinone and 2 after pre-treatment removal of impurities, 3-acid, in 60 minutes, be warming up to 80 ℃, the suction phosphorus trichloride slowly from the bottom of reactor, in temperature, it is 40 ℃, in 50 minutes, suction is complete, at 50 ℃, continue reaction 20 minutes again, then from the disposable suction quadrol in bottom of reactor, again by the triphenyl phosphite of purifying slowly suction from bottom, in temperature, it is 45 ℃, in 30 minutes, suction is complete, and then continue reaction 120 minutes at 50 ℃, condensation reaction is complete is pressed into tank filter by material, with pressurized air press filtration, isolate after solvent, join in methanol solution agitator treating 40 minutes, then methanol solution is isolated in press filtration, obtain crude product azoic coupling component AS-BI, the isolated methanol solution of press filtration reclaims the methanol wash for next batch material, the isolated solvent recuperation of press filtration is for the condensation reaction solvent of next batch material.
In alkali cleaning still, adding weight is the softening water of 1.3 times of solvent N-Methyl pyrrolidone, will in crude product azoic coupling component AS-BI, add in batches, is heated to 80 ℃ and dissolves 70 minutes, is cooled to 45 ℃, and spray adds Na
2cO
3content is 4% Na of 2,3-acid weight
2cO
3solution, is made into and approaches saturated solution, stirs alkali cleaning 40 minutes, is then warming up to 95 ℃ and continues alkali cleaning 15 minutes, and alkaline solution is isolated in press filtration.
In alkali cleaning still, adding weight is the softening water of 1.35 times of solvent N-Methyl pyrrolidone, crude product azoic coupling component AS-BI after alkali cleaning is added, be heated to 85 ℃, to alkali cleaning still, passing into pressurized air adjusting pressure is 0.1MPa, stir washing 60 minutes, above water-washing step in triplicate, in the time of 105 ℃, carry out dries quantity in Table 1 azoic coupling component AS-BI product.
Table 1
Claims (8)
1. the synthetic method of an azoic coupling component AS-BI, it is characterized in that comprising the following steps: solvent N-Methyl pyrrolidone is joined in reactor, in vacuum tightness, be 0.06～0.098MPa, under agitation condition, add the 5-Amino-2-benzimidazolinone and 2 after pre-treatment removal of impurities, 3-acid, in 50～70 minutes, be warming up to 60～90 ℃, the suction phosphorus trichloride slowly from the bottom of reactor, in temperature, it is 30～50 ℃, in 30～60 minutes, suction is complete, at 40～65 ℃, continue reaction 10～30 minutes again, then from the disposable suction quadrol in bottom of reactor, again by the triphenyl phosphite of purifying slowly suction from bottom, in temperature, it is 35～55 ℃, in 20～40 minutes, suction is complete, and then continue reaction 100～150 minutes at 40～60 ℃, solvent is isolated in the complete press filtration of condensation reaction, obtain crude product azoic coupling component AS-BI, by described crude product azoic coupling component AS-BI through alkali cleaning and washing after, it is azoic coupling component AS-BI product more than 99.5wt% that oven dry obtains content,
The pre-treatment removal of impurities of described raw material 5-Amino-2-benzimidazolinone, that 5-Amino-2-benzimidazolinone is joined in ethanolic soln according to the weight ratio of 1:1.2～1.5,20～40 ℃ of stirring reactions 20～40 minutes, then in vacuum tightness 0.02～0.08MPa, 40～60 ℃ of oven dry of temperature, and after the deironing of iron ion trap, then participate in condensation reaction;
The purification of described triphenyl phosphite is that triphenyl phosphite is heated to 60～80 ℃, by vacuum, sucks still kettle distillation, the phlegma that the distillation vacuum tightness 0.098～0.10MPa of intercepting, top gas phase temperature are 178～190 ℃.
2. the synthetic method of azoic coupling component AS-BI as claimed in claim 1, it is characterized in that: the complete press filtration of described condensation reaction is isolated after solvent, join in methanol solution agitator treating 30～60 minutes, then methanol solution is isolated in press filtration, obtains crude product azoic coupling component AS-BI.
3. the synthetic method of azoic coupling component AS-BI as claimed in claim 2, it is characterized in that: described N-Methyl pyrrolidone, 5-Amino-2-benzimidazolinone, 2, the weight ratio of 3-acid, triphenyl phosphite, phosphorus trichloride, quadrol, methyl alcohol is 100:8.5～9.5:12～14:17～28:2～10:1.4～7.2:40～50.
4. the synthetic method of azoic coupling component AS-BI as claimed in claim 2, is characterized in that: the isolated methanol solution of described press filtration reclaims the methanol wash for next batch material.
5. the synthetic method of azoic coupling component AS-BI as claimed in claim 1, is characterized in that: the isolated solvent recuperation of the complete press filtration of described condensation reaction is for the condensation reaction solvent of next batch material.
6. the synthetic method of azoic coupling component AS-BI as claimed in claim 1, it is characterized in that: during described alkali cleaning, in described crude product azoic coupling component AS-BI, adding weight is the softening water of 1.05～1.5 times of solvent N-Methyl pyrrolidone, at 60～95 ℃, dissolve 50～80 minutes, be cooled to 40～55 ℃, spray adds Na
2cO
3content is 3～5% Na of 2,3-acid weight
2cO
3solution, stirs alkali cleaning 30～50 minutes, is then warming up to 90～98 ℃ and continues alkali cleaning 10～20 minutes, and alkaline solution is isolated in press filtration.
7. the synthetic method of azoic coupling component AS-BI as claimed in claim 1, it is characterized in that described washing comprises following water-washing step at least in triplicate: in the crude product azoic coupling component AS-BI after alkali cleaning, adding weight is the softening water of 1.05～1.5 times of solvent N-Methyl pyrrolidone, in temperature, be that 60～95 ℃, pressure are 0.08～0.2MPa, stir washing 50～80 minutes, drying and obtaining content is azoic coupling component AS-BI product more than 99.5wt%.
8. the synthetic method of azoic coupling component AS-BI as claimed in claim 7, is characterized in that: described oven dry is carried out in the time of 100～110 ℃.
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| CN105509415A (en) * | 2015-12-18 | 2016-04-20 | 常熟市柏伦精细化工有限公司 | Purification type vacuum drier and method |
| CN111790172A (en) * | 2020-07-29 | 2020-10-20 | 濮阳市盛源能源科技股份有限公司 | Solvent distillation recovery system and use method |
| CN111777524B (en) * | 2020-08-10 | 2022-10-21 | 山东安迪新型材料有限公司 | Post-treatment method for preparing naphthol AS-PH |
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| DE2758818A1 (en) * | 1977-12-30 | 1979-07-12 | Hoechst Ag | NEW CRYSTAL MODIFICATION OF 5- (2'-HYDROXY-3'-NAPHTHOYL-AMINO) -BENZIMIDAZOLONE- (2), METHOD FOR MANUFACTURING AND USING IT |
| US5756757A (en) * | 1994-11-18 | 1998-05-26 | Hoechst Aktiengesellschaft | Process for the preparation of 3-hydroxy-N-benzimidazolon-5-yl-2-naphthamide in the high purity required of azo pigments |
| CN1251834A (en) * | 1999-11-15 | 2000-05-03 | 湖北楚源精细化工集团股份有限公司 | Process for preparing Naphthol AS products |
| CN101838244A (en) * | 2010-06-03 | 2010-09-22 | 山东金城医药化工股份有限公司 | Organic solvent synthetic method of azoic coupling component ASBI |
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2011
- 2011-12-30 CN CN201110456136.XA patent/CN102532035B/en not_active Expired - Fee Related
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| DE2758818A1 (en) * | 1977-12-30 | 1979-07-12 | Hoechst Ag | NEW CRYSTAL MODIFICATION OF 5- (2'-HYDROXY-3'-NAPHTHOYL-AMINO) -BENZIMIDAZOLONE- (2), METHOD FOR MANUFACTURING AND USING IT |
| US5756757A (en) * | 1994-11-18 | 1998-05-26 | Hoechst Aktiengesellschaft | Process for the preparation of 3-hydroxy-N-benzimidazolon-5-yl-2-naphthamide in the high purity required of azo pigments |
| CN1251834A (en) * | 1999-11-15 | 2000-05-03 | 湖北楚源精细化工集团股份有限公司 | Process for preparing Naphthol AS products |
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