CN106280534B - A kind of orchil compound and preparation method thereof - Google Patents
A kind of orchil compound and preparation method thereof Download PDFInfo
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- CN106280534B CN106280534B CN201610666293.6A CN201610666293A CN106280534B CN 106280534 B CN106280534 B CN 106280534B CN 201610666293 A CN201610666293 A CN 201610666293A CN 106280534 B CN106280534 B CN 106280534B
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
- C09B29/00—Monoazo dyes prepared by diazotising and coupling
- C09B29/0003—Monoazo dyes prepared by diazotising and coupling from diazotized anilines
- C09B29/0007—Monoazo dyes prepared by diazotising and coupling from diazotized anilines containing acid groups, e.g. CO2H, SO3H, PO3H2, OSO3H, OPO2H2; Salts thereof
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
- C09B29/00—Monoazo dyes prepared by diazotising and coupling
- C09B29/24—Monoazo dyes prepared by diazotising and coupling from coupling components containing both hydroxyl and amino directing groups
- C09B29/28—Amino naphthols
- C09B29/30—Amino naphtholsulfonic acid
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Abstract
The invention discloses a kind of orchil compound and preparation method thereof, the preparation method of the Ink-jet dye compound comprises the following steps：(1) H acid is condensed with Cyanuric Chloride in acid condition, is filtered after condensation with filter paper；(2) by compoundWherein R is SO3H, carry out diazonium and be coupled with condensation product；(3) by compound B1It is added in above-mentioned solution and carries out secondary condensation；(4) add quantitative activated carbon and diatomite is handled, then desalination and concentration；(5) concentrate is subjected to acidic hydrolysis, then desalination and concentration obtains required compound again.The product synthesized using technical scheme, purity is high, and solubility is good, and stability is high, simple to operate, easily amplification production.Compared to more conventional synthesis mode, it is not necessary to which saltouing just can reach very high purity, reduce the yield of waste water, improve production efficiency, saved cost.There is good promotion prospect.
Description
Technical field
The present invention relates to technical field of dye, more particularly, to a kind of orchil compound and preparation method thereof.
Background technology
Red ink-jet dye in the market, most of is active orchil, such as：Active red 180, active red
195, some row dyestuffs of the grade of active red 141.Because these dyestuffs are all reactive dye, have during use and much ask
Topic, such as：PH value is unstable, coloured light problem of color etc..And red used is most of is magenta currently on the market, and
It is not gold-tinted red.
With the continuous progress of printer technology, the classification of ink-jet ink is also increasingly thinner, particularly wide format printer.
The ink of present color printer has four colors, six colors, seven colors, 12 colors etc..The species of the ink images printed also more
Add clear distinctness.But the gold-tinted in printer is red substantially based on colorant match, is mixed by pinkish red and two kinds of colors of yellow
Large red is combined into, Ye You companies are replaced with Reactive Red 24, but due to being reactive dye, are equally deposited with traditional reactive dye
PH value is unstable the problems such as.
The content of the invention
In view of this, the invention provides a kind of compound of orchil and its synthetic method, dye provided by the invention
Expect that purity is high, color is vivid, and filterability is good, and pH is stable, and stability is good.
In order to realize foregoing invention purpose, the present invention provides following technical scheme：
The invention provides a kind of orchil compound with structure shown in Formulas I：
Wherein R is SO3H, B are：Anilino-, methylphenylamine base, N-ethylaniline base, o ethyl aniline base, adjacent methyl
One kind in anilino-.
The invention provides the preparation method of the dye composition described in above-mentioned technical proposal with Formulas I structure, including such as
Lower step：
(1) Cyanuric Chloride and the H acid with structure shown in Formula II are subjected to condensation reaction, obtain the structure as shown in formula III
Compound：
(2) compound with structure shown in formula IV and natrium nitrosum are subjected to diazo-reaction in an hcl ambient, obtained
With structure diazenium compound shown in Formula V：
(3) tool that the diazenium compound with Formula V structure for obtaining the step (2) obtains with the step (1)
The compound for having structure shown in formula III carries out coupling reaction, obtains structural compounds shown in Formula IV：
(4) compound with structure shown in Formula IV that aniline or anil obtain with the step (5) is carried out
Secondary condensation, obtain having the compound of structure shown in Formula VII：
(5) compound of structure is hydrolyzed in acid condition shown in the Formula VII for obtaining the step (4), obtains
The compound of structure shown in Formulas I；
There is no time sequencing between described step (1) and step (2).
Preferably, the temperature of condensation reaction is 0~5 DEG C in step (1), and the time of condensation reaction is 1~2h；Condensation reaction
Carried out under conditions of being 5.5~7 in pH value.
Preferably, the diazo reaction temperature in step (2) is 5~15 DEG C, and the diazo reaction time is 0.8~1.2h；Diazonium
Reaction is carried out under conditions of being 6~7 in pH value.
Preferably, couple temperature is 5~15 DEG C in the step (3), and Coupling time is 0.8~1.2h；Coupling reaction exists
PH value is carried out under conditions of being 6~7.
Preferably, secondary condensation temperature is 15~30 DEG C in the step (4), and the secondary condensation time is 1.5~2.5h；Two
Secondary condensation reaction is carried out under conditions of being 6.3~7.5 in pH value.
Hydrolysis temperature is 85~97 DEG C in step (5), and hydrolysis time is 3.5~4.5h；Hydrolyze in the bar that pH value is 1~2
Carried out under part.
The mol ratio of Cyanuric Chloride and the H acid with structure shown in Formula II is 1.03~1.5 in step (1)：1；
The have compound of structure shown in formula IV and the mol ratio of natrium nitrosum described in step (2) are 1：1.03~
1.5；
The diazenium compound with Formula V structure described in step (3) and rubbing with structural compounds shown in Formula II
You are than being 1：1.03~1.5；
Aniline or anil described in step (4) have structure shown in Formula IV with what the step (5) obtained
The mol ratio of compound is 1.05~1.5：1.
Anil is methylphenylamine in step (4), N-ethylaniline, o ethyl aniline, in o-toluidine
It is a kind of.
Advantageous effects：The invention provides the orchil compound with structure shown in Formulas I, and dyestuffs purity is high,
Color is vivid, and filterability is good, and pH and heat endurance are good；
Present invention also offers the preparation method of orchil compound described in above-mentioned technical proposal, with existing synthesis side
Method is compared, and preparation method building-up process provided by the invention is simple；The purity of product is high after synthesis, eliminates that to be conventionally synthesized be salt
The step of analysis, reduce the discharge of waste water；The problem of hydrolysis acidic hydrolysis, is solved in basic hydrolysis, and accessory substance is more；Close
The stabilization synthesized into the finished product gone out with conventional synthesis process is more preferable；Make product more competitive superiority.It is test result indicates that of the invention
The orchil compound fluency of offer is good, and coloured light, pH and heat endurance are good, and purity is high.
Brief description of the drawings：
The embodiment of the present invention is described in further detail below in conjunction with the accompanying drawings：
Fig. 1：The orchil liquid chromatogram that conventional method disclosed in prior art synthesizes；
Fig. 2：The orchil liquid chromatogram synthesized in embodiment 1；
Fig. 3：The orchil liquid chromatogram synthesized in embodiment 2；
Fig. 4：The orchil liquid chromatogram synthesized in embodiment 3.
Embodiment
The invention provides a kind of orchil compound with structure shown in Formulas I：
Wherein R is SO3H, B are：Anilino-, methylphenylamine base, N-ethylaniline base, o ethyl aniline base, adjacent methyl
One kind in anilino-.
The orchil compound is preferably：
Present invention also offers described in above-mentioned technical proposal have the dye composition of structure shown in Formulas I preparation method,
Comprise the following steps：
(1) Cyanuric Chloride and the H acid with structure shown in Formula II are subjected to condensation reaction, obtain the structure as shown in formula III
Compound：
(2) compound with structure shown in formula IV and natrium nitrosum are subjected to diazo-reaction in an hcl ambient, obtained
With structure diazenium compound shown in Formula V：
(3) tool that the diazenium compound with Formula V structure for obtaining the step (2) obtains with the step (1)
The compound for having structure shown in formula III carries out coupling reaction, obtains structural compounds shown in Formula IV：
(4) compound with structure shown in Formula IV that aniline or anil obtain with the step (5) is carried out
Secondary condensation, obtain having the compound of structure shown in Formula VII：
(5) compound of structure is hydrolyzed in acid condition shown in the Formula VII for obtaining the step (4), obtains
The compound of structure shown in Formulas I；
There is no time sequencing between described step (1) and step (2).
Cyanuric Chloride and the H acid with structure shown in Formula II are carried out condensation reaction by the present invention, are obtained with shown in formula III
The compound of structure.The present invention preferably dissolves H acid, obtains H acid solutions；Cyanuric Chloride is disperseed, Cyanuric Chloride is obtained and disperses
Liquid；The H acid solutions are added drop-wise in Cyanuric Chloride dispersion liquid, carry out condensation reaction.
In the present invention, H acid is preferably distributed in water by the H acid solutions, and pH value is adjusted with alkali, makes all dissolvings of H acid
Obtain.In the present invention, the mass concentration of the H acid solutions is preferably 10~15%；The alkali is preferably sodium hydroxide or hydrogen
Lithia, more preferably sodium hydroxide；The concentration of the alkali is 15~25%, preferably 20%；The pH value of the H acid solutions is excellent
Elect 6~6.5 as.
In the present invention, Cyanuric Chloride is preferably distributed in frozen water by the Cyanuric Chloride dispersion liquid, and mashing obtains.At this
In invention, the mass concentration of the Cyanuric Chloride dispersion liquid is preferably 8~12%；The time of the mashing is preferably 20~
40min；More preferably 30min.
In the present invention, rate of addition is changed to：Per minute to be added dropwise 1% or so of total amount, time for adding control is small in 1.5-2
When.In the present invention, the temperature of the condensation reaction is preferably 0~5 DEG C, more preferably 0~3 DEG C；The condensation reaction when
Between be preferably 1~2h, more preferably 1.5 hours；The condensation reaction is preferably to carry out under conditions of 5.5~7 preferably in pH value,
More preferably 6~6.5.In the present invention, the pH value of the condensation reaction is preferably adjusted by alkali compounds, the alkalization
Compound is preferably sodium acid carbonate.
In the present invention, the Cyanuric Chloride and the mol ratio of the H acid with structure shown in Formula II for preferably 1.03~
1.5：1, more preferably 1.03~1.3：1.
After the completion of condensation, the present invention preferably filters the reaction solution of the condensation reaction, removes unreacted Cyanuric Chloride, obtains
It is standby to the compound condensation liquid with structure shown in formula III.In the present invention, the filtering is preferably entered using Medium speed filter paper
OK.
Compound with structure shown in formula IV and natrium nitrosum are carried out diazo-reaction by the present invention in an hcl ambient,
Obtain with structure diazenium compound shown in Formula V.In the Formula V, R is preferably-SO3H；In the present invention, the R substitutions tool
Body is ortho position, contraposition or meta substitution.
The present invention preferably dissolves the compound of structure shown in formula IV, obtains the solution of compound shown in formula IV；By nitrous
Sour sodium is added in the solution of compound shown in the formula IV, obtains mixed solution；By the mixed solution be added drop-wise to hydrochloric acid with
In the mixed liquor of frozen water, diazo-reaction is carried out, obtains the diazonium compound with Formula V locking-type structure.The present invention preferably will tool
The compound for having formula IV structure is dissolved into water, first adjusts pH value with alkali, the alkali is preferably sodium hydroxide, and the pH value is preferred
For 6~6.5.
In the present invention, the speed that the mixed solution is added drop-wise in the mixed liquor of hydrochloric acid and frozen water is preferably ....
In the present invention, the temperature of the diazo-reaction is preferably 5~15 DEG C, more preferably 5~10 DEG C；The diazo-reaction when
Between be preferably 0.8~1.2h, more preferably 1h；The diazo-reaction is carried out under conditions of being preferably 6~7 in pH value, more excellent
Elect 6~6.5 as.
In the present invention, described the have compound of structure shown in formula IV and the mol ratio of natrium nitrosum are preferably 1：
1.03~1.5, more preferably 1：1.03~1.3；
After the diazo-reaction, the preferred weight for removing excessive natrium nitrosum, obtaining having structure shown in Formula V of the present invention
Nitrogen salt compound.In the present invention, the natrium nitrosum is preferably removed by solid sulfamic acid, specifically, to the diazonium
Change and the natrium nitrosum that solid sulfamic acid removes excess is added in the reaction solution that reaction obtains.The use of described solid sulfamic acid
Measure as the 0.1% of natrium nitrosum addition quality.
After obtaining the compound of structure shown in formula III and formula IV, the diazonium salinization with Formula V structure of the invention that will be obtained
Compound and the obtained compound with structure shown in formula III carry out coupling reaction, obtain the compound of structure shown in Formula IV.
Obtained diazenium compound is preferably added directly into the good condensation solution of above-mentioned filtering by the present invention to be reacted, and is had
There is the coupling material liquid of structure shown in Formula IV.
The temperature of heretofore described coupling reaction is preferably 5~15 DEG C, more preferably 5~10 DEG C；The coupling reaction
Time is preferably 0.8~1.2h, more preferably 1h；The pH of the coupling reaction is preferably 6~7, and more preferably 6~6.5.
In the present invention, the described diazenium compound with Formula V structure and the mol ratio with structural compounds shown in formula III are preferred
For 1：1.03~1.5, more preferably 1：1.03~1.3.
After obtaining the compound of structure shown in Formula IV, the present invention is by aniline or anil and has structure shown in Formula IV
Compound carry out secondary condensation, obtain having the compound of structure shown in Formula VII.The present invention is preferably by aniline or aniline derivatives
Thing is added in the even summation reactant feed liquid of gained and carries out secondary condensation.
In the present invention, the anil is preferably methylphenylamine, N-ethylaniline, o ethyl aniline and adjacent first
One kind in base aniline.
In the present invention, the temperature of the secondary condensation is preferably 15~30 DEG C, more preferably 15~20 DEG C；The secondary contracting
It is preferably 1.5~2.5h to close the reaction time, more preferably 2h；The consecutive condensation pH value is preferably 6.3~7.5, more excellent
Elect 6.5~7 as.In the present invention, the rubbing with aniline or anil and the compound with structure shown in Formula IV
You are 1.03~1.5 than being preferably：1, more preferably 1.03~1.3：1.
After the secondary condensation, the feed liquid that the present invention preferably obtains the secondary condensation is adsorbed, filtered, taken off successively
Salt and concentration, obtain having the compound of structure shown in Formula VII.In the present invention, the adsorbent that the absorption uses preferably wraps
Activated carbon and diatomite are included, activated carbon and diatomite are added in the feed liquid that can be specifically obtained to the secondary condensation.In this hair
In bright, described activated carbon, diatomaceous dosage are preferably be condensed feed liquid quality 0.5~1.5%.The present invention is to the filtering
Method there is no special limitation, using the technical scheme of filtering well known to those skilled in the art, specifically, in this hair
In bright embodiment, the filtering can be carried out with press filtration bed, and the filter core specification of described press filtration bed is preferably PP1.0 μm.
In the present invention, the desalination is preferably carried out using NF membrane.The NF membrane molecular weight between 500-1000,
The temperature of heretofore described desalination is preferably 15~35 DEG C, more preferably 20~30 DEG C；The time of the desalination is preferably 3.5
~4.5h, more preferably 4h；The pH value during desalination is preferably 6~7.5, and more preferably 6.5~7.
In the present invention, when the electrical conductivity for being concentrated in the salt waste water that desalination obtains is less than 0.5ms/cm, obtain
Concentrate with Formula VII structural compounds.The concentration concentration is preferably 13~17%, and more preferably 15%.
After obtaining the compound of structure shown in Formula VII, the present invention is by the compound with structure shown in Formula VII in acid
It is hydrolyzed under the conditions of property, obtains the compound of structure shown in Formulas I.In the present invention, the acid condition is preferably carried by hydrochloric acid
For in the concentrate with Formula VII structural compounds of the invention for preferably adding hydrochloric acid to obtain, reaction is hydrolyzed.
In the present invention, described hydrolysis temperature is preferably 85~97 DEG C, more preferably 95~97 DEG C；The hydrolysis time
Preferably 3.5~4.5h, more preferably 4h；The hydrolysis pH value is preferably 1~2, and more preferably 1~1.5.
After the hydrolysis, the present invention filters obtained hydrolysis feed liquid successively, desalination, concentration and secondary mistake
Filter, obtains the finished product with Formulas I structure.In the present invention, described filtering is preferably to be carried out with PP1.0um filter core；
In the present invention, described desalination is preferably carried out using NF membrane；The pH value of the desalination is preferably 7.5~9, more
Preferably 8~8.5；The temperature of the desalination is preferably 15~35 DEG C, more preferably 20~30 DEG C；The time of the desalination is preferred
For 5.5~6.5h, more preferably 6h.
In the present invention, the degree of the concentration is preferably 20~30%, and more preferably 25%.
In the present invention, the secondary filter is preferably carried out using nylon filter core.
Advantageous effects：Compared with existing synthetic method, technical scheme, there is following technological merit：
Building-up process is simple；Purity after synthesis is high, eliminates that to be conventionally synthesized be the discharge for reducing waste water the step of saltouing；Hydrolysis
With acidic hydrolysis, solve in basic hydrolysis, the problem of accessory substance is more；What the finished product synthesized synthesized with conventional synthesis process
It is stable more preferable；Make product more competitive superiority.
The compound extremely synthetic method of orchil provided by the invention is carried out specifically with reference to embodiment
It is bright, but they can not be interpreted as limiting the scope of the present invention.
Embodiment 1
(1) H acid dissolving：0.1mol H acid is distributed in 300g water, then adjusted the pH of solution with 20% sodium hydroxide
It is whole all after dissolving, to stir 0.5h between 6-6.5, it is standby；
Cyanuric Chloride disperses：0.103mol Cyanuric Chloride is distributed in 200g frozen water, disperses 0.5h, make it scattered
Uniformly；
Condensation：The H acid solutions that will have been dissolved, are slowly added drop-wise in Cyanuric Chloride dispersion liquid, during dropwise addition, do not control
PH processed, 0-5 DEG C of temperature is controlled, after dripping, it is 1.8-2.2 to adjust pH value with sodium bicarbonate powder.Control temperature and pH until
Reaction terminates.TLC (chromatography) detects terminal.
Filtering：The condensation solution reacted is filtered with Medium speed filter paper, removes excessive Cyanuric Chloride, in filter process,
0-5 DEG C of keeping temperature.After having filtered, insulation is standby.
(2) diazonium：0.1mol orthanilic acids, it is distributed in 100g water, then adjusts pH with 20% sodium hydroxide
It is worth 8, it is all dissolved, 0.5h is stirred after dissolving, then 0.103mol natrium nitrosum dry powder is added in solution, stirs
It is standby to whole dissolvings.
0.3mol hydrochloric acid is added in 100g frozen water, stirs, is then slowly added drop-wise to above-mentioned orthanilic acid and Asia
In nitramine solution, 0-5 DEG C of temperature is controlled during dropwise addition, after being added dropwise to complete, hydrochloric acid is detected and whether natrium nitrosum is excessive, keep
Hydrochloric acid and the micro- excess of natrium nitrosum, 0-5 DEG C is incubated, is incubated 1h, then added 0.5g sulfamic acids, remove excessive nitrous acid
Sodium, it is standby to obtain diazol.
(3) it is coupled：Diazol is all added in the condensation product in the step (1) filtered, then with 15% carbon
Sour sodium adjusts pH value between 6-6.5,5-10 DEG C of temperature control in coupled processes, after pH value is adjusted, is incubated 2h.
(4) secondary condensation：0.103mol methylphenylamine is added in coupling solution, pH is adjusted with 15% sodium carbonate
It is worth between 7-7.5, and slowly between 15-20 DEG C of heating, and keeping temperature and pH, until reaction terminates, TLC (chromatography) is examined
Survey terminal.
Filter desalination：Two feed liquids to have contracted are separately added into be condensed the activated carbon of feed liquid mass fraction 1%, 1% silicon
Diatomaceous earth, filtered with press filtration bed, then the filter element filtering with PP1.0um, desalination then is carried out with NF membrane, has kept liquid level, dyestuff
Concentration is 5%, starts to concentrate until the electrical conductivity of desalinization wastewater is less than 0.5ms/cm, concentration concentration to 15% or so.
(5) hydrolyze：The hydrochloric acid that 0.09mol concentration is 30% is added in concentrate solution into step (4) after filtering desalination,
Adjustment pH value insulation, terminates between 1-1.5, being then warming up to 95 DEG C until reacting.TLC (chromatography) detects terminal, then
PH value is adjusted to 8 with 20% sodium hydroxide.
(6) desalination：By the feed liquid hydrolyzed in step (5) with after PP1.0um filter element filtering, with NF membrane desalination,
25% concentration is concentrated to, then finished product is obtained after nylon filter element filtering.
Gained finished product 166g, mass concentration be 25% concentration finished product, yield 95.6%.(according to real income finished product
Quality reacts the mass ratio calculated yield of gained finished product with throwing raw material completely in the ideal situation)
Embodiment 2
(1) H acid dissolving：0.1mol H acid is distributed in 300g water, then adjusted the PH of solution with 20% sodium hydroxide
It is whole all after dissolving, to stir 0.5h between 6-6.5, it is standby；
Cyanuric Chloride disperses：0.13mol Cyanuric Chloride is distributed in 200g frozen water, disperses 0.5h, make it scattered equal
It is even；
Condensation：The H acid solutions that will have been dissolved, are slowly added drop-wise in Cyanuric Chloride dispersion liquid, during dropwise addition, do not control
PH, 0~5 DEG C of temperature is controlled, be 1.8~2.2 with sodium bicarbonate powder adjustment pH value after dripping.Control temperature and pH until
Reaction terminates.TLC (chromatography) detects terminal.
Filtering：The condensation solution reacted is filtered with Medium speed filter paper, removes excessive Cyanuric Chloride, in filter process,
0-5 DEG C of keeping temperature.After having filtered, insulation is standby.
(2) diazonium：0.1mol metanilic acids, it is distributed in 100g water, then adjusts pH with 20% sodium hydroxide
It is worth 8, it is all dissolved, 0.5h is stirred after dissolving, then 0.13mol natrium nitrosum dry powder is added in solution, stirs
It is standby to whole dissolvings.
0.3mol hydrochloric acid is added in 100g frozen water, stirs, is then slowly added drop-wise to above-mentioned metanilic acid and Asia
In nitramine solution, 0~5 DEG C of temperature is controlled during dropwise addition, after being added dropwise to complete, hydrochloric acid is detected and whether natrium nitrosum is excessive, protect
Hydrochloric acid and the micro- excess of natrium nitrosum are held, is incubated 0~5 DEG C, is incubated 1h, 0.5g sulfamic acids is then added, removes excessive nitrous
Sour sodium, it is standby to obtain diazol.
(3) it is coupled：Diazol is all added in the condensation product in the step (1) filtered, then with 15% carbon
Sour sodium adjusts pH value between 6~6.5,5~10 DEG C of temperature control in coupled processes, after pH value is adjusted, is incubated 2h.
(4) secondary condensation：By 0.13mol, o ethyl aniline, it is added in coupling solution, pH is adjusted with 15% sodium carbonate
It is worth between 7~7.5, and slowly between 15~20 DEG C of heating, and keeping temperature and pH, terminate until reacting, TLC (chromatography)
Detect terminal.
Filter desalination：Two feed liquids to have contracted are separately added into be condensed the activated carbon of feed liquid mass fraction 1%, 1% silicon
Diatomaceous earth, filtered with press filtration bed, then the filter element filtering with PP1.0um, desalination then is carried out with NF membrane, has kept liquid level, dyestuff
Concentration is 5%, starts to concentrate until the electrical conductivity of desalinization wastewater is less than 0.5ms/cm, concentration concentration to 15% or so.
(5) hydrolyze：The hydrochloric acid that 0.09mol concentration is 30% is added in concentrate solution into step (4) after filtering desalination,
PH value is adjusted between 1~1.5, being then warming up to 95 DEG C, insulation, until reaction terminates.TLC (chromatography) detects terminal, so
PH value is adjusted to 8 with 20% sodium hydroxide afterwards.
(6) desalination：By the feed liquid hydrolyzed in step (5) with after PP1.0um filter element filtering, with NF membrane desalination,
25% concentration is concentrated to, then finished product is obtained after nylon filter element filtering.
Gained finished product 166g, mass concentration be 25% concentration finished product, yield 95.6%.(according to real income finished product
Quality reacts the mass ratio calculated yield of gained finished product with throwing raw material completely in the ideal situation)
Embodiment 3
(1) H acid dissolving：0.1mol H acid is distributed in 300g water, then adjusted the pH of solution with 20% sodium hydroxide
It is whole all after dissolving, to stir 0.5h between 6-6.5, it is standby；
Cyanuric Chloride disperses：0.15mol Cyanuric Chloride is distributed in 200g frozen water, disperses 0.5h, make it scattered equal
It is even；
Condensation：The H acid solutions that will have been dissolved, are slowly added drop-wise in Cyanuric Chloride dispersion liquid, during dropwise addition, do not control
PH, 0~5 DEG C of temperature is controlled, be 1.8~2.2 with sodium bicarbonate powder adjustment pH value after dripping.Control temperature and pH until
Reaction terminates.TLC (chromatography) detects terminal.
Filtering：The condensation solution reacted is filtered with Medium speed filter paper, removes excessive Cyanuric Chloride, in filter process,
0-5 DEG C of keeping temperature.After having filtered, insulation is standby.
(2) diazonium：0.1mol p-aminobenzene sulfonic acid, it is distributed in 100g water, then adjusts pH with 20% sodium hydroxide
It is worth 8, it is all dissolved, 0.5h is stirred after dissolving, then 0.15mol natrium nitrosum dry powder is added in solution, stirs
It is standby to whole dissolvings.
0.3mol hydrochloric acid is added in 100g frozen water, stirs, is then slowly added drop-wise to above-mentioned p-aminobenzene sulfonic acid and Asia
In nitramine solution, 0~5 DEG C of temperature is controlled during dropwise addition, after being added dropwise to complete, hydrochloric acid is detected and whether natrium nitrosum is excessive, protect
Hydrochloric acid and the micro- excess of natrium nitrosum are held, is incubated 0~5 DEG C, is incubated 1h, 0.5g sulfamic acids is then added, removes excessive nitrous
Sour sodium, it is standby to obtain diazol.
(3) it is coupled：Diazol is all added in the condensation product in the step (1) filtered, then with 15% carbon
Sour sodium adjusts pH value between 6~6.5,5~10 DEG C of temperature control in coupled processes, after pH value is adjusted, is incubated 2h.
(4) secondary condensation：0.15mol N-ethylaniline is added in coupling solution, pH value is adjusted with 15% sodium carbonate
Between 7~7.5, and slowly between 15~20 DEG C of heating, and keeping temperature and pH, until reaction terminates, TLC (chromatography) is examined
Survey terminal.
Filter desalination：Two feed liquids to have contracted are separately added into be condensed the activated carbon of feed liquid mass fraction 1%, 1% silicon
Diatomaceous earth, filtered with press filtration bed, then the filter element filtering with PP1.0um, desalination then is carried out with NF membrane, has kept liquid level, dyestuff
Concentration is 5%, starts to concentrate until the electrical conductivity of desalinization wastewater is less than 0.5ms/cm, concentration concentration to 15% or so.
(5) hydrolyze：The hydrochloric acid that 0.09mol concentration is 30% is added in concentrate solution into step (4) after filtering desalination,
PH value is adjusted between 1~1.5, being then warming up to 95 DEG C, insulation, until reaction terminates.TLC (chromatography) detects terminal, so
PH value is adjusted to 8 with 20% sodium hydroxide afterwards.
(6) desalination：By the feed liquid hydrolyzed in step (5) with after PP1.0um filter element filtering, with NF membrane desalination,
25% concentration is concentrated to, then finished product is obtained after nylon filter element filtering.
Gained finished product 166g, mass concentration be 25% concentration finished product, yield 95.6%.(according to real income finished product
Quality reacts the mass ratio calculated yield of gained finished product with throwing raw material completely in the ideal situation)
Implementation result：It is shown in Table shown in 1.2.3.4..
The each component of the final product that embodiment 1-3 is obtained and mass ratio in following form is mixed, used successively
0.45 micron and 0.22 micron of nylon membrane filtration, obtain the ink for being adapted to inkjet printing.
Table 1
| Composition | Ink A | Ink B | Ink C | Ink D |
| The final product compound sodium salt of embodiment 1 | 3 | - | - | - |
| ReactiveRed180 | - | 3 | - | - |
| ReactiveRed141 | - | - | 3 | - |
| ReactiveRed24 | - | - | - | 3 |
| Ultra-pure water | 35 | 35 | 35 | 35 |
| Glycerine | 5 | 5 | 5 | 5 |
| Diethylene glycol (DEG) | 15 | 15 | 15 | 15 |
| Diethylene glycol monobutyl ether | 5 | 5 | 5 | 5 |
| 1-Methyl-2-Pyrrolidone | 5 | 5 | 5 | 5 |
| Isopropanol | 5 | 5 | 5 | 5 |
Dyestuff in ink A for the final product sodium salt of embodiment 1 can respectively with the final product of embodiment 2 of equal quality,
The final product of embodiment 3 replaces that ink A is prepared.
(1) fluency
Test：Epson R 230, print software：Photo shop, printing model：High-quality photo prints (image
Enhancing technology), print paper type:Bloom printing paper and Alhue paper.
It is continuous to print more than page 20, printing head test, do not break to be tested by fluency.
Ink A, B, C, D are tested by printing fluency.
(2) coloured light：
With the L.A.B values of EYE-ONE test printing color lumps, color distortion is contrasted, it is as a result as follows：
Table 2
From test result it can be seen that the coloured light that ink A is shown on different print media is gold-tinted red, ink
What water B was shown on different print media is blue light red, and ink C, color is also blue light under different print media
Red, coloured light of the ink D from ink A on different print media approach.
(3) stability test
1. after in the following table, being observed 4 weeks with 60 DEG C and 2 DEG C of condition of storage respectively filterability situations of change with whether there is it is heavy
Form sediment【Each ink filter 150g；PVDF filter paper (aperture 0.45um, diameter 47mm)】.Normal temperature is placed into start to filter.
Table 3
Note：
2.pH value changes situations：
Table 4
From test result as can be seen that it 4 weeks is still in stable state that ink A is stored under the conditions of 60 DEG C and 2 DEG C, its filterability
Do not change significantly and do not precipitate, and ink B, C, D have filtering sex chromosome mosaicism in various degree, subject matter is because activity
Dyestuff heat endurance is bad, and pH easily changes, and causes stability to change.
(4) comparison or purity of compound is synthesized
The chemical combination of purity and the conventional method synthesis for the compound that embodiment 1.2.3 synthesizes according to technical scheme
The purity of thing compares：The purity for the compound that embodiment 1~3 synthesizes it can be seen from liquid chromatogram in Figure of description
Respectively：97.167%, 98.097%, 97.275%, and the compound of conventional method synthesis only has 95.694%.
As seen from the above embodiment, the dyestuff synthesized by technical scheme is in coloured light, filterability, stability
The upper dyestuff that better than in the market is sold.
Described above is only the preferred embodiment of the present invention, it is noted that for the ordinary skill people of the art
For member, under the premise without departing from the principles of the invention, some improvements and modifications can also be made, these improvements and modifications also should
It is considered as protection scope of the present invention.
Claims (8)
- A kind of 1. preparation method of the orchil compound with structure shown in Formulas I：Wherein R is SO3H, B are：Anilino-, methylphenylamine base, N-ethylaniline base, o ethyl aniline base, o-methyl-benzene amido One kind；The preparation method of the orchil compound with structure shown in Formulas I comprises the following steps：(1) Cyanuric Chloride and the H acid with structure shown in Formula II are subjected to condensation reaction, obtain the change of the structure as shown in formula III Compound：(2) compound with structure shown in formula IV and natrium nitrosum are subjected to diazo-reaction in an hcl ambient, had Structure diazenium compound shown in Formula V：(3) by the diazenium compound with Formula V structure that the step (2) obtains and the step (1) obtain with formula The compound of structure shown in III carries out coupling reaction, obtains structural compounds shown in Formula IV：(4) aniline or anil are carried out with the compound with structure shown in Formula IV that the step (5) obtains secondary Condensation, obtain having the compound of structure shown in Formula VII：(5) compound of structure is hydrolyzed in acid condition shown in the Formula VII for obtaining the step (4), obtains Formulas I institute Show the compound of structure；There is no time sequencing between described step (1) and step (2).
- 2. preparation method as claimed in claim 1, it is characterised in that the temperature of condensation reaction is 0~5 in the step (1) DEG C, the time of condensation reaction is 1~2 hour；Condensation reaction is carried out under conditions of being 5.5~7 in pH value.
- 3. preparation method as claimed in claim 1, it is characterised in that the diazo reaction temperature in the step (2) is 5~15 DEG C, the diazo reaction time is 0.8~1.2h；Diazo reaction is carried out under conditions of being 6~7 in pH value.
- 4. preparation method as claimed in claim 1, it is characterised in that couple temperature is 5~15 DEG C in the step (3), even The conjunction time is 0.8~1.2h；Coupling reaction is carried out under conditions of being 6~7 in pH value.
- 5. preparation method as claimed in claim 1, it is characterised in that secondary condensation temperature is 15~30 in the step (4) DEG C, the secondary condensation time is 1.5~2.5h；Consecutive condensation is carried out under conditions of being 6.3~7.5 in pH value.
- 6. preparation method as claimed in claim 1, it is characterised in that hydrolysis temperature is 85~97 DEG C in the step (5), water The solution time is 3.5~4.5h；Hydrolysis is carried out under conditions of being 1~2 in pH value.
- 7. preparation method as claimed in claim 1, it is characterised in that Cyanuric Chloride is with having Formula II institute in the step (1) The mol ratio for showing the H acid of structure is 1.03~1.5：1；The have compound of structure shown in formula IV and the mol ratio of natrium nitrosum described in step (2) are 1：1.03~1.5；The diazenium compound with Formula V structure described in step (3) and the mol ratio with structural compounds shown in Formula II For 1：1.03~1.5；The chemical combination with structure shown in Formula IV that aniline or anil described in step (4) obtain with the step (5) The mol ratio of thing is 1.03~1.5：1.
- 8. preparation method as claimed in claim 1, it is characterised in that anil is methylphenylamine in step (4), N- MEA, o ethyl aniline or o-toluidine.
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| US5599386A (en) * | 1994-05-12 | 1997-02-04 | Mitsubishi Chemical Corporation | Recording liquid |
| JPH09202043A (en) * | 1996-01-29 | 1997-08-05 | Mitsubishi Chem Corp | Formation of color image |
| JP2000265099A (en) * | 1999-01-13 | 2000-09-26 | Mitsubishi Chemicals Corp | Ink jet recording method |
| GB0208444D0 (en) * | 2002-04-12 | 2002-05-22 | Clariant Int Ltd | Composition for printing recording materials |
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