CN105860571A - Preparation method of acid yellow N-R - Google Patents
Preparation method of acid yellow N-R Download PDFInfo
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- CN105860571A CN105860571A CN201610210566.6A CN201610210566A CN105860571A CN 105860571 A CN105860571 A CN 105860571A CN 201610210566 A CN201610210566 A CN 201610210566A CN 105860571 A CN105860571 A CN 105860571A
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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
- C09B35/00—Disazo and polyazo dyes of the type A<-D->B prepared by diazotising and coupling
- C09B35/02—Disazo dyes
- C09B35/037—Disazo dyes characterised by two coupling components of different types
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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
- C09B35/00—Disazo and polyazo dyes of the type A<-D->B prepared by diazotising and coupling
- C09B35/02—Disazo dyes
- C09B35/039—Disazo dyes characterised by the tetrazo component
- C09B35/34—Disazo dyes characterised by the tetrazo component the tetrazo component being heterocyclic
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Abstract
The invention discloses a preparation method of acid yellow N-R. The method comprises the following steps: (S1) introducing a benzidine compound with a structural general formula shown in the specification and an acid reagent into a reactor, and stirring and mixing uniformly; (S2) adding nitrite into the reactor and stirring for reacting to obtain diazonium salt; (S3) preparing an alkaline solution containing 5-pyrazolone; (S4) adding the alkaline solution containing 5-pyrazolone in the step (S3) into the reactor in the step (S2) for reacting with the diazonium salt to obtain an azo intermediate I; (S5) preparing an alkaline solution of 5-pyrazolone with the same concentration as (S3), and adding into the reactor in the (S4) for reacting with the azo intermediate I to obtain an azo intermediate II; and (S6) after the reaction, performing salting-out, filtration and drying in the reactor to obtain acid yellow N-R powder, wherein R1 is (CH2)nCH3, and n>=0. The method disclosed by the invention has the following beneficial effects: by mainly adopting the benzidine compound as a raw material, the hydrophilic groups contained in the synthesis product acid yellow are reduced, and an effect of improving the washing fastness of acid yellow is realized.
Description
Technical field
The present invention relates to the preparation method of a kind of chemical dye, particularly relate to the preparation method of a kind of Indian yellow N-R.
Background technology
Indian yellow is a kind of acidic mono azo dyestuffs, and due to it, to have lovely luster, coloring good, therefore by extensively
For numerous areas such as textile printing and dyeing, coated coating or Fypros.Indian yellow is also known as acid fluorescence yellow simultaneously, is a kind of
Fluorescent material, owing to having conjugatedπbond in its structure, can dissipate green-yellow light under ultra violet lamp, thus use this dyestuff
Printed fabrics is more bright-coloured, dazzling.Furthermore, the gold with fastness to light after being coordinated by Indian yellow, can be formed with transition metal ions
Metal complex dyestuff, after the azo group in Indian yellow and transition metal ions generation complex reaction, it is not easy to light oxygen occurs again
Change reaction and fade.
The patent of Publication No. CN105176134A discloses a kind of high-dissolvability acid yellow dye such as at present, and it prepares step
Suddenly include: metanilic acid is in inorganic acid medium and sodium nitrite reaction obtains diazol, is then added thereto to 2-acetyl
Base dimethyl succinate, adds acid binding agent and carries out being condensed to diazol and disappear, and adds adjusting PH with base to after alkalescence.P-aminophenyl sulphur
Acid is in inorganic acid medium and sodium nitrite reaction obtains diazol, and with condensation liquid coupling, coupling solution heats up after adding alkali again and hydrolyzes,
It is spray-dried to obtain finished product again.
In such scheme, the acid yellow dye of preparation is applied in printed fabrics, substantial amounts of owing to containing in Indian yellow molecular structure
Sulfonic group, and sulfonic group is hydrophilic radical, therefore printed fabrics etc. are when washing, and stain is easily dissolved in aqueous solution and causes
It is eluted down from printed fabrics, the low range constraining this acid yellow dye of washing fastness performance.Indian yellow exists simultaneously
In dyestuff, its yellow is as dominant hue, and the importance of its washing fastness is especially prominent.Indian yellow the most of the prior art is resistance to
Washing fastness aspect needs to improve and improves.
Summary of the invention
The deficiency existed for prior art, it is an object of the invention to provide the preparation method of a kind of Indian yellow N-R, mainly
By using diphenyl amine compound as raw material, reduce the hydrophilic radical contained in synthetic product Indian yellow, reach to improve
Indian yellow is in the effect of washing fastness.
For achieving the above object, the technical scheme is that the preparation method of a kind of Indian yellow N-R, including with
Lower step: step S1, the diphenyl amine compound and acid reagent with following general structural formula are passed through in reactor, and add
Frozen water mixes, stirring and evenly mixing 5～20min；Step S2, in above-mentioned reactor, add nitrite stirring reaction 1～3h obtain
Diazol；Step S3,5-pyrazolone is dissolved in sodium hydroxide solution preparation containing the alkaline solution of 5-pyrazolone；Step
S4, the alkaline solution of the 5-pyrazolone in step S3 is joined the reactor in step S2 reacts with diazol 2～4h
Obtain azo intermediate I；Step S5, preparation join step with the alkaline solution of the 5-pyrazolone of step S3 same concentrations
Reactor in S4 reacts 2～4 hours with azo intermediate I and obtains azo intermediate II；Step S6, question response terminate backward
Reactor adds fine salt saltout, filter after analysis is clear, dry and obtain the Indian yellow N-R powder that power part is 260%；
Wherein, diphenyl amine compound:
Azo intermediate I:
Azo intermediate II:Wherein R1
For (CH2) nCH3, n >=0.
As preferably, when R1 is CH3Time, being passed through the nitrite in reactor in step S2 is sodium nitrite, and its with
The mol ratio of diphenyl amine compound is 1:(0.5～0.3).
As preferably, in described step S3, in terms of molal weight, described 5-pyrazolone and the use of diphenyl amine compound
Amount ratio is 1:(1～0.8).
The present invention has an advantage that for S1 and S2, in the ice water solution containing acid reagent, and diphenyl amine chemical combination
Thing reacts with nitrite, and the diazol generated at low ambient temperatures is not easy to decompose.Preferably employ hydrochloric acid or sulphuric acid is made
For acid reagent, it provides strong acidic environment for reaction, and frozen water provides low temperature environment for reaction, in low temperature strongly acidic solution
Being more beneficial for the generation of diazol, favors low temperature preserves in diazol simultaneously, slows down its decomposition rate.Use sodium nitrite simultaneously
As nitrite, the metallic sodium ion in sodium nitrite is present in reaction solution and reaction will not be produced impact, the most corresponding
Need to use in S6 and saltout to fine salt, containing substantial amounts of metallic sodium ion in fine salt, the most also will not produce cation miscellaneous
Matter.
When n is 0, diphenyl amine compound is 3, and 3'-dimethylbenzidine is used for preparing Indian yellow compared to prior art
Aminobenzenesulfonic acid, aminobenzenesulfonic acid contains hydrophilic sulfonic group, and sulfonic group is not involved in reaction in course of reaction, because of
Indian yellow of this final synthesis has a big hydrophilic, and the present invention uses 3, its sulfonic acid not contained of 3'-dimethylbenzidine
Base, does not brings hydrophilic radical from reactant feed angle in the product therefore synthesized, therefore water-fast relative to existing Indian yellow
The advantage washing fastness high is apparent.
And when n is 0, control sodium nitrite and 3, the scope of the mol ratio of 3'-dimethylbenzidine is at 1:(0.5～0.3) between,
Realize under appropriate sodium nitrite, it is possible to 3,3'-dimethylbenzidine fully reacts production diazol, the most beneficially diazol
Generating, the most later in S3, appropriate nitrate ion is conducive to using sodium bicarbonate quickly by reaction solution pH regulator to 5～6
In the range of.Contrary when the consumption of sodium nitrite exceeds this scope, containing a large amount of unreacted nitrite ions in solution,
Easily decompose under acid reagent and then impact is to experimental situation.
The 5-pyrazolone that in the present invention, reactor containing diazol adds in S2, control its with 3,3'-dimethylbenzidine
The scope of mol ratio at 1:(1～0.8) between, advantageous as coupling component 5-pyrazolone with as diazo component
Diazol generation coupling reaction generates has coloured azo intermediate I, and after reacting certain time, then add in reactor
Entering 5-pyrazolone, and control and 3, the scope of the mol ratio of 3'-dimethylbenzidine is still in 1:(1～0.8) between, from
And obtain having coloured azo intermediate II.And 5-pyrazolone again after S4 reaction 2～4h again, its reason is the 5-of excess
Pyrazolone is difficult to generate azo intermediate II with diazol, and is gradually added the yield improving azo intermediate II.
A kind of common Nacl of fine salt, is readily obtained and has characteristic soluble in water, in the present invention can rapid solution
In mixed solution, reduce the dissolubility of azo intermediate II, beneficially azo intermediate II within a short period of time completely from mixing
Separating out in solution, after saltouing, filtering drying improves its productivity ratio.
As preferably, after step S4 adds 5-pyrazolone, use sodium bicarbonate regulation pH value of solution to 5.5～7.5.
The present invention has an advantage that in the present invention, the azo of 5-pyrazolone and diazol reacts at the model that pH is 5.5～7.5
Enclose interior most preferably, sodium bicarbonate is acid salt NaHCO3, present alkalescence when being dissolved in water, regulate the reagent of pH value of solution as the present invention,
NaHCO3Reagent has the advantages that alkalescence is weak, owing to optimal pH scope is only between 5.5～7.5, and drips to reactor
The NaHCO that alkalescence is weak3Reagent, though add acidic materials that volume neutralizes also only some, be thus advantageous to experimenter
Operation and control；What is more important, when pH value is less than 5.5, the amine in diazol becomes ammonium salt, is unfavorable for coupling reaction,
Accommodative excess causes pH value of solution too high, solution alkaline, when pH value is more than 7.5, then can destroy diazol, and diazol generates
Diazotic acid or the diazonium acid radical anion of coupling reaction can not be carried out, be unfavorable for the generation of azo intermediate I, otherwise easily give birth to
Become symmetrical product, and symmetrical products to be present in azo intermediate I be even as a kind of impurity with azo intermediate II precipitation,
Because the water solublity of symmetrical products is too big, washing fastness is poor, so needing to use sodium bicarbonate regulation pH and should not be too high.
As preferably, after step S5 adds 5-pyrazolone, use soda regulation pH value of solution to 8～10.
The present invention has an advantage that when the pH of solution is in the range of 8～10, increases solution alkaline, promotes 5-pyrazolone
Coupling with azo intermediate I generates azo intermediate II, and diazol reaction completely, reaches second in this alkaline range
Solution does not contains after secondary coupling reaction the purpose of diazol so that reactant all generates principal product；Alkalescence should not mistake simultaneously
Height, pH is too high, has by-product and generates, and diazol is not easy to 5-pyrazolone generation coupling, and pH is in the range of 8～10
Then avoid this phenomenon, improve raw material availability and productivity；Furthermore soda is sodium hydroxide, its solution relatively NaHCO3Alkali
Property strong, relatively easily by pH regulator to 8～10.
As preferably, the alkaline solution in step S3 is also dissolved with 4-nitro phenyl ester, and 5-pyrazolone and 4-nitro phenyl ester
Mol ratio be 1:(0.06～0.03).
The present invention has an advantage that coupling reaction is the choice that diazol decomposes and product generates, and typically can only obtain as far as possible
Many synthetic products, but diazol can not be stopped and decompose, mixed solution adds 4-nitro phenyl ester, although to generation afterwards
Thing azo intermediate I and azo intermediate II have carried impurity, but impurity is a small amount of, and Nitrobenzol fat can suppress diazol
Decomposing generation 3,3-1 dimethyl diphenyl ion and nitrogen, and then prevent 3,3-1 dimethyl diphenyl ion generates phenol with water molecule reaction,
By reducing the decomposition amount of diazol, thus avoid diazol to generate relatively large impurity, improve the utilization rate of diazol.
As preferably, the alkaline solution in step S5 is also dissolved with pyridine, and the mol ratio of 5-pyrazolone and pyridine is 1:
(0.08～0.05).
The present invention has an advantage that when carbon atom in azo intermediate I ion attack 5-pyrazolone, often due to carbon
The reason that Atomic Electron Cloud density is higher hinders coupling reaction, does not utilize and generates azo intermediate II, and pyridine conduct in the present invention
Base catalyst, pyridine, owing to having lone pair electrons on its nitrogen-atoms, can be activated in the middle of azo by the attack of its nucleophilic electronics
Body I, promotes the carbon atom that in azo intermediate I attack 5-pyrazolone, cloud density is higher, reduces space resistance, thus
It is not only able to shorten the response time, and makes generation azo intermediate I thoroughly react generation azo intermediate II, thus improve
Yield.
As preferably, nitrite and compound I in step S2 react under the conditions of magnetic agitation.
The present invention has an advantage that magnetic agitation accelerates nitrate and compound I response speed so that in frozen water temperature
Complete reaction under conditions of low, be not easy at low temperatures due to diazol to decompose, can decompose after temperature rises, it will decrease
The reactant feed of coupling reaction in S3.
Detailed description of the invention
Comparative example, use Publication No. CN105176134A patent in operating procedure, take the m-aminophenyl of 0.05mol
Sulfonic acid prepares a certain amount of Indian yellow.
Embodiment 1,
S1, in 500ml there-necked flask, put into 3,3'-dimethylbenzidine 10.6g, water 100ml, ice 100g, hydrochloric acid 10ml, mixed
Even and stir 5 minutes；
S2, in above-mentioned reactor, add sodium nitrite 6.9g react 2h under magnetic stirring and obtain diazol；S3, to 200ml burn
Add sodium hydroxide 4g in Bei and add 100ml water dissolution, in dissolving backward beaker, adding 5-pyrazolone 8.4g；
S4, the alkaline solution of the 5-pyrazolone in S3 is joined and the reactor in S2 reacts 2h with diazol obtains in azo
Mesosome I；
S5, in 200ml beaker, add sodium hydroxide 4g add 100ml water dissolution, in dissolving backward beaker, add 5-pyrazoline
Ketone 8.4g, and add it to the reactor in S4 reacts 2 hours with azo intermediate I obtain azo intermediate II；
S6, question response terminate to add 50g fine salt in backward reactor and saltout, and filter, and put into dehydrator baking after saltouing completely
Dry, obtain the Indian yellow N-R powder that power part is 260%.
Embodiment 2,
It is with the difference of embodiment 1: the mol ratio of sodium nitrite and 3,3'-dimethylbenzidine is 1:0.4, i.e. S1, at 500ml
Input 3 in there-necked flask, 3'-dimethylbenzidine 10.6g (0.05mol), water 100ml, ice 100g, hydrochloric acid 10ml, mixing
And stir 6 minutes；
S2, in above-mentioned reactor, add sodium nitrite 8.6g (0.125mol) react 2h under magnetic stirring and obtain diazol；S3、
In 200ml beaker, add sodium hydroxide 4g and add 100ml water dissolution, in dissolving backward beaker, adding 5-pyrazolone 8.4g
(0.1mol)；
S4, the alkaline solution of the 5-pyrazolone in S3 is joined and the reactor in S2 reacts 2h with diazol obtains in azo
Mesosome I；
S5, in 200ml beaker, add sodium hydroxide 4g add 100ml water dissolution, in dissolving backward beaker, add 5-pyrazoline
Ketone 8.4g (0.1mol), and add it to the reactor in S4 reacts 2 hours with azo intermediate I obtain in the middle of azo
Body II；
S6, question response terminate to add 50g fine salt in backward reactor and saltout, and filter, and put into dehydrator baking after saltouing completely
Dry, obtain the Indian yellow N-R powder that power part is 260%.
Embodiment 3,
It is with the difference of embodiment 2: the mol ratio of 5-pyrazolone and 3,3'-dimethylbenzidine is 1:0.9, i.e. S1, at 500ml
Input 3 in there-necked flask, 3'-dimethylbenzidine 10.6g (0.05mol), water 100ml, ice 100g, hydrochloric acid 10ml, mixing
And stir 6 minutes；
S2, in above-mentioned reactor, add sodium nitrite 8.6g (0.125mol) react 2h under magnetic stirring and obtain diazol；S3、
In 200ml beaker, add sodium hydroxide 4g and add 100ml water dissolution, in dissolving backward beaker, adding 5-pyrazolone 4.6g
(0.055mol)；
S4, the alkaline solution of the 5-pyrazolone in S3 is joined and the reactor in S2 reacts 2h with diazol obtains in azo
Mesosome I；
S5, in 200ml beaker, add sodium hydroxide 4g add 100ml water dissolution, in dissolving backward beaker, add 5-pyrazoline
Ketone 4.6g (0.055mol), and add it to the reactor in S4 reacts 2 hours with azo intermediate I obtain in azo
Mesosome II；
S6, question response terminate to add 50g fine salt in backward reactor and saltout, and filter, and put into dehydrator baking after saltouing completely
Dry, obtain the Indian yellow N-R powder that power part is 260%.
Embodiment 4,
Be with the difference of embodiment 3: after adding 5-pyrazolone in S4, use sodium bicarbonate regulation pH value of solution is to 5.5, i.e. S1,
Input 3 in 500ml there-necked flask, 3'-dimethylbenzidine 10.6g (0.05mol), water 100ml, ice 100g, hydrochloric acid 10ml,
Mix and stir 6 minutes；
S2, in above-mentioned reactor, add sodium nitrite 4.2g (0.125mol) react 2h under magnetic stirring and obtain diazol；S3、
In 200ml beaker, add sodium hydroxide 4g and add 100ml water dissolution, in dissolving backward beaker, adding 5-pyrazolone 4.6g
(0.055mol)；
S4, the alkaline solution of the 5-pyrazolone in S3 is joined in the reactor in S2, and use carbonate reagent to be adjusted by solution
Joint is to 5.5, and reaction 2h obtains azo intermediate I；
S5, in 200ml beaker, add sodium hydroxide 4g add 100ml water dissolution, in dissolving backward beaker, add 5-pyrazoline
Ketone 4.6g (0.055mol), and add it to the reactor in S4 reacts 2 hours with azo intermediate I obtain in azo
Mesosome II；
S6, question response terminate to add 50g fine salt in backward reactor and saltout, and filter, and put into dehydrator baking after saltouing completely
Dry, obtain the Indian yellow N-R powder that power part is 260%.
Embodiment 5,
Be with the difference of embodiment 3: after adding 5-pyrazolone in S4, use sodium bicarbonate regulation pH value of solution is to 7.5, i.e. S1,
Input 3 in 500ml there-necked flask, 3'-dimethylbenzidine 10.6g (0.05mol), water 100ml, ice 100g, hydrochloric acid 10ml,
Mix and stir 6 minutes；
S2, in above-mentioned reactor, add sodium nitrite 2.76g (0.4mol) react 2h under magnetic stirring and obtain diazol；S3、
In 200ml beaker, add sodium hydroxide 4g and add 100ml water dissolution, in dissolving backward beaker, adding 5-pyrazolone 4.6g
(0.055mol)；
S4, the alkaline solution of the 5-pyrazolone in S3 is joined in the reactor in S2, and use carbonate reagent to be adjusted by solution
Joint is to 7.5, and reaction 2h obtains azo intermediate I；
S5, in 200ml beaker, add sodium hydroxide 4g add 100ml water dissolution, in dissolving backward beaker, add 5-pyrazoline
Ketone 4.6g (0.055mol), and add it to the reactor in S4 reacts 2 hours with azo intermediate I obtain in azo
Mesosome II；
S6, question response terminate to add 50g fine salt in backward reactor and saltout, and filter, and put into dehydrator baking after saltouing completely
Dry, obtain the Indian yellow N-R powder that power part is 260%.
Embodiment 6,
Be with the difference of embodiment 3: after adding 5-pyrazolone in S4, use sodium bicarbonate regulation pH value of solution is to 6, i.e. S1,
Input 3 in 500ml there-necked flask, 3'-dimethylbenzidine 10.6g (0.05mol), water 100ml, ice 100g, hydrochloric acid 10ml,
Mix and stir 6 minutes；
S2, in above-mentioned reactor, add sodium nitrite 2.76g (0.4mol) react 2h under magnetic stirring and obtain diazol；S3、
In 200ml beaker, add sodium hydroxide 4g and add 100ml water dissolution, in dissolving backward beaker, adding 5-pyrazolone 4.6g
(0.055mol)；
S4, the alkaline solution of the 5-pyrazolone in S3 is joined in the reactor in S2, and use carbonate reagent to be adjusted by solution
Joint is to 6, and reaction 2h obtains azo intermediate I；
S5, in 200ml beaker, add sodium hydroxide 4g add 100ml water dissolution, in dissolving backward beaker, add 5-pyrazoline
Ketone 4.6g (0.055mol), and add it to the reactor in S4 reacts 2 hours with azo intermediate I obtain in azo
Mesosome II；
S6, question response terminate to add 50g fine salt in backward reactor and saltout, and filter, and put into dehydrator baking after saltouing completely
Dry, obtain the Indian yellow N-R powder that power part is 260%.
Embodiment 7,
With main difference is that of embodiment 3: after adding 5-pyrazolone in S5, use soda regulation pH value of solution is to 8, i.e.
S1, in 500ml there-necked flask put into 3,3'-dimethylbenzidine 10.6g (0.05mol), water 100ml, ice 100g, hydrochloric acid
10ml, mixes and stirs 6 minutes；
S2, in above-mentioned reactor, add sodium nitrite 2.76g (0.4mol) react 2h under magnetic stirring and obtain diazol；S3、
In 200ml beaker, add sodium hydroxide 4g and add 100ml water dissolution, in dissolving backward beaker, adding 5-pyrazolone 4.6g
(0.055mol)；
S4, the alkaline solution of the 5-pyrazolone in S3 is joined and the reactor in S2 reacts 2h with diazol obtains in azo
Mesosome I；
S5, in 200ml beaker, add sodium hydroxide 4g add 100ml water dissolution, in dissolving backward beaker, add 5-pyrazoline
Ketone 4.6g (0.055mol), adds it in the reactor in S4, and use soda by the pH regulator of solution to 8, then
React and obtain azo intermediate II in 2 hours；
S6, question response terminate to add 50g fine salt in backward reactor and saltout, and filter, and put into dehydrator baking after saltouing completely
Dry, obtain the Indian yellow N-R powder that power part is 260%.
Embodiment 8,
With main difference is that of embodiment 3: after adding 5-pyrazolone in S5, use soda regulation pH value of solution is to 10, i.e.
S1, in 500ml there-necked flask put into 3,3'-dimethylbenzidine 10.6g (0.05mol), water 100ml, ice 100g, hydrochloric acid
10ml, mixes and stirs 6 minutes；
S2, in above-mentioned reactor, add sodium nitrite 2.76g (0.4mol) react 2h under magnetic stirring and obtain diazol；S3、
In 200ml beaker, add sodium hydroxide 4g and add 100ml water dissolution, in dissolving backward beaker, adding 5-pyrazolone 4.6g
(0.055mol)；
S4, the alkaline solution of the 5-pyrazolone in S3 is joined and the reactor in S2 reacts 2h with diazol obtains in azo
Mesosome I；
S5, in 200ml beaker, add sodium hydroxide 4g add 100ml water dissolution, in dissolving backward beaker, add 5-pyrazoline
Ketone 4.6g (0.055mol), adds it in the reactor in S4, and use soda by the pH regulator of solution to 10,
React again 2 hours and obtain azo intermediate II；
S6, question response terminate to add 50g fine salt in backward reactor and saltout, and filter, and put into dehydrator baking after saltouing completely
Dry, obtain the Indian yellow N-R powder that power part is 260%.
Embodiment 9,
With main difference is that of embodiment 3: after adding 5-pyrazolone in S5, use soda regulation pH value of solution is to 9, i.e.
S1, in 500ml there-necked flask put into 3,3'-dimethylbenzidine 10.6g (0.05mol), water 100ml, ice 100g, hydrochloric acid
10ml, mixes and stirs 6 minutes；
S2, in above-mentioned reactor, add sodium nitrite 2.76g (0.4mol) react 2h under magnetic stirring and obtain diazol；S3、
In 200ml beaker, add sodium hydroxide 4g and add 100ml water dissolution, in dissolving backward beaker, adding 5-pyrazolone 4.6g
(0.055mol)；
S4, the alkaline solution of the 5-pyrazolone in S3 is joined and the reactor in S2 reacts 2h with diazol obtains in azo
Mesosome I；
S5, in 200ml beaker, add sodium hydroxide 4g add 100ml water dissolution, in dissolving backward beaker, add 5-pyrazoline
Ketone 4.6g (0.055mol), adds it in the reactor in S4, and use soda by the pH regulator of solution to 9, then
React and obtain azo intermediate II in 2 hours；
S6, question response terminate to add 50g fine salt in backward reactor and saltout, and filter, and put into dehydrator baking after saltouing completely
Dry, obtain the Indian yellow N-R powder that power part is 260%.
Embodiment 10,
With main difference is that of embodiment 3: after adding 5-pyrazolone in S4, use sodium bicarbonate regulation pH value of solution is to 6,
After adding 5-pyrazolone in S5, use soda regulation pH value of solution is to 9, i.e. S1, input 3 in 500ml there-necked flask, 3'-bis-
Methyl biphenyl amine 10.6g (0.05mol), water 100ml, ice 100g, hydrochloric acid 10ml, mix and stir 6 minutes；
S2, in above-mentioned reactor, add sodium nitrite 2.76g (0.4mol) react 2h under magnetic stirring and obtain diazol；S3、
In 200ml beaker, add sodium hydroxide 4g and add 100ml water dissolution, in dissolving backward beaker, adding 5-pyrazolone 4.6g
(0.055mol)；
S4, the alkaline solution of the 5-pyrazolone in S3 is joined in the reactor in S2, and use carbonate reagent to be adjusted by solution
Joint is to 6, and reaction 2h obtains azo intermediate I；
S5, in 200ml beaker, add sodium hydroxide 4g add 100ml water dissolution, in dissolving backward beaker, add 5-pyrazoline
Ketone 4.6g (0.055mol), adds it in the reactor in S4, and use soda by the pH regulator of solution to 9, then
React and obtain azo intermediate II in 2 hours；
S6, question response terminate to add 50g fine salt in backward reactor and saltout, and filter, and put into dehydrator baking after saltouing completely
Dry, obtain the Indian yellow N-R powder that power part is 260%.
Embodiment 11,
With main difference is that of embodiment 10: the alkaline solution in S3 is also dissolved with 4-nitro phenyl ester, and 5-pyrazolone
Be 1:0.04 with the mol ratio of 4-nitro phenyl ester, i.e. S1, input 3 in 500ml there-necked flask, 3'-dimethylbenzidine 10.6g
(0.05mol), water 100ml, ice 100g, hydrochloric acid 10ml, mix and stir 6 minutes；
S2, in above-mentioned reactor, add sodium nitrite 2.76g (0.4mol) react 2h under magnetic stirring and obtain diazol；S3、
In 200ml beaker, add sodium hydroxide 4g and add 100ml water dissolution, in dissolving backward beaker, adding 5-pyrazolone 4.6g
(0.055mol) 4-nitro phenyl ester 1.84g mixing, it is simultaneously introduced；
S4, the alkaline solution of the 5-pyrazolone in S3 is joined in the reactor in S2, and use carbonate reagent to be adjusted by solution
Joint is to 6, and reaction 2h obtains azo intermediate I；
S5, in 200ml beaker, add sodium hydroxide 4g add 100ml water dissolution, in dissolving backward beaker, add 5-pyrazoline
Ketone 4.6g (0.055mol), adds it in the reactor in S4, and use soda by the pH regulator of solution to 9, then
React and obtain azo intermediate II in 2 hours；
S6, question response terminate to add 50g fine salt in backward reactor and saltout, and filter, and put into dehydrator baking after saltouing completely
Dry, obtain the Indian yellow N-R powder that power part is 260%.
Embodiment 12,
With main difference is that of embodiment 10: the alkaline solution in S5 is also dissolved with pyridine, and 5-pyrazolone and pyridine
Mol ratio be 1:0.06, i.e. S1, in 500ml there-necked flask put into 3,3'-dimethylbenzidine 10.6g (0.05mol),
Water 100ml, ice 100g, hydrochloric acid 10ml, mix and stir 6 minutes；
S2, in above-mentioned reactor, add sodium nitrite 2.76g (0.4mol) react 2h under magnetic stirring and obtain diazol；S3、
In 200ml beaker, add sodium hydroxide 4g and add 100ml water dissolution, in dissolving backward beaker, adding 5-pyrazolone 4.6g
(0.055mol)；
S4, the alkaline solution of the 5-pyrazolone in S3 is joined in the reactor in S2, and use carbonate reagent to be adjusted by solution
Joint is to 6, and reaction 2h obtains azo intermediate I；
S5, in 200ml beaker, add sodium hydroxide 4g add 100ml water dissolution, in dissolving backward beaker, add 5-pyrazoline
Ketone 4.6g (0.055mol), is simultaneously introduced pyridine 0.2g mixing, is joined by mixed solution in the reactor in S4, and make
With soda by the pH regulator of solution to 9, then react 2 hours and obtain azo intermediate II；
S6, question response terminate to add 50g fine salt in backward reactor and saltout, and filter, and put into dehydrator baking after saltouing completely
Dry, obtain the Indian yellow N-R powder that power part is 260%.
Embodiment 13,
With main difference is that of embodiment 10: the alkaline solution in S5 is also dissolved with pyridine, and 5-pyrazolone and pyridine
Mol ratio be 1:0.06, i.e. S1, in 500ml there-necked flask put into 3,3'-dimethylbenzidine 10.6g (0.05mol),
Water 100ml, ice 100g, hydrochloric acid 10ml, mix and stir 6 minutes；
S2, in above-mentioned reactor, add sodium nitrite 2.76g (0.4mol) react 2h under magnetic stirring and obtain diazol；S3、
In 200ml beaker, add sodium hydroxide 4g and add 100ml water dissolution, in dissolving backward beaker, adding 5-pyrazolone 4.6g
(0.055mol) 4-nitro phenyl ester 1.84g mixing, it is simultaneously introduced；
S4, the alkaline solution of the 5-pyrazolone in S3 is joined in the reactor in S2, and use carbonate reagent to be adjusted by solution
Joint is to 6, and reaction 2h obtains azo intermediate I；
S5, in 200ml beaker, add sodium hydroxide 4g add 100ml water dissolution, in dissolving backward beaker, add 5-pyrazoline
Ketone 4.6g (0.055mol), is simultaneously introduced pyridine 0.2g mixing, is joined by mixed solution in the reactor in S4, and make
With soda by the pH regulator of solution to 9, then react 2 hours and obtain azo intermediate II；
S6, question response terminate to add 50g fine salt in backward reactor and saltout, and filter, and put into dehydrator baking after saltouing completely
Dry, obtain the Indian yellow N-R powder that power part is 260%.
Embodiment 14,
It is with the difference of embodiment 1, when n is 2, i.e. uses 3,3'-dipropyl benzidine, S1, in 500ml tri-mouthfuls burning
In Ping, input 3,3'-dipropyl benzidine 12g (0.05mol), water 100ml, ice 100g, hydrochloric acid 10ml, mix and stir 5
Minute；
S2, in above-mentioned reactor, add sodium nitrite 1.7g (0.25mol) react 2h under magnetic stirring and obtain diazol；S3、
In 200ml beaker, add sodium hydroxide 4g and add 100ml water dissolution, in dissolving backward beaker, adding 5-pyrazolone 4.6g
(0.055mol)；
S4, the alkaline solution of the 5-pyrazolone in S3 is joined and the reactor in S2 reacts 2h with diazol obtains in azo
Mesosome I；
S5, in 200ml beaker, add sodium hydroxide 4g add 100ml water dissolution, in dissolving backward beaker, add 5-pyrazoline
Ketone 4.6g (0.055mol), and add it to the reactor in S4 reacts 2 hours with azo intermediate I obtain in azo
Mesosome II；
S6, question response terminate to add 50g fine salt in backward reactor and saltout, and filter, and put into dehydrator baking after saltouing completely
Dry, obtain the Indian yellow N-R powder that power part is 260%.
Test performance one: productivity, by embodiment 1 to embodiment 14 and comparative example dry product be placed into purchase in
Measure quality on the FA2204 electronic analytical balance of the horizontal flat instrument and meter factory in Shanghai, and calculate the productivity of each group, productivity
Shown in result form 1:
Test performance two: embodiment 1 to embodiment 14 and comparative example are respectively organized and used enough product 10g to common 40mm*100mm
Terylene cloth print and dye, after 5 day time, cloth is carried out washing fastness test, its method of testing use national standard
GB/T3921.1-1997 " textile color stability test color fastness to washing " tests, test result as shown in Table 1:
Form 1 productivity and water-fastness color fastness
The above is only the preferred embodiment of the present invention, and protection scope of the present invention is not limited merely to above-described embodiment, all belongs to
Technical scheme under thinking of the present invention belongs to protection scope of the present invention.It should be pointed out that, the ordinary skill for the art
For personnel, some improvements and modifications without departing from the principles of the present invention, these improvements and modifications also should be regarded as the present invention
Protection domain.
Claims (8)
1. a preparation method of Indian yellow N-R, comprises the following steps:
Step S1, the diphenyl amine compound and acid reagent with following general structural formula are passed through in reactor, and
Add frozen water mixing, stirring and evenly mixing 5～20min；
Step S2, in above-mentioned reactor, add nitrite stirring reaction 1～3h obtain diazol；
Step S3,5-pyrazolone is dissolved in sodium hydroxide solution preparation containing the alkaline solution of 5-pyrazolone；
Step S4, the alkaline solution of the 5-pyrazolone in step S3 is joined in the reactor in step S2 with
Diazol reaction 2～4h obtains azo intermediate I；
Step S5, preparation join the reaction in step S4 with the alkaline solution of the 5-pyrazolone of S3 same concentrations
Device reacts 2～4 hours with azo intermediate I and obtains azo intermediate II；
Step S6, question response terminate to add fine salt in backward reactor and saltout, and filter, dry and obtain power part after analysis is clear
It it is the Indian yellow N-R powder of 260%；
Wherein, diphenyl amine compound:
Azo intermediate I:
Azo intermediate II:
Wherein R1For (CH2)nCH3, n >=0.
The preparation method of a kind of Indian yellow N-R the most according to claim 1, it is characterised in that: work as R1For
CH3Time, being passed through the nitrite in reactor in S2 is sodium nitrite, and it is with diphenyl amine compound
Mol ratio is 1:(0.5～0.3).
The preparation method of a kind of Indian yellow N-R the most according to claim 2, it is characterised in that: described step
In S3, in terms of molal weight, described 5-pyrazolone is 1:(1～0.8 with the amount ratio of diphenyl amine compound).
The preparation method of a kind of Indian yellow N-R the most according to claim 3, it is characterised in that: step S4
Use sodium bicarbonate regulation pH value of solution to 5.5～7.5 after middle addition 5-pyrazolone.
The preparation method of a kind of Indian yellow N-R the most according to claim 4, it is characterised in that: step S5
Use soda regulation pH value of solution to 8～10 after middle addition 5-pyrazolone.
The preparation method of a kind of Indian yellow N-R the most according to claim 5, it is characterised in that: step S3
In alkaline solution be also dissolved with 4-nitro phenyl ester, and the mol ratio of 5-pyrazolone and 4-nitro phenyl ester is 1:
(0.06～0.03).
The preparation method of a kind of Indian yellow N-R the most according to claim 5, it is characterised in that: step S5
In alkaline solution be also dissolved with pyridine, and the mol ratio of 5-pyrazolone and pyridine is 1:(0.08～0.05).
The preparation method of a kind of Indian yellow N-R the most according to claim 1, it is characterised in that: step S2
In nitrite and compound I react under the conditions of magnetic agitation.
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| JPS5767677A (en) * | 1980-10-15 | 1982-04-24 | Ricoh Co Ltd | Ink composition for ink jet recording |
| JP2652071B2 (en) * | 1990-01-25 | 1997-09-10 | 日本化薬株式会社 | Color filter |
| CN101575459A (en) * | 2009-05-25 | 2009-11-11 | 安徽省凤阳染料化工有限公司 | Reactive acid yellow dye for nylon and preparation method thereof |
| CN105176134A (en) * | 2015-09-25 | 2015-12-23 | 恒升化工有限公司 | High-dissolvability acid yellow dye and preparation method thereof |
-
2016
- 2016-04-06 CN CN201610210566.6A patent/CN105860571B/en not_active Expired - Fee Related
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5767677A (en) * | 1980-10-15 | 1982-04-24 | Ricoh Co Ltd | Ink composition for ink jet recording |
| JP2652071B2 (en) * | 1990-01-25 | 1997-09-10 | 日本化薬株式会社 | Color filter |
| CN101575459A (en) * | 2009-05-25 | 2009-11-11 | 安徽省凤阳染料化工有限公司 | Reactive acid yellow dye for nylon and preparation method thereof |
| CN105176134A (en) * | 2015-09-25 | 2015-12-23 | 恒升化工有限公司 | High-dissolvability acid yellow dye and preparation method thereof |
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