CN108129875A - A kind of double-active radical blue active dye and its preparation method and application - Google Patents
A kind of double-active radical blue active dye and its preparation method and application Download PDFInfo
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- CN108129875A CN108129875A CN201711370187.4A CN201711370187A CN108129875A CN 108129875 A CN108129875 A CN 108129875A CN 201711370187 A CN201711370187 A CN 201711370187A CN 108129875 A CN108129875 A CN 108129875A
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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
- C09B62/00—Reactive dyes, i.e. dyes which form covalent bonds with the substrates or which polymerise with themselves
- C09B62/44—Reactive dyes, i.e. dyes which form covalent bonds with the substrates or which polymerise with themselves with the reactive group not directly attached to a heterocyclic ring
- C09B62/78—Reactive dyes, i.e. dyes which form covalent bonds with the substrates or which polymerise with themselves with the reactive group not directly attached to a heterocyclic ring with other reactive groups
- C09B62/82—Azo dyes
- C09B62/83—Disazo or polyazo dyes
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
- D06P1/00—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed
- D06P1/38—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed using reactive dyes
- D06P1/384—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed using reactive dyes reactive group not directly attached to heterocyclic group
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
- D06P3/00—Special processes of dyeing or printing textiles, or dyeing leather, furs, or solid macromolecular substances in any form, classified according to the material treated
- D06P3/58—Material containing hydroxyl groups
- D06P3/60—Natural or regenerated cellulose
- D06P3/66—Natural or regenerated cellulose using reactive dyes
- D06P3/666—Natural or regenerated cellulose using reactive dyes reactive group not directly attached to heterocyclic group
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Abstract
The present invention provides a kind of double-active radical blue active dyes, belong to reactive dyestuff field.Double-active radical blue dyes provided by the invention is diazo component by using the arylamine of β hydroxyethyl sulfone sulfates aryl amine derivatives and fluorine-containing pyrimidine group, and coupling reaction occurs under acid and alkaline condition with H acid derivatives c respectively and prepares.4 [2 [2 (sulfonic acid oxygen ethyl sulfuryl) ethyl] carbamyl] the phenyl class active groups contained in blue active dye of the present invention have higher alkali resistance hydrolytic stability; and the fluoropyrimidine active group contained has compared with high reaction activity, and the reactivity matching between two kinds of active groups.The double-active radical blue dyes is bright-colored, with higher degree of fixation with higher hydrolytic stability and on fiber.Embodiment statistics indicate that, degree of fixation of the double-active radical blue active dye provided by the invention on fiber is up to 86.6%.
Description
Technical field
The present invention relates to active dye technical field more particularly to a kind of double-active radical blue active dye and its preparation sides
Method and application.
Background technology
Reactive dye are to contain reactive group in molecular structure, can on fiber hydroxyl, amino groups react and
A kind of synthetic dyestuffs being covalently bonded on fiber.Fiber through reactive dyeing has high water-fastness and rub resistance jail
Degree, therefore, reactive dye have just been received by the market since exploitation.Since the dyeing of reactive dye typically carries out in water,
Therefore, the reactive group in reactive dye structure on fiber hydroxyl, amino groups react when also can exist hydrolysis
This side reaction.Reactive dye after hydrolysis can not be again with fiber-reactive, and remaining in becomes dyeing waste-water in dyeing liquor, not only unrestrained
Take resource and cause environmental pollution.
The degree of fixation for improving dyestuff is a kind of effective ways for improving reactive dye utilization rate and reducing dyeing waste water.Increase
The respond of reactive group and fiber in reactive dyestuff molecule structure, improve reactive group stability in water and
The raising of reactive dye color fixing rate can be realized by increasing the content of reactive group.Existing double-active radical dye mainly has double chlorine
S-triazine type, bishydroxyethylsulfone sulfuric acid ester type and the mixed type of a chloro-s-triazine and beta-hydroxyethyl sulfone sulfate.Double chlorine
The dyeing of s-triazine type dye usually requires to carry out at higher temperature, it would be desirable to be able to which consumption is higher.Bishydroxyethylsulfone sulfuric acid ester type
The more double chloro-s-triazine type dyes of dyeing temperature are low, but stability to hydrolysis resistance is poor.One chloro-s-triazine and beta-hydroxyethyl sulfuryl sulphur
Then there are two kinds of unmatched problems of reaction-ity group reaction ability for acid esters dyestuff.Therefore, with chloro-s-triazine and beta-hydroxyethyl sulfuryl
Sulfuric ester is the reactive dye of active group, and degree of fixation does not increase significantly.
Invention content
In view of this, the purpose of the present invention is to provide a kind of double-active radical blue active dyes, improve the stabilization of dyestuff
Property and degree of fixation.
In order to achieve the above-mentioned object of the invention, the present invention provides following technical scheme：
A kind of double-active radical blue active dye has structure shown in Formulas I：
R in Formulas I1For-H ,-OCH3Or-SO3Na；R2For-SO3Na or-H；M is Na.
The present invention also provides the preparation method of double-active radical blue active dye described in above-mentioned technical proposal, including following
Step：
The beta-hydroxyethyl sulfone sulfate aryl amine derivatives of structure shown in formula a and concentrated hydrochloric acid and sodium nitrite are subjected to diazotising
Reaction, obtains the diazol with structure shown in formula b；
R1For-H ,-OCH3Or-SO3Na, M Na；
Under the conditions of pH value 1~2, the H acid derivatives with structure shown in the diazol of structure shown in formula b and formula c are existed
First time coupling reaction is carried out in water, obtains the coupling component with structure shown in formula d；
M is Na；
Under the conditions of pH value 3~4, by the m-phenylene diamine (MPD) class compound of structure shown in 2,4,6- trifluoropyrimidines and formula e in water
Middle carry out condensation reaction, obtains the compound with structure shown in formula f；
R2For-SO3Na or-H, M are-Na；
Diazo-reaction will be carried out with the compound of structure shown in formula f and concentrated hydrochloric acid and sodium nitrite, obtained with formula g
The diazol of shown structure；
R2For-SO3Na or-H；M is Na；
It, will be with the diazol of structure shown in formula g and the coupling component with structure shown in formula d under the conditions of pH value 6~7
Second of coupling reaction is carried out in water, obtains having the double-active radical blue active dye of structure shown in Formulas I.
Preferably, the temperature of the first time coupling reaction is 0~10 DEG C, and the time of the first time coupling reaction is 4
~8h.
Preferably, described 2, the molar ratio of 4,6- trifluoropyrimidines and m-phenylene diamine (MPD) class compound e are 1:1~1.05:1.
Preferably, described 2, the temperature of the condensation reaction of 4,6- trifluoropyrimidines is 20~30 DEG C, described 2,4,6- trifluoros are phonetic
The time of the condensation reaction of pyridine is 2~6h.
Preferably, the temperature of the coupling reaction is 0~10 DEG C, and the time of the coupling reaction is 3~6h.
Preferably, the molar ratio with the diazol of structure shown in formula b and H acid derivatives c is 1:1~1.02:1.
Preferably, the molar ratio with the diazol of structure shown in formula g and H acid derivatives c is 1:1~1.03:1.
The present invention also provides the double-active radical blue active dye described in above-mentioned technical proposal or above-mentioned technical proposal institutes
Application of the double-active radical blue active dye that the preparation method stated obtains in printing and dyeing.
The present invention provides a kind of double-active radical blue active dyes, are derived by using beta-hydroxyethyl sulfone sulfate arylamine
The arylamine of object and fluorine-containing pyrimidine group is diazo component, and it is anti-that coupling occurs under acid and alkaline condition with H acid derivatives c respectively
It answers and prepares.4- [2- [2- (sulfonic acid oxygen ethyl sulfuryl) ethyl]-the carbamyl]-benzene contained in blue active dye of the present invention
Base class active group has higher alkali resistance hydrolytic stability, and the fluoropyrimidine active group contained has compared with high reaction activity,
And the reactivity matching between two kinds of active groups.The double-active radical blue dyes is bright-colored, has higher hydrolysis surely
It is qualitative and on fiber have higher degree of fixation.Embodiment statistics indicate that, double-active radical blue provided by the invention is lived
Degree of fixation of the property dyestuff on fiber is up to 86.6%, and staining fastness has reached 4~5 grades.
Double-active radical blue active dye provided by the invention contains fluoropyrimidine and (sulfonic acid oxygen ethyl sulfuryl) ethyl ammonia
Both active groups of formoxyl, in terms of electronic structure, the cloud density in fluoropyrimidine molecule at reaction center carbon atom
It is higher than triazine ring, and pyrimidine ring nitrogen cloud density is lower than triazine, therefore in nucleophilic substitution, difluoro
Pyrimidine active group has higher stability；(sulfonic acid oxygen ethyl sulfuryl) ethyl carbamyl is a kind of novel active group
Group, it is different from traditional beta-hydroxyethyl sulfone sulfate phenyl, connected between sulfone ethyl and phenyl ring by amide groups in molecular structure
It is connected together, further reduced electronic effect of the phenyl ring to active group, therefore, such contains (sulfonic acid oxygen ethyl sulfuryl) ethyl
The blue active dye of carbamyl active group has higher alkali resistance hydrolytic stability.Embodiment statistics indicate that, this hair
Crocking resistance of the double-active radical blue active dye of bright offer on fiber is also improved.
Description of the drawings
The present invention will be further described in detail below with reference to the accompanying drawings and specific embodiments.
Fig. 1 is the flow chart that the present invention prepares double-active radical blue active dye；
Fig. 2 is the infrared spectrum of double-active radical blue dyes I-A solids made from the embodiment of the present invention 1.
Specific embodiment
The present invention provides a kind of double-active radical blue active dyes, have structure shown in Formulas I：
R in Formulas I1For-H ,-OCH3Or-SO3Na；R2For-SO3Na or-H；M is Na.
In the present invention, the R1The preferably ortho position of anilino- or meta position.
In the present invention, the double-active radical blue active dye with structure shown in Formulas I obtained preferably includes following several
Kind compound：
The present invention also provides the preparation method of double-active radical blue active dye described in above-mentioned technical proposal, including following
Step：
The beta-hydroxyethyl sulfone sulfate aryl amine derivatives of structure shown in formula a and concentrated hydrochloric acid and sodium nitrite are subjected to diazotising
Reaction, obtains the diazol with structure shown in formula b；
R1For-H ,-OCH3Or-SO3Na, M Na；
Under the conditions of pH value 1~2, the H acid derivatives with structure shown in the diazol of structure shown in formula b and formula c are existed
First time coupling reaction is carried out in water, obtains the coupling component with structure shown in formula d；
M is Na；
Under the conditions of pH value 3~4, by the m-phenylene diamine (MPD) class compound of structure shown in 2,4,6- trifluoropyrimidines and formula e in water
Middle carry out condensation reaction, obtains the compound with structure shown in formula f；
R2For-SO3Na or-H, M Na；
Diazo-reaction will be carried out with the compound of structure shown in formula f and concentrated hydrochloric acid and sodium nitrite, obtained with formula g
The diazol of shown structure；
R2For-SO3Na or-H；M is Na；
It, will be with the diazol of structure shown in formula g and the coupling component with structure shown in formula d under the conditions of pH value 6~7
Second of coupling reaction is carried out in water, obtains having the double-active radical blue active dye of structure shown in Formulas I.
The present invention carries out the beta-hydroxyethyl sulfone sulfate aryl amine derivatives of structure shown in formula a and concentrated hydrochloric acid and sodium nitrite
Diazo-reaction obtains the diazol with structure shown in formula b；
R1For-H ,-OCH3Or-SO3Na, M Na.
In the present invention, the beta-hydroxyethyl sulfone sulfate aryl amine derivatives of structure and mole of concentrated hydrochloric acid shown in the formula a
Than being preferably 1:2~3, more preferably 1:2.6~2.8.In the present invention, the mass fraction of the concentrated hydrochloric acid is preferably 30%.
In the present invention, the beta-hydroxyethyl sulfone sulfate aryl amine derivatives of structure shown in the formula a and the mass ratio of sodium nitrite are preferred
It is 35.2:7.1.
In the present invention, the temperature of the diazo-reaction be preferably 10 DEG C hereinafter, more preferably 0~5 DEG C, most preferably
2~3 DEG C；The time of the diazo-reaction is preferably 30~60min, more preferably 40~50min.The present invention preferably passes through ice
The mode of bath reaches the temperature of the diazo-reaction.
In the present invention, the beta-hydroxyethyl sulfone sulfate aryl amine derivatives of structure shown in the formula a are preferably with aqueous solution
Form adds in, and the beta-hydroxyethyl sulfone sulfate aryl amine derivatives aqueous solution of structure shown in the formula a more preferably uses sodium bicarbonate
It is 6~7 to adjust pH value；The sodium nitrite preferably adds in form of an aqueous solutions.The present invention is to the sodium nitrite in aqueous solution
There is no special restriction with the concentration of the beta-hydroxyethyl sulfone sulfate aryl amine derivatives aqueous solution of structure shown in formula a, using ability
The beta-hydroxyethyl sulfone sulfate aryl amine derivatives aqueous solution of sodium nitrite in aqueous solution known to field technique personnel, structure shown in formula a
.
The present invention is to the beta-hydroxyethyl sulfone sulfate aryl amine derivatives of structure shown in the formula a and concentrated hydrochloric acid and sodium nitrite
Addition sequence there is no special restriction, using charging sequence well known to those skilled in the art, it is preferable that first by formula a
The beta-hydroxyethyl sulfone sulfate aryl amine derivatives of shown structure mix, then concentrated hydrochloric acid is added dropwise with sodium nitrite in aqueous solution.In this hair
In bright, the concentrated hydrochloric acid is preferably pre-chilled, and the temperature of the precooling is identical with the temperature of diazo-reaction, no longer superfluous herein
It states.In the present invention, the time of the diazo-reaction be added dropwise to complete with concentrated hydrochloric acid after start to calculate.
In the present invention, it is preferred to the reaction end of diazo-reaction is judged using ehrlich reagent.
After the completion of diazo-reaction, the present invention preferably will add in sulfamic acid removal in the system after diazo-reaction excessive
, the nitrous acid generated during diazo-reaction.
It obtains after there is the diazol of structure shown in formula b, the present invention will have shown in formula b and tie under the conditions of pH value 1~2
The H acid derivatives of structure carry out first time coupling reaction in water shown in the diazol of structure and formula c, obtain with being tied formula d Suo Shi
The coupling component of structure；
M is Na.
In the present invention, mole with the H acid derivatives of structure shown in the diazol of structure shown in formula b and formula c
Than being preferably 1:1~1.02:1, more preferably 1.01:1.
In the present invention, as R in the H acid derivatives of structure shown in the formula c2When for-H, M being-H, tied shown in the formula c
The H acid derivatives of structure are H acid.
In the present invention, the temperature of the first time coupling reaction is preferably 0~10 DEG C, more preferably 4~8 DEG C；It is described
The time of first time coupling reaction is preferably 4~8h, more preferably 6~7h.Mode present invention preferably employs ice bath reaches institute
State the temperature of first time coupling reaction.
In the present invention, the H acid derivatives of structure preferably add in form of an aqueous solutions shown in the formula c, the formula c institutes
The mass concentration for showing the H acid derivative aqueous solutions of structure is preferably 10~25%, and more preferably 15~20%.In the present invention,
It is preferred that first the pH value of the H acid derivative aqueous solutions of structure shown in the formula c is adjusted to 1~2, in the present invention, it is preferred to use
Sodium hydroxide or sodium carbonate adjust pH value.The present invention is to the H with structure shown in the diazol of structure shown in formula b and formula c
The addition sequence of acid derivative does not have special restriction, using charging sequence well known to those skilled in the art, preferably
By the diazol with structure shown in formula b be added to pH value be adjusted to 1~2 and formula c shown in structure H acid derivatives it is water-soluble
In liquid, the temperature of first time coupling reaction is then heated to, then it is 1~2 to adjust the pH value of reaction system with sodium bicarbonate, then
Carry out even condensation reaction for the first time.In the present invention, the time of the first time coupling reaction using the pH value of reaction system as 1~
Start to calculate after 2.
The present invention, without processing, is obtained containing with formula d preferably to the system after the completion of the first time coupling reaction
The first time coupling reaction liquid of the coupling component of shown structure.
The present invention is under the conditions of pH value 3~4, by the m-phenylene diamine (MPD) class chemical combination of structure shown in 2,4,6- trifluoropyrimidines and formula e
Object carries out condensation reaction in water, obtains the compound with structure shown in formula f；
R2For-SO3H or-H, M independently are-H or alkali metal.In the present invention, described 2,4,6- trifluoropyrimidines and formula e institutes
The molar ratio for showing the m-phenylene diamine (MPD) class compound of structure is preferably 1:1~1:1.05, more preferably 1:1.02~1:1.03.At this
, it is preferable to use sodium bicarbonate adjusts pH value to 3~4 in invention.
In the present invention, described 2, the setting-up point of 4,6- trifluoropyrimidines is preferably 20~30 DEG C, more preferably 24
~28 DEG C；Described 2, the condensation reaction time of 4,6- trifluoropyrimidines is preferably 2~6h, more preferably 4~5h.The present invention preferably adopts
Reach the setting-up point of the 2,4,6- trifluoropyrimidines with the mode of water-bath.
The present invention does not have the charging sequence of the m-phenylene diamine (MPD) class compound of structure shown in the 2,4,6- trifluoropyrimidines and formula e
There is special restriction, using charging sequence well known to those skilled in the art, it is preferable that first will be between structure shown in formula e
Phenylene diamine compound is soluble in water, obtains the m-phenylene diamine (MPD) class compound water solution of structure shown in formula e, with sodium bicarbonate by institute
The pH value for stating the m-phenylene diamine (MPD) class compound water solution of structure shown in formula e is adjusted to 3~4, is then 3~4 isophthalic two by pH value
Aminated compounds e aqueous solutions are cooled to the temperature of condensation reaction, then 2,4,6- trifluoropyrimidines are added dropwise to the aqueous solution after cooling
In, then the pH value of reaction system is adjusted to 3~4 with sodium bicarbonate, then carries out condensation reaction.In the present invention, it is described
The time of condensation reaction starts to calculate after being added dropwise to complete with 2,4,6- trifluoropyrimidines.The present invention is between structure shown in the formula e
The source of phenylene diamine compound does not have special restriction, using commercial goods well known to those skilled in the art.
In the present invention, it is preferred to the reaction end of the condensation reaction of 2,4,6- trifluoropyrimidines is judged using thin-layered chromatography.
The present invention preferably to the system after the completion of the condensation reaction of the 2,4,6- trifluoropyrimidines without handle directly into
Row reacts in next step, obtains containing the condensation reaction solution with the condensation product of structure shown in formula f.
It obtains after there is the compound of structure shown in formula f, it is of the invention by compound and concentrated hydrochloric acid with structure shown in formula f
Diazo-reaction is carried out with sodium nitrite, obtains the diazol with structure shown in formula g；
R2For-SO3H or-H；M is-H or alkali metal.
It is in the present invention, described that have the compound of structure shown in formula f and the molar ratio of concentrated hydrochloric acid be preferably 1:2~3, more
Preferably 1:2.6~2.8.In the present invention, the mass fraction of the concentrated hydrochloric acid is preferably 30%.In the present invention, described 2,
The mass ratio of 4,6- trifluoropyrimidines and sodium nitrite is preferably 13.94:6.9.
In the present invention, the temperature of the diazo-reaction be preferably 10 DEG C hereinafter, more preferably 0~5 DEG C, most preferably
2~3 DEG C；The time of the diazo-reaction is preferably 30~60min, more preferably 40~50min.The present invention preferably passes through ice
The mode of bath reaches the temperature of the diazo-reaction.
In the present invention, the compound with structure shown in formula f is preferably to contain the condensation with structure shown in formula f
The form of the condensation reaction solution of product adds in；The sodium nitrite preferably adds in form of an aqueous solutions.The present invention is to the Asia
The concentration of sodium nitrate aqueous solution does not have special restriction, using sodium nitrite in aqueous solution well known to those skilled in the art.
The present invention does not have special limit to described with the compound of structure shown in formula f and the addition sequence of concentrated hydrochloric acid and sodium nitrite
It is fixed, using charging sequence well known to those skilled in the art, it is preferable that first by with the compound of structure shown in formula f with
Concentrated hydrochloric acid mixes, then sodium nitrite solution is added dropwise.In the present invention, the drop rate of the sodium nitrite in aqueous solution preferably makes
Starch KI test paper is in subject to micro- blue.In the present invention, the time of the diazo-reaction is dripped with sodium nitrite in aqueous solution
Start to calculate after.
In the present invention, it is preferred to the reaction end of diazo-reaction is judged using ehrlich reagent.
After the completion of diazo-reaction, the present invention preferably will add in sulfamic acid removal in the system after diazo-reaction excessive
, the nitrous acid generated during diazo-reaction.
After obtaining with the diazol of structure shown in formula g and with the coupling component of structure shown in formula d, the present invention is in pH value
Under the conditions of 6~7, second will be carried out in water with the diazol of structure shown in formula g and the coupling component with structure shown in formula d
Secondary coupling reaction obtains having the double-active radical blue active dye of structure shown in Formulas I.In the present invention, it is described that there is formula d institutes
The coupling component for showing structure is preferably containing the first time coupling reaction liquid with the coupling component of structure shown in formula d.In this hair
It is described to be preferably with the diazol of structure shown in formula g and the molar ratio with the coupling component of structure shown in formula d in bright
0.97:1~1.03:1, more preferably 0.99:1~1.01:1.
In the present invention, the temperature of the coupling reaction is preferably 0~10 DEG C, more preferably 4~6 DEG C；The coupling is anti-
The time answered is preferably 4~6h, more preferably 5h.In the present invention, it is preferred to reach the coupling reaction by the way of ice bath
Temperature.
The present invention is to described with the diazol of structure shown in formula g and the addition with the coupling component of structure shown in formula d
Sequence is without special restriction, using feed way well known to those skilled in the art, specifically, as that will have formula g institutes
Show structure diazol be added to containing with the coupling component of structure shown in formula d first time coupling reaction liquid in, Ran Housheng
After temperature to the temperature of coupling reaction, pH value is adjusted to 6~7 with sodium bicarbonate and carries out coupling reaction.In the present invention, the idol
The time for closing reaction starts to calculate to reach during the temperature of coupling reaction.
After coupling reaction, the present invention is preferably saltoutd, is filtered, washed and done to the system after coupling reaction successively
It is dry, the double-active radical blue active dye of structure shown in Formulas I is made.The present invention is to the tool saltoutd, be filtered, washed and dried
Body mode does not have special restriction, using the conventional technical means of those skilled in the art.
The present invention also provides the double-active radical blue active dye described in above-mentioned technical proposal or above-mentioned technical proposal institutes
State the application of double-active radical blue active dye that preparation method obtains in printing and dyeing.
In the present invention, the double-active radical blue active dye is used in printing and dyeing include the following steps：
The double-active radical blue dyes, anhydrous sodium sulphate, soda ash and water are mixed, are made into bath raio 1:15 dye baths, are routinely grasped
Make method to cotton fabric under the conditions of 60 DEG C, dye 60min, then neutralize, wash, finally soap again, hot water wash, cold water are washed,
Drying, cotton fabric after being printed and dyed.
In the present invention, the mass ratio of the double-active radical blue dyes, anhydrous sodium sulphate and soda ash is 3:6:1.
With reference to embodiment to double-active radical blue active dye provided by the invention and its preparation method and application into
Row detailed description, but they cannot be interpreted as limiting the scope of the present invention.
Fig. 1 is the flow chart that the present invention prepares double-active radical blue active dye.
Embodiment 1
A kind of double-active radical blue dyes Formulas I-A：
Preparation method includes the following steps：
(1) 2, the 4- diamino benzene sulfonic acids solution (18.8g) for rolling over 100% is added in 400mL water, is added with stirring carbonic acid
Hydrogen sodium solid, it is 4 to adjust pH value, and 20 DEG C are slowly ramped to after dissolving, and 13.94g (99%) 2 is added dropwise, and 4,6- trifluoropyrimidines control pH
Value is 4, and the reaction was continued 2 hours, and reaction end is detected by thin-layer chromatography, and reaction solution is for use after the completion of condensation；
(2) 4- [2- [2- (sulfonic acid oxygen ethyl sulfuryl) ethyl]-the carbamyl]-aniline 35.2g for rolling over 100% is added in
In 400mL water, with sodium bicarbonate tune pH value 6 under stirring, the 7.1g sodium nitrite solids of folding 100%, stirring and dissolving are added in after dissolving.
Dissolved mixed solution is added to and is cooled in 5 DEG C of aqueous hydrochloric acid solution that (34.1g technical hydrochloric acids (30%) are dissolved in 100mL
In water), after being added dropwise, continue diazo-reaction 45 minutes, ehrlich reagent detection reaction end.After reaction,
Excessive nitrous acid is removed with sulfamic acid.
(3) the condensation product solution of 2,4,6- trifluoropyrimidines and 2,4- diamino benzene sulfonic acid is cooled to 5 DEG C, added in
34.1g technical hydrochloric acids (30%), continue to stir.23g sodium nitrite solutions (30% mass concentration) are added at 5 DEG C, and speed is added dropwise
Degree be subject to reaction solution make starch KI test paper in it is micro- blue.After being added dropwise, continue diazo-reaction 45 minutes, Paul Ehrlich
Reagent detects reaction end.After reaction, excessive nitrous acid is removed with sulfamic acid.
(4) 40.1g H acid monosodium salts (85%) are added in 400mL water, is added with stirring 20% NaOH solution, adjust pH
Value 6.5 makes its dissolving, is cooled to 5 DEG C.Diazol obtained in step (2) is slowly added dropwise in the solution of H acid, is controlled
The pH value of reaction system is maintained at pH=2 2, and temperature is to be reacted 6 hours at 5 DEG C；Ooze circle method detection reaction end, reaction knot
Shu Hou, with the pH value of sodium bicarbonate solid tune reaction system 6.5 or so.Diazol obtained in step (3) is slowly added dropwise
Enter in above-mentioned solution, be maintained at pH=6.5, temperature is to be reacted 4 hours at 5 DEG C；Circle method detection reaction end is oozed, reaction terminates
Afterwards, after reaction, it saltouts, be filtered, washed, drying and to obtain active blue dyestuff I-A solids.
Infrared analysis is carried out to double-active radical blue dyes I-A solids made from embodiment 1, the results are shown in Figure 2, by scheming
2 in infrared spectrum as can be seen that there is triazine ring absorption peak (1493cm-1), C-F absorption peaks (1015cm-1), sulfate group-
Bimodal (the 1400 and 1135cm of OSO3--1) sulfuryl-SO2Absorption peak (1340cm-1) and sulfonic group (1221 and 1048cm-1)
Characteristic absorption peak, it was demonstrated that solid made from the present embodiment really have structure shown in I-A.
Embodiment 2
A kind of double-active radical blue dyes Formulas I-B：
Preparation method includes the following steps：
With above-described embodiment 1 the difference lies in, in this example, with 4- [2- [2- (sulfonic acid oxygen ethyl sulfuryl) ethyl]-
Carbamyl]-aniline -2- sulfonic acid is prepared into phase instead of 4- [2- [2- (sulfonic acid oxygen ethyl sulfuryl) ethyl]-carbamyl]-aniline
The diazol answered is coupled with H acid in acid condition after being prepared into H acid monoazo dyes, then with 2,4,6- trifluoropyrimidines and 2,
Blue active dye I-B is made in diazonium reactant salt prepared by the condensation product of 4- diamino benzene sulfonic acids.
Embodiment 3
A kind of double-active radical blue dyes Formulas I-C：
Preparation method includes the following steps：
With above-described embodiment 1 the difference lies in, in this example, with 4- [2- [2- (sulfonic acid oxygen ethyl sulfuryl) ethyl]-
Carbamyl] -2- aminoanisoles are prepared into instead of 4- [2- [2- (sulfonic acid oxygen ethyl sulfuryl) ethyl]-carbamyl]-aniline
Corresponding diazol is coupled with H acid in acid condition after being prepared into H acid monoazo dyes, then with 2,4,6- trifluoropyrimidines with
Blue active dye I-C is made in diazonium reactant salt prepared by the condensation product of 2,4- diamino benzene sulfonic acids.
Embodiment 4
A kind of double-active radical blue dyes I-D：
Preparation method includes the following steps：
(1) 4,6- diaminobenzenes -1, the 3- disulfonic acid (26.8g) for rolling over 100% is added in 400mL water, be added with stirring
Sodium bicarbonate solid, it is 4 to adjust pH value, and 20 DEG C are slowly ramped to after dissolving, and 13.94g (99%) 2,4,6- trifluoropyrimidines, control is added dropwise
PH value processed is 4, and the reaction was continued 2 hours, and reaction end is detected by thin-layer chromatography, and reaction solution is for use after the completion of condensation；
(2) 4- [2- [2- (sulfonic acid oxygen ethyl sulfuryl) ethyl]-the carbamyl]-aniline 35.2g for rolling over 100% is added in
In 400mL water, with sodium bicarbonate tune pH value 6 under stirring, the 7.1g sodium nitrite solids of folding 100%, stirring and dissolving are added in after dissolving.
Dissolved mixed solution is added to and is cooled in 5 DEG C or so of aqueous hydrochloric acid solution that (34.1g technical hydrochloric acids (30%) are dissolved in
In 100mL water), after being added dropwise, continue diazo-reaction 45 minutes, ehrlich reagent detection reaction end.Reaction knot
Shu Hou, excessive nitrous acid are removed with sulfamic acid.
(3) the condensation product solution of 2,4,6- trifluoropyrimidines and 4,6- diaminobenzene -1,3- disulfonic acid is cooled to 5 DEG C,
34.1g technical hydrochloric acids (30%) are added in, continue to stir.23g sodium nitrite solutions (30% mass concentration), drop are added at 5 DEG C
Acceleration be subject to reaction solution make starch KI test paper in it is micro- blue.After being added dropwise, continue diazo-reaction 45 minutes, angstrom
The uncommon reagent detection reaction end of profit.After reaction, excessive nitrous acid is removed with sulfamic acid.
(4) 40.1g H acid monosodium salts (85%) are added in 400mL water, is added with stirring 20% NaOH solution, adjust pH
Value 6.5 makes its dissolving, is cooled to 5 DEG C.Diazol obtained in step (2) is slowly added dropwise in the solution of H acid, is controlled
The pH value of reaction system is maintained at pH=2 2 or so, and temperature is to be reacted 6 hours at 5 DEG C；Circle method detection reaction end is oozed, instead
After answering, with the pH value of sodium bicarbonate solid tune reaction system 6.5 or so.By diazol obtained in step (3) slowly
It is added dropwise in above-mentioned solution, is maintained at pH=6.5, temperature is to be reacted 4 hours at 5 DEG C；Ooze circle method detection reaction end, reaction knot
Shu Hou, after reaction, saltout, be filtered, washed, drying and to obtain active blue dyestuff I-D solids.
Embodiment 5
A kind of double-active radical blue dyes I-E：
Preparation method includes the following steps：
With above-described embodiment 4 the difference lies in, in this example, with 4- [2- [2- (sulfonic acid oxygen ethyl sulfuryl) ethyl]-
Carbamyl]-aniline -2- sulfonic acid is prepared into phase instead of 4- [2- [2- (sulfonic acid oxygen ethyl sulfuryl) ethyl]-carbamyl]-aniline
The diazol answered is coupled with H acid in acid condition after being prepared into H acid monoazo dyes, then with 2,4,6- trifluoropyrimidines and 4,
Blue active dye I-E is made in diazonium reactant salt prepared by the condensation product of 6- diaminobenzene -1,3- disulfonic acid.
Embodiment 6
A kind of double-active radical blue dyes I-F：
Preparation method includes the following steps：
With above-described embodiment 4 the difference lies in, in this example, with 4- [2- [2- (sulfonic acid oxygen ethyl sulfuryl) ethyl]-
Carbamyl] -2- aminoanisoles are prepared into instead of 4- [2- [2- (sulfonic acid oxygen ethyl sulfuryl) ethyl]-carbamyl]-aniline
Corresponding diazol is coupled with H acid in acid condition after being prepared into H acid monoazo dyes, then with 2,4,6- trifluoropyrimidines with
Blue active dye I-F is made in diazonium reactant salt prepared by the condensation product of 4,6- diaminobenzene -1,3- disulfonic acid.
3 parts of double-active radical blue dyes made from Example 1~6 respectively, adds in 6 parts of anhydrous sodium sulphate, 1 part of soda ash and water,
It is made into bath raio 1:Routinely to cotton fabric under the conditions of 60 DEG C, then dyeing 60min is neutralized, is washed, most operating method for 15 dye baths
Soap again afterwards, hot water wash, cold water are washed, are dried, and obtain blue cotton fabric, properties of product test result is shown in Table 1, can be seen by table 1
Go out, double-active radical blue dyes provided by the invention has good degree of fixation, staining fastness and stability.
The performance test results of double-active radical blue dyes made from 1 Examples 1 to 6 of table
| Serial number | Staining fastness/grade | Antifriction dries/and it is wet | Degree of fixation |
| Embodiment 1 | 4~5 | 4~5/3-4 | 86.1% |
| Embodiment 2 | 4~5 | 4/3-4 | 85.5% |
| Embodiment 3 | 4~5 | 4~5/3-4 | 85.8% |
| Embodiment 4 | 4~5 | 4/3-4 | 86.6% |
| Embodiment 5 | 4~5 | 4~5/3-4 | 85.2% |
| Embodiment 6 | 4~5 | 4~5/3-4 | 84.8% |
The above is only the preferred embodiment of the present invention, it is noted that for the ordinary skill people of the art
For member, various improvements and modifications may be made without departing from the principle of the present invention, these improvements and modifications also should
It is considered as protection scope of the present invention.
Claims (9)
1. a kind of double-active radical blue active dye has structure shown in Formulas I：
R in Formulas I1For-H ,-OCH3Or-SO3Na；R2For-SO3Na or-H；M is Na.
2. the preparation method of double-active radical blue active dye, includes the following steps described in claim 1：
The beta-hydroxyethyl sulfone sulfate aryl amine derivatives of structure shown in formula a and concentrated hydrochloric acid and sodium nitrite progress diazotising are anti-
Should, obtain the diazol with structure shown in formula b；
R1For-H ,-OCH3Or-SO3Na, M are-Na；
Under the conditions of pH value 1~2, by the H acid derivatives with structure shown in the diazol of structure shown in formula b and formula c in water
First time coupling reaction is carried out, obtains the coupling component with structure shown in formula d；
M is Na；
Under the conditions of pH value 3~4, by the m-phenylene diamine (MPD) class compound of structure shown in 2,4,6- trifluoropyrimidines and formula e in water into
Row condensation reaction obtains the compound with structure shown in formula f；
R2For-SO3Na or-H, M Na；
Diazo-reaction will be carried out with the compound of structure shown in formula f and concentrated hydrochloric acid and sodium nitrite, obtained with shown in formula g
The diazol of structure；
R2For-SO3Na or-H；M is Na；
Under the conditions of pH value 6~7, by with the diazol of structure shown in formula g and the coupling component with structure shown in formula d in water
Second of coupling reaction of middle progress obtains having the double-active radical blue active dye of structure shown in Formulas I.
3. preparation method according to claim 2, which is characterized in that the temperature of the first time coupling reaction is 0~10
DEG C, the time of the coupling reaction is 4~8h.
4. preparation method according to claim 2, which is characterized in that described 2,4,6- trifluoropyrimidines and m-phenylene diamine (MPD) class
The molar ratio for closing object e is 1:1~1.05:1.
5. preparation method according to claim 2, which is characterized in that described 2, the setting-up point of 4,6- trifluoropyrimidines
It it is 20~30 DEG C, the time of the condensation reaction is 2~6h.
6. preparation method according to claim 2, which is characterized in that the temperature of second of coupling reaction is 0~10
DEG C, the time of the coupling reaction is 3~6h.
7. preparation method according to claim 2, which is characterized in that described that there is the diazol of structure shown in formula b and H acid
The molar ratio of derivative c is 1:1~1.02:1.
8. preparation method according to claim 7, which is characterized in that described that there is the diazol of structure shown in formula g and H acid
The molar ratio of derivative c is 1:1~1.03:1.
9. the preparation method described in double-active radical blue active dye described in claim 1 or claim 2~8 any one
Application of the obtained double-active radical blue active dye in printing and dyeing.
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| CN105745282B (en) * | 2013-08-29 | 2017-06-23 | 德司达染料分销有限公司 | Reactive dye mixture, and its preparation method and application |
| CN107189491A (en) * | 2017-06-21 | 2017-09-22 | 江苏德美科化工有限公司 | A kind of fluorine-containing multi-active base orchil and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4766206A (en) * | 1985-10-03 | 1988-08-23 | Ciba-Geigy Corporation | Reactive dyestuffs comprising a vinylsulfonylalkylaminocarbonyl moiety |
| CN1329457C (en) * | 2000-12-11 | 2007-08-01 | 德意志戴斯达纺织品及染料两合公司 | Black dyestuff mixture of active azo dyes for fibers, production and use thereof |
| CN105745282B (en) * | 2013-08-29 | 2017-06-23 | 德司达染料分销有限公司 | Reactive dye mixture, and its preparation method and application |
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