CN106634045A - Dark red reactive dye and preparation method thereof - Google Patents
Dark red reactive dye and preparation method thereof Download PDFInfo
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- CN106634045A CN106634045A CN201611124091.5A CN201611124091A CN106634045A CN 106634045 A CN106634045 A CN 106634045A CN 201611124091 A CN201611124091 A CN 201611124091A CN 106634045 A CN106634045 A CN 106634045A
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- Prior art keywords
- formula
- reaction
- crimson
- dyestuff
- diazo
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- 0 *c1cc2cc(N)ccc2c(O)c1 Chemical compound *c1cc2cc(N)ccc2c(O)c1 0.000 description 6
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Nc1ccccc1 Chemical compound Nc1ccccc1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- 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
- C09B67/00—Influencing the physical, e.g. the dyeing or printing properties of dyestuffs without chemical reactions, e.g. by treating with solvents grinding or grinding assistants, coating of pigments or dyes; Process features in the making of dyestuff preparations; Dyestuff preparations of a special physical nature, e.g. tablets, films
- C09B67/0071—Process features in the making of dyestuff preparations; Dehydrating agents; Dispersing agents; Dustfree compositions
- C09B67/0072—Preparations with anionic dyes or reactive dyes
-
- 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
- C09B62/503—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 the reactive group being an esterified or non-esterified hydroxyalkyl sulfonyl or mercaptoalkyl sulfonyl group, a quaternised or non-quaternised aminoalkyl sulfonyl group, a heterylmercapto alkyl sulfonyl group, a vinyl sulfonyl or a substituted vinyl sulfonyl group, or a thiophene-dioxide group
- C09B62/507—Azo dyes
- C09B62/513—Disazo or polyazo dyes
-
- 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
- C09B67/00—Influencing the physical, e.g. the dyeing or printing properties of dyestuffs without chemical reactions, e.g. by treating with solvents grinding or grinding assistants, coating of pigments or dyes; Process features in the making of dyestuff preparations; Dyestuff preparations of a special physical nature, e.g. tablets, films
- C09B67/0033—Blends of pigments; Mixtured crystals; Solid solutions
- C09B67/0046—Mixtures of two or more azo dyes
- C09B67/0055—Mixtures of two or more disazo dyes
- C09B67/0057—Mixtures of two or more reactive disazo dyes
- C09B67/0059—Mixtures of two or more reactive disazo dyes all the reactive groups are not directly attached to a heterocyclic system
-
- 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
-
- 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
Abstract
The invention discloses dark red reactive dye and a preparation method thereof. The dark red reactive dye is one material selected from general formulas of the formula (I) or is a mixture obtained through compounding two or more structures selected from the general formulas of the formula (I) according to any proportion. One material shown by the formula (I) is selected from any one of materials of the following structure general formulas or is a mixture of two or more materials of the structural general formulas, wherein R1, R2, R3 and R4 in the formula (I) respectively and independently represent -H, -CH3, -OCH3 or -SO3M; Y1 and Y2 respectively and independently represent -CH=CH2 or -C2H4OSO3M; M represents hydrogen or alkali metal. The dark red reactive dye has the advantages that the lifting performance is good; the friction firmness, the water washing firmness, the light fastness and the heat stability are high. The formula (I) is shown as the accompanying drawing.
Description
Technical field
The invention belongs to the reactive dyestuff field in new material technology, more particularly to a kind of crimson active dyestuff and its
Preparation method.
Background technology
Reactive dye occupation rate at present commercially is more and more, and people also increasingly pay close attention to for its research.Activity
Dyestuff research starts from 1956, so far existing half a century.In recent years the survey article about reactive dye is also delivered much, no
The development of reactive dye itself is only related to, also including the application performance and technique of reactive dye, emphasis is improving its application performance
And the feature of environmental protection.
General red reactive dyes are all the shape in combination with various aromatic amine diazo components with H acid, J acid as coupling component
Into colour base.Enhancing, depth of active deep red dyestuff of wherein J acid structures etc. will compared with the active red dye of H acid structures
It is good, but the active red dye of J acid structures is on the low side because of water soluble group, the activity of its crock fastness, washing fastness compared with H acid structures
Red is far short of what is expected.Particularly do some it is dark big dark red when, it is difficult to accomplish both there is good enhancing and depth,
There is good crock fastness, washing fastness again, therefore be often difficult to meet requirement of the client to these performances.
The content of the invention
First invention mesh of the present invention is to provide a kind of crock fastness and washing fastness is good, light fastness and heat-resisting steady
Qualitative high crimson active dyestuff.Meanwhile, the colouring synchronism of the crimson active dyestuff, dye-uptake, degree of fixation and lifting
Property is also very high.
Based on first goal of the invention, second goal of the invention of the present invention is intended to provide a kind of above-mentioned crimson active
The preparation method of dyestuff.
The crimson active dyestuff provided based on first goal of the invention, the 3rd goal of the invention of the present invention is also resided in
The crimson active dyestuff of another kind of auxiliary agent improvement is provided.
In order to realize the goal of the invention that above three is technically associated, the technical solution used in the present invention is：
A kind of crimson active dyestuff, it includes any one compound in formula (1) formula, or formula (1) is led to
The mixture that any two or more compounds are compounded according to arbitrary proportion in formula；
Wherein in formula (1)：
R1、R2、R3、R4- H ,-CH are represented independently of one another3、-OCH3Or-SO3M；
Y1And Y2Representative-CH=CH independently of one another2Or-C2H4OSO3M；
M represents hydrogen or alkali metal.
Preferably, Y1And Y2Represent independently of one another：-C2H4OSO3M；
M represents-Na ,-K or-Li.
Preferably, Y1Represent：- CH=CH2；Or Y2Represent：- CH=CH2；Or Y1And Y2Represent：- CH=CH2；
M represents-Na ,-K or-Li.
Specifically, the crimson active dyestuff shown in formula (1) is the one kind or any in following formula (1-1) to formula (1-16)
The mixture of several concrete structure formulas：
A kind of preparation method of above-mentioned crimson active dyestuff, using the following raw material：Sodium hydrogensulfite, aniline, formula (I),
Formula (II) and formula (III).
Wherein in formula (I), formula (II) and formula (III)：
R1、R2、R3、R4- H ,-CH are represented independently of one another3、-OCH3Or-SO3M；
Y3And Y4Representative-C independently of one another2H4OSO3M；
M represents hydrogen or alkali metal；
Through preparation process include it is as follows：
A. condensation reaction：Aniline and formula (I) are mixed in water phase, and with sulfurous hydracid sodium as being contracted under catalyst
Reaction is closed, the phenyl J for synthesizing following structural formula is sour；
B. diazo reaction：Formula (III) is carried out into diazo-reaction in the presence of natrium nitrosum and hydrochloric acid；
C. an even reaction：The phenyl J acid that the diazo-reaction product of above-mentioned formula (III) walks synthesis with a carries out an even reaction；
D. diazo reaction：Formula (II) is carried out into diazo-reaction in the presence of natrium nitrosum and hydrochloric acid；
E. two even reaction：The even thing of phenyl J acid one that the diazo-reaction product of above-mentioned formula (II) is synthesized with c steps is carried out
Two even reactions, reaction obtains the crimson active dyestuff as shown in formula (A) after terminating；
Formula (A):
Y i.e. in formula (A)3And Y4As Y in formula (1)1And Y2Represent independently of one another：-C2H4OSO3M；A class situation；
Y in the formula (1) described in claim 11Or Y2Wherein any one representative-CH=CH2When, or Y1Or Y2
Representative-CH=CH2When, the preparation process also includes：
F. de-ester reaction, by the step e synthetic formula (A) dyestuff uniform temperature is warmed up to, then to carry out alkali process anti-
Formula (B) should be obtained：
In formula, Y1Or Y2Wherein any one representative-CH=CH2, or Y1Or Y2Representative-CH=CH2。
Preferably, the setting-up point control described in step a is at 100-120 DEG C, pH is controlled in 4.0-8.0；Step
Diazo reaction described in b, step d is required to be carried out in the presence of natrium nitrosum and hydrochloric acid, and, at 0-20 DEG C, pH is in control for temperature control
Carry out under 1.0-2.0 processed；At 5-25 DEG C, pH controls are carried out under 0.5-3.0 for an even reaction temperature control described in step c；Step
Two even reactions described in rapid e need to be carried out in the presence of sodium bicarbonate or soda ash, and at 5-25 DEG C, pH controls exist for reaction temperature control
Carry out under 3.0-7.0.
Further, the de-ester reaction described in step f is that synthetic dyestuff is warmed up to into 50-70 DEG C, uses soda ash powder
PH value is adjusted in 8.0-9.0, alkali process reaction is carried out, after de- ester terminal is arrived, hydrochloric acid readjustment section pH to 5.0-6.5 is added.
Another kind of crimson active dyestuff, it is made up of above-mentioned crimson active dyestuff and auxiliary agent mixing；Above-mentioned auxiliary agent
One kind or any two kinds in glauber salt, calgon, methyl naphthalene sulfonic acid aniline condensation thing, naphthalene sulfonic acids aniline condensation thing
Mixture above；Further, above-mentioned auxiliary agent is glauber salt.
Compared with prior art, beneficial effects of the present invention are as follows：
First, the present invention by formula (1) select or mixing and acquisition crimson active dyestuff, be suitable for cellulose fibre
Dyeing.With the China disclosed in Application No. 201510214052.3, entitled crimson active dyestuff and preparation method thereof
Application for a patent for invention is compared, and the present invention carries out phenylating reaction to the amino of the J of dyestuff acid structure, improve dyestuff enhancing,
Degree of fixation, depth, so as to improve the crock fastness and washing fastness of dyestuff；And the present invention carries out protection to amino can be with
Dye oxidation is prevented, such that it is able to improve the light fastness and heat-resistant stability of dyestuff.
2nd, crimson active dyestuff of the invention also has an excellent colouring synchronism, high dye-uptake and degree of fixation, high
Level-dyeing property, it is also particularly suitable with the cotton fiber for having high request to washing fastness, crock fastness, light fastness, heat-resistant stability
Dyeing.The premium properties such as the dyeing and weaving thing thermal sensitivity of acquisition is stable, sun-proof, washable, rub resistance.
3rd, present invention employs J acid structures to react the phenylating of amino, the Dyestuff synthesis, its enhancing, depth,
The J such as degree of fixation, light fastness acid structure will get well to the active deep red dyestuff of phenylating.
4th, in order to preferably improve the printing and dyeing effect such as the water solubility of dyestuff, level-dyeing property, the above-mentioned dyestuff of the present invention can be with
Add different types of auxiliary agent, carry out auxiliary agent improvement, it goes back after printed fabrics after above-mentioned dyestuff with the addition of different auxiliary agents
There is more preferable effect at aspects such as dye uptake, dyestuff diffusivity and alkaline resistance properties.
Specific embodiment
The invention will be further described to synthesize specific example below, but is not therefore to limit the scope of the present invention
Facilitate explanation, dye composition will be represented in the form of sodium salt, but its actual form is likely to be metal base, is more likely
Slaine, especially free acid.
Illustrate technical scheme, but protection scope of the present invention not limited to this with specific embodiment below：
Embodiment 1
A kind of crimson active dyestuff, by simple formula (1-1) structure compound group into：
(1-1) its synthetic method step of the compound of structure is as follows：
1st, condensation reaction：Add bottom water 100g in beaker, control temperature adds the stirring of 20g sodium hydrogensulfites at 25-45 DEG C
To completely molten clear, the J for adding 25g is sour, with 10g sodium bicarbonate regulation pH=5.0-6.0, the aniline solution of 9g is added slowly, plus
PH is surveyed after finishing in 5.0-6.0, then 100-120 DEG C of intensification, is incubated pH value and continues stirring reaction 20-30 hour.Condensation is anti-
Shown in Ying Shiru formulas (a)：
2nd, diazo reaction：Beating 1 hour is carried out during 50g sulfonation para-esters are added to into 100g water and 50g trash ice solution.So
Add 10g hydrochloric acid (30%) afterwards, after stirring 1 minute, molten clear 30% sodium nitrite solution 23g is added dropwise with 20 minutes
Diazo-reaction is carried out in the sulfonation para-ester being beaten, temperature 8-10 DEG C, pH value control 1.0- are controlled during dropwise addition
1.2.And make the micro- indigo plant of starch potassium iodide paper, the micro- indigo plant of the dark red test paper of the Congo.After sodium nitrite solution completion of dropping, keep
Temperature 8-10 DEG C, pH value control 1.0-1.2 is stirred for reaction 30 minutes, then balances excessive nitrous acid with 0.5g sulfamic acids
Sodium.Shown in following (b) formula of diazo reaction equation：
3. an even reaction：The phenyl J lowered the temperature in step 1 is sour, and solution is added drop-wise to 10-30 minutes and is balanced
Sulfonation para-ester diazol in, control temperature 8-10 DEG C, carry out an even reaction, pH value is 0.8-1.5, and stirring reaction 2-3 is little
Up to an even terminal.Shown in one even reaction equation following (c)：
4. diazo reaction：Beating 1 hour is carried out during 28g para-esters are added to into 100g water and 50g trash ice solution.Then plus
Enter 12g hydrochloric acid (30%), after stirring 1 minute, molten clear 30% sodium nitrite solution 23g is added drop-wise to 20 minutes and is beaten
Diazo-reaction is carried out in the para-ester starched, temperature 8-10 DEG C, pH value control 1.0-1.2 are controlled during dropwise addition.And make
The micro- indigo plant of starch potassium iodide paper, the micro- indigo plant of the dark red test paper of the Congo.After sodium nitrite solution completion of dropping, keeping temperature 8-10
DEG C, pH value control 1-1.2 is stirred for reaction 30 minutes, then balances excessive natrium nitrosum with 0.5g sulfamic acids.Diazonium is anti-
Answer shown in following (d) formula of equation：
5. two even reaction：Para-ester diazonium thing is added in an idol carries out two even reactions, adjusts pH with 20g sodium bicarbonate and exists
5.0-6.0, at 10-15 DEG C, in 5.0-6.0, it is two even reaction ends to react to diazol disappearance to pH value to control temperature, obtains two
Even reactant, shown in two even reaction equations following (e)：
Embodiment 2
A kind of crimson active dyestuff, by simple formula (1-2) structure compound group into：
(1-2) its synthetic method step of the compound of structure is as follows：
1st, condensation reaction：Add bottom water 100g in beaker, control temperature adds the stirring of 20g sodium hydrogensulfites at 25-45 DEG C
To completely molten clear, the J for adding 25g is sour, with 10g sodium bicarbonate regulation pH=5.0-6.0, the aniline solution of 9g is added slowly, plus
PH is surveyed after finishing in 5.0-6.0, then 100-120 DEG C of intensification, is incubated pH value and continues stirring reaction 20-30 hour.Condensation is anti-
Shown in Ying Shiru formulas (a)：
2nd, diazo reaction：Beating 1 hour is carried out during 50g sulfonation para-esters are added to into 100g water and 50g trash ice solution.So
Add 10g hydrochloric acid (30%) afterwards, after stirring 1 minute, molten clear 30% sodium nitrite solution 23g is added dropwise with 20 minutes
Diazo-reaction is carried out in the sulfonation para-ester being beaten, temperature 8-10 DEG C, pH value control 1.0- are controlled during dropwise addition
1.2.And make the micro- indigo plant of starch potassium iodide paper, the micro- indigo plant of the dark red test paper of the Congo.After sodium nitrite solution completion of dropping, keep
Temperature 8-10 DEG C, pH value control 1-1.2 is stirred for reaction 30 minutes, then balances excessive nitrous acid with 0.5g sulfamic acids
Sodium.Shown in following (b) formula of diazo reaction equation：
3. an even reaction：The phenyl J acid solution 10-30 minutes lowered the temperature are added drop-wise to into Balanced sulfonation pair
In the ester diazol of position, temperature 8-10 DEG C is controlled, carry out an even reaction, pH value is 0.8-1.5, and stirring reaction 2-3 hour to one is even
Terminal.Shown in one even reaction equation following (c)：
4. diazo reaction：Beating 1 is carried out during 33g O-methoxy para-esters are added to into 100g water and 50g trash ice solution little
When.12g hydrochloric acid (30%) is subsequently adding, after stirring 1 minute, during by molten clear 30% sodium nitrite solution 23g with 20 minutes
Between be added drop-wise in the O-methoxy para-ester being beaten and carry out diazo-reaction, temperature 8-10 DEG C, pH value are controlled during dropwise addition
Control 1.0-1.2.And make the micro- indigo plant of starch potassium iodide paper, the micro- indigo plant of the dark red test paper of the Congo.Sodium nitrite solution is dripped
Bi Hou, keeping temperature 8-10 DEG C, pH value control 1-1.2 is stirred for reaction 30 minutes, then excessive with 0.5g sulfamic acids balance
Natrium nitrosum.Shown in following (e) formula of diazo reaction equation：
5. two even reaction：O-methoxy para-ester diazonium thing is added in an idol carries out two even reactions, is adjusted with 22g sodium bicarbonate
In 5.0-6.0, at 10-15 DEG C, in 5.0-6.0, it is two even reaction ends to react to diazol disappearance to pH value to control temperature to section pH,
Two even reactants are obtained, shown in two even reaction equations following (e)：
Embodiment 3
A kind of crimson active dyestuff, by simple formula (1-3) structure compound group into：
(1-3) its synthetic method step of the compound of structure is as follows：
1st, condensation reaction：Add bottom water 100g in beaker, control temperature adds the stirring of 20g sodium hydrogensulfites at 25-45 DEG C
To completely molten clear, the J for adding 25g is sour, with 10g sodium bicarbonate regulation pH=5.0-6.0, the aniline solution of 9g is added slowly, plus
PH is surveyed after finishing in 5.0-6.0, then 100-120 DEG C of intensification, is incubated pH value and continues stirring reaction 20-30 hour.Condensation is anti-
Shown in Ying Shiru formulas (a)：
2nd, diazo reaction：Beating 1 hour is carried out during 50g sulfonation para-esters are added to into 100g water and 50g trash ice solution.So
Add 10g hydrochloric acid (30%) afterwards, after stirring 1 minute, molten clear 30% sodium nitrite solution 23g is added dropwise with 20 minutes
Diazo-reaction is carried out in the sulfonation para-ester being beaten, temperature 8-10 DEG C, pH value control 1.0- are controlled during dropwise addition
1.2.And make the micro- indigo plant of starch potassium iodide paper, the micro- indigo plant of the dark red test paper of the Congo.After sodium nitrite solution completion of dropping, keep
Temperature 8-10 DEG C, pH value control 1-1.2 is stirred for reaction 30 minutes, then balances excessive nitrous acid with 0.5g sulfamic acids
Sodium.Shown in following (b) formula of diazo reaction equation：
3. an even reaction：The phenyl J acid solution 10-30 minutes lowered the temperature are added drop-wise to into Balanced sulfonation pair
In the ester diazol of position, temperature 8-10 DEG C is controlled, carry out an even reaction, pH value is 0.8-1.5, and stirring reaction 2-3 hour to one is even
Terminal.Shown in one even reaction equation following (c)：
4. diazo reaction：Beating 1 is carried out during 36.0g gram of Li Xiding para-ester is added to into 100g water and 50g trash ice solution
Hour.12g hydrochloric acid (30%) is subsequently adding, after stirring 1 minute, by molten clear 30% sodium nitrite solution 23g with 20 minutes
Time is added drop-wise in gram Li Xiding para-esters being beaten and carries out diazo-reaction, and temperature 8-10 DEG C, pH are controlled during dropwise addition
Value control 1.0-1.2.And make the micro- indigo plant of starch potassium iodide paper, the micro- indigo plant of the dark red test paper of the Congo.Sodium nitrite solution is added dropwise
After finishing, keeping temperature 8-10 DEG C, pH value control 1-1.2 is stirred for reaction 30 minutes, then equilibrated with 0.5g sulfamic acids
The natrium nitrosum of amount.Shown in following (d) formula of diazo reaction equation：
5. two even reaction：Ke Lixiding para-ester diazonium things are added in an idol carries out two even reactions, is adjusted with 21g sodium bicarbonate
In 5.0-6.0, at 10-15 DEG C, in 5.0-6.0, it is two even reaction ends to react to diazol disappearance to pH value to control temperature to section pH,
Two even reactants are obtained, shown in two even reaction equations following (e)：
Embodiment 4
A kind of crimson active dyestuff, by simple formula (1-4) structure compound group into：
(1-4) its synthetic method step of the compound of structure is as follows：
1st, condensation reaction：Add bottom water 100g in beaker, control temperature adds the stirring of 20g sodium hydrogensulfites at 25-45 DEG C
To completely molten clear, the J for adding 25g is sour, with 10g sodium bicarbonate regulation pH=5.0-6.0, the aniline solution of 9g is added slowly, plus
PH is surveyed after finishing in 5.0-6.0, then 100-120 DEG C of intensification, is incubated pH value and continues stirring reaction 20-30 hour.Condensation is anti-
Shown in Ying Shiru formulas (a)：
2nd, diazo reaction：Beating 1 hour is carried out during 50g sulfonation para-esters are added to into 100g water and 50g trash ice solution.So
Add 10g hydrochloric acid (30%) afterwards, after stirring 1 minute, molten clear 30% sodium nitrite solution 23g is added dropwise with 20 minutes
Diazo-reaction is carried out in the sulfonation para-ester being beaten, temperature 8-10 DEG C, pH value control 1.0- are controlled during dropwise addition
1.2.And make the micro- indigo plant of starch potassium iodide paper, the micro- indigo plant of the dark red test paper of the Congo.After sodium nitrite solution completion of dropping, keep
Temperature 8-10 DEG C, pH value control 1-1.2 is stirred for reaction 30 minutes, then balances excessive nitrous acid with 0.5g sulfamic acids
Sodium.Shown in following (b) formula of diazo reaction equation：
3. an even reaction：The phenyl J acid solution 10-30 minutes lowered the temperature are added drop-wise to into Balanced sulfonation pair
In the ester diazol of position, temperature 8-10 DEG C is controlled, carry out an even reaction, pH value is 0.8-1.5, and stirring reaction 2-3 hour to one is even
Terminal.Shown in one even reaction equation following (c)：
4. diazo reaction：Beating 1 is carried out during 39g bi-methoxy para-esters are added to into 100g water and 50g trash ice solution little
When.12g hydrochloric acid (30%) is subsequently adding, after stirring 1 minute, during by molten clear 30% sodium nitrite solution 23g with 20 minutes
Between be added drop-wise in the bi-methoxy para-ester being beaten and carry out diazo-reaction, temperature 8-10 DEG C, pH value are controlled during dropwise addition
Control 1.0-1.2.And make the micro- indigo plant of starch potassium iodide paper, the micro- indigo plant of the dark red test paper of the Congo.Sodium nitrite solution is dripped
Bi Hou, keeping temperature 8-10 DEG C, pH value control 1-1.2 is stirred for reaction 30 minutes, then excessive with 0.5g sulfamic acids balance
Natrium nitrosum.Shown in following (d) formula of diazo reaction equation：
5. two even reaction：Bi-methoxy para-ester diazonium thing is added in an idol carries out two even reactions, is adjusted with 21g sodium bicarbonate
In 5.0-6.0, at 10-15 DEG C, in 5.0-6.0, it is two even reaction ends to react to diazol disappearance to pH value to control temperature to section pH,
Two even reactants are obtained, shown in two even reaction equations following (e)：
Embodiment 5
A kind of crimson active dyestuff, by simple formula (1-5) structure compound group into：
Formula (1-5) its preparation method adopts the following raw material：Sodium hydrogensulfite, aniline, sodium bicarbonate,
Its preparation process is identical with embodiment 1,2,3,4.
Embodiment 6
A kind of crimson active dyestuff, by simple formula (1-6) structure compound group into：
Formula (1-6) its preparation method adopts the following raw material：Sodium hydrogensulfite, aniline, sodium bicarbonate,
Its preparation process is identical with embodiment 1,2,3,4.
Embodiment 7
A kind of crimson active dyestuff, by simple formula (1-7) structure compound group into：
Formula (1-7) its preparation method adopts the following raw material：Sodium hydrogensulfite, aniline, sodium bicarbonate,
Its preparation process is identical with embodiment 1,2,3,4.
Embodiment 8
A kind of crimson active dyestuff, by simple formula (1-8) structure compound group into：
Formula (1-8) its preparation method adopts the following raw material：Sodium hydrogensulfite, aniline, sodium bicarbonate,
Its preparation process is identical with embodiment 1,2,3,4.
Embodiment 9
A kind of crimson active dyestuff, is that degreasing is further carried out after its preparation process e terminates with the difference of embodiment 1
Process：50-70 DEG C is warmed up in above-mentioned product, with soda ash powder pH8.0-9.0 is adjusted, reacted 1 hour, carry out alkali process anti-
Should.After degreasing terminal is arrived, hydrochloric acid readjustment section pH to 5.0-6.5, magma is added to be spray-dried and peony particle dye is obtained.
Shown in reaction equation such as following formula (f)：
Embodiment 10
A kind of crimson active dyestuff, by simple formula (1-10) structure compound group into：
Its preparation process is same as Example 9.
Embodiment 11
A kind of crimson active dyestuff, by simple formula (1-11) structure compound group into：
Its preparation process is same as Example 9.
Embodiment 12
A kind of crimson active dyestuff, by simple formula (1-12) structure compound group into：
Its preparation process is same as Example 9.
Embodiment 13
A kind of crimson active dyestuff, by simple formula (1-13) structure compound group into：
Its preparation process is same as Example 9.
Embodiment 14
A kind of crimson active dyestuff, by simple formula (1-14) structure compound group into：
Its preparation process is same as Example 9.
Embodiment 15
A kind of crimson active dyestuff, by simple formula (1-15) structure compound group into：
Its preparation process is same as Example 9.
Embodiment 16
A kind of crimson active dyestuff, by simple formula (1-16) structure compound group into：
Its preparation process is same as Example 9.
Embodiment 17
A kind of crimson active dyestuff, by formula (1-1) the structural compounds 80g in embodiment 1, the formula (1- in embodiment 2
2) structural compounds 10g, mixes in Chinese style (1-16) the structural compounds 10g tempering tanks of embodiment 16, or sprays after co-dissolve
It is dried.
Embodiment 18
A kind of crimson active dyestuff, by Chinese style (1-3) the structural compounds 5g of embodiment 3, the Chinese style of embodiment 4 (1-4) knot
Structure compound 50g, Chinese style (1-5) the structural compounds 5g of embodiment 5, the mixing of Chinese style (1-6) the structural compounds 40g of embodiment 6
Thing mixes with 10g glauber salt in tempering tank, or is spray-dried after co-dissolve.
Embodiment 19
A kind of crimson active dyestuff, by Chinese style (1-1) the structural compounds 50g of embodiment 1, the Chinese style of embodiment 2 (1-2) knot
Structure compound 20g's, Chinese style (1-10) the structural compounds 10g of embodiment 10, Chinese style (1-7) the structural compounds 20g of embodiment 7 is mixed
Compound mixes with 20g glauber salt in tempering tank, or is spray-dried after co-dissolve.
Embodiment 20
A kind of crimson active dyestuff, by Chinese style (1-1) the structural compounds 20g of embodiment 1, the Chinese style of embodiment 2 (1-2) knot
The mixture of structure compound 80g is mixed with glauber salt 50g and mixed in tempering tank, or is spray-dried after co-dissolve.
Embodiment 21：A kind of crimson active dyestuff, by Chinese style (1-5) the structural compounds 50g of embodiment 5, embodiment 12
Chinese style (1-12) structural compounds 50g and calgon 15g mix in tempering tank, or are spray-dried after co-dissolve.
Embodiment 22
A kind of crimson active dyestuff, by Chinese style (1-6) the structural compounds 30g of embodiment 6, the Chinese style of embodiment 11 (1-11)
Mix in structural compounds 70g and methyl naphthalene sulfonic acid aniline condensation thing 20g tempering tanks, or be spray-dried after co-dissolve.
Embodiment 23
A kind of crimson active dyestuff, is to change in the reaction raw materials sodium bicarbonate in preparation process 4 with the difference of embodiment 1
Into saleratus.
The part Dyeing Example of above-mentioned crimson active dyestuff：
Respectively weigh the above-mentioned dyestuffs of 1g (1-1) --- either its two kinds or two kinds of dye monomer compound obtained in (1-16)
More than mixture (embodiment 12-17) be placed in dyeing cup, dyestuff weighs 2% and is dyeed with fabric, glauber salt containing 60g/L,
Bath raio is 1:In 20 dye bath, 30min, plus soda ash (consumption 15-20g/L) fixation 45min are adsorbed at 60 DEG C.Dyeing and weaving thing Jing water
Wash, soap, being dried.The peony cotton for obtaining has the peony of homogeneity, the Exposure to Sunlight of satisfaction and fastness to rubbing, concrete
1 can be shown in Table.
Table 1
The crimson active of the crimson active dyestuff than traditional J acid structures of the present invention is drawn according to many experiments detection
Dyestuff has excellent application performance, and concrete correction data is shown in Table 2.
Table 2
Finally, in addition it is also necessary to it is noted that listed above is only that the present invention is embodied as example.Obviously, the present invention not
It is limited to above example, there can also be many deformations.One of ordinary skill in the art can be straight from present disclosure
The all deformations derived or associate are connect, protection scope of the present invention is considered as.
Claims (9)
1. a kind of crimson active dyestuff, it is characterised in that：It includes any one compound in formula (1) formula, or
The mixture that any two or more compounds are compounded according to arbitrary proportion in person's formula (1) formula；
Wherein in formula (1)：
R1、R2、R3、R4- H ,-CH are represented independently of one another3、-OCH3Or-SO3M；
Y1And Y2Representative-CH=CH independently of one another2Or-C2H4OSO3M；
M represents hydrogen or alkali metal.
2. a kind of crimson active dyestuff according to claim 1, it is characterised in that：
Y1And Y2Represent independently of one another：-C2H4OSO3M；
M represents-Na ,-K or-Li.
3. a kind of crimson active dyestuff according to claim 1, it is characterised in that：
Y1Represent：- CH=CH2；Or Y2Represent：- CH=CH2；Or Y1And Y2Represent：- CH=CH2；
M represents-Na ,-K or-Li.
4. a kind of crimson active dyestuff according to claim 1, it is characterised in that：Crimson active shown in formula (1)
Dyestuff is the mixture of the one kind in following formula (1-1) to formula (1-16) or any several concrete structure formulas：
5. a kind of preparation method of crimson active dyestuff as claimed in claim 1, it is characterised in that：
Using the following raw material：Sodium hydrogensulfite, aniline, formula (I), formula (II) and formula (III).
Wherein in formula (I), formula (II) and formula (III)：
R1、R2、R3、R4- H ,-CH are represented independently of one another3、-OCH3Or-SO3M；
Y3And Y4Representative-C independently of one another2H4OSO3M；
M represents hydrogen or alkali metal；
Through preparation process include it is as follows：
A. condensation reaction：Aniline and formula (I) are mixed in water phase, and it is anti-as carrying out being condensed under catalyst with sulfurous hydracid sodium
Should, the phenyl J for synthesizing following structural formula is sour；
B. diazo reaction：Formula (III) is carried out into diazo-reaction in the presence of natrium nitrosum and hydrochloric acid；
C. an even reaction：The phenyl J acid that the diazo-reaction product of above-mentioned formula (III) walks synthesis with a carries out an even reaction；
D. diazo reaction：Formula (II) is carried out into diazo-reaction in the presence of natrium nitrosum and hydrochloric acid；
E. two even reaction：It is even that the diazo-reaction product of above-mentioned formula (II) carries out two with the even thing of phenyl J acid one that c steps are synthesized
Reaction, reaction obtains the crimson active dyestuff as shown in formula (A) after terminating；
Formula (A):
Y i.e. in formula (A)3And Y4As Y in formula (1)1And Y2Represent independently of one another：-C2H4OSO3M；A class situation；
Y in the formula (1) described in claim 11Or Y2Wherein any one representative-CH=CH2When, or Y1Or Y2Equal generation
Table-CH=CH2When, the preparation process also includes：
F. de-ester reaction, is warmed up to the step e synthetic formula (A) dyestuff uniform temperature, then carries out alkali process reaction and obtain
Obtain formula (B)：
In formula, Y1Or Y2Wherein any one representative-CH=CH2, or Y1Or Y2Representative-CH=CH2。
6. the preparation method of a kind of crimson active dyestuff according to claim 5, it is characterised in that：
At 100-120 DEG C, pH is controlled in 4.0-8.0 for setting-up point control described in step a；
Diazo reaction described in step b, step d is required to be carried out in the presence of natrium nitrosum and hydrochloric acid, and temperature control is in 0-20
DEG C, pH is carried out under control 1.0-2.0；
At 5-25 DEG C, pH controls are carried out under 0.5-3.0 for an even reaction temperature control described in step c；
Two even reactions described in step e need to be carried out in the presence of sodium bicarbonate or soda ash, reaction temperature control at 5-25 DEG C, pH
Control is carried out under 3.0-7.0.
7. the preparation method of a kind of crimson active dyestuff according to claim 5 or 6, it is characterised in that：
De-ester reaction described in step f is that synthetic dyestuff is warmed up to into 50-70 DEG C, and pH value is adjusted in 8.0- with soda ash powder
9.0, alkali process reaction is carried out, after de- ester terminal is arrived, add hydrochloric acid readjustment section pH to 5.0-6.5.
8. a kind of crimson active dyestuff, it is characterised in that：Mixed by the crimson active dyestuff described in claim 1 and auxiliary agent
Composition；The auxiliary agent is in glauber salt, calgon, condensation compound of methyl naphthalene sulfonic acid and formaldehyde, naphthalene sulfonic acid-formaldehyde condensation product
A kind of or arbitrarily two or more mixture.
9. a kind of crimson active dyestuff according to claim 8, it is characterised in that：The auxiliary agent is glauber salt.
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| CN112300601A (en) * | 2020-10-26 | 2021-02-02 | 苏州澳缘盛新材料科技有限公司 | Preparation method of active dye red jade |
| CN112409819A (en) * | 2020-10-26 | 2021-02-26 | 苏州澳缘盛新材料科技有限公司 | Reactive dye red jade and application thereof |
| CN114634428A (en) * | 2022-03-29 | 2022-06-17 | 仁景(苏州)生物科技有限公司 | Microwave condition preparation method of 6-anilino/p-toluidino-2-naphthalenesulfonic acid |
| CN114634428B (en) * | 2022-03-29 | 2024-05-10 | 仁景(苏州)生物科技有限公司 | Microwave condition preparation method of 6-anilino/p-toluidinyl-2-naphthalene sulfonic acid |
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