CN104861739A - Red reactive dye and preparation method thereof - Google Patents
Red reactive dye and preparation method thereof Download PDFInfo
- Publication number
- CN104861739A CN104861739A CN201510214052.3A CN201510214052A CN104861739A CN 104861739 A CN104861739 A CN 104861739A CN 201510214052 A CN201510214052 A CN 201510214052A CN 104861739 A CN104861739 A CN 104861739A
- Authority
- CN
- China
- Prior art keywords
- formula
- reaction
- reactive dyes
- red reactive
- representative
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 0 COc(cc(*)cc1)c1N=N[C@@](C(c1ccc2*)O)C(*)=Cc1c2N=Nc1ccc(*)cc1* Chemical compound COc(cc(*)cc1)c1N=N[C@@](C(c1ccc2*)O)C(*)=Cc1c2N=Nc1ccc(*)cc1* 0.000 description 3
Abstract
The invention relates to a red reactive dye and a preparation method thereof. The dye is a mixture compounded by one or more than two structures selected from a formula (1) according to any proportion. One shown on the formula (1) is a mixture selected from any one or more than two of the following structural general formula: R1, R2, R3 and R4 represent -H, -CH3, -OCH3 or -SO3 independently respectively, Y1 and Y2 represent -CH=CH2 or -C2H4OSO3M independently respectively, and M represents hydrogen or alkali metal. The red reactive dye has the advantages of being good in crocking fastness and washing fastness and high in light fastness and heat-resistant stability. (img file= 'DDA0000708189600000011. TIF' wi = '917' he = '725').
Description
Technical field
The invention belongs to the reactive dyestuff field in new material technology, particularly relate to a kind of red reactive dyes, with and preparation method thereof.
Background technology
The current occupation rate commercially of reactive dyestuffs gets more and more, and people also more and more pay close attention to for its research.Reactive dyestuffs research starts from 1956, so far existing half a century.The survey article of regarding dyestuff is also delivered much in recent years, not only relates to the development of reactive dyestuffs itself, also comprises application performance and the technique of reactive dyestuffs, and emphasis is in its application performance of raising and the feature of environmental protection.
General red reactive dyes is all to combine with various aromatic amine diazo component formation color base for coupling component so that H acid, J are sour.Wherein the enhancing, depth etc. of active red dye of J acid structure will be got well compared with the active red dye of the sour structure of H, but the active red dye of the sour structure of J because of water soluble group on the low side, its crock fastness, washing fastness are far short of what is expected compared with the active red dye of the sour structure of H.Particularly do some dark bright red time, it is difficult to accomplish both have good enhancing and depth, has again good crock fastness, washing fastness, is therefore often difficult to meet the requirement of client to these performances.
Summary of the invention
First invention order of the present invention be to provide a kind of crock fastness and washing fastness good, light fastness and the high red reactive dyes of heat-resistant stability.Meanwhile, the colouring synchronism of this red reactive dyes, dye uptake, degree of fixation and enhancing are also very high.
Based on first goal of the invention, second goal of the invention of the present invention is intended to the preparation method providing a kind of above-mentioned red reactive dyes.
Based on the red reactive dyes that first goal of the invention provides, the 3rd goal of the invention of the present invention is also the red reactive dyes providing another kind of auxiliary agent to improve.
In order to realize above-mentioned three goals of the invention be technically associated, the technical solution used in the present invention is:
A kind of red reactive dyes, it comprises any one compound in the formula of being selected from (1) general formula, or in formula (1) general formula any two or more compound according to the composite mixture of arbitrary proportion;
In its Chinese style (1):
R
1, R
2, R
3, R
4represent-H ,-CH independently of one another
3,-OCH
3or-SO
3m;
Y
1and Y
2representative-CH=CH independently of one another
2or-C
2h
4oSO
3m;
M represents hydrogen or basic metal.
As preferably, Y
1and Y
2represent independently of one another :-C
2h
4oSO
3m;
M represents-Na ,-K or-Li.
As preferably, Y
1representative :-CH=CH
2; Or Y
2representative :-CH=CH
2; Or Y
1and Y
2all represent :-CH=CH
2;
M represents-Na ,-K or-Li.
Particularly, the red reactive dyes shown in formula (1) is the mixture of following formula (1-1) to a kind of or any several concrete structure formula in formula (1-16):
A preparation method for above-mentioned red reactive dyes, adopts following raw material: Sodium Pyrosulfite, formaldehyde, formula I, formula II and formula III.
Wherein in formula I, formula II and formula III:
R
1, R
2, R
3, R
4represent-H ,-CH independently of one another
3,-OCH
3or-SO
3m;
Y
3and Y
4representative-C independently of one another
2h
4oSO
3m;
M represents hydrogen or basic metal.
The preparation process of process comprises as follows:
A. condensation reaction: Sodium Pyrosulfite and formaldehyde are carried out condensation reaction, synthesis sulphur methyl salt;
Na
2S
2O
5+2HCHO+H
2O→2HOCH
2SO
3Na
B. sulfomethylation: formula I 2-amino-5-naphthols-7-sulfonic acid and a are walked completely reacted sulphur methyl salt carry out sulfomethylation under the effect of alkali, synthesizes the sulphur methyl J acid of following structural formula;
C. doazo reaction: formula III is carried out diazotization reaction under the effect of Sodium Nitrite and hydrochloric acid;
D. an even reaction: the diazotization reaction product of above-mentioned formula III and b walk the sulphur methyl J acid of synthesizing to carry out an idol and react;
E. doazo reaction: formula II is carried out diazotization reaction under the effect of Sodium Nitrite and hydrochloric acid;
F. two even reactions: the sulphur methyl J acid one even thing that the diazotization reaction product of above-mentioned formula II and d walks Reactive Synthesis carries out two and occasionally reacts, and reacts and terminates rear acquisition such as formula the red reactive dyes shown in (A);
Formula (A):
Namely the Y in formula (A)
3and Y
4as Y in formula (1)
1and Y
2represent independently of one another :-C
2h
4oSO
3m; A class situation;
Y in the formula (1) described in claim 1
1or Y
2wherein any one representative-CH=CH
2time, or Y
1or Y
2all representative-CH=CH
2time, described preparation process also comprises:
G. de-ester reaction, is warmed up to certain temperature by described f step by synthetic formula (A) dyestuff, then carries out alkaline purification reaction acquisition formula (B):
In formula, Y
1or Y
2wherein any one representative-CH=CH
2, or Y
1or Y
2all representative-CH=CH
2.
As preferably, the setting-up point described in step a controls to control at 5.0-9.0 at 50-70 DEG C, pH.
Sulfomethylation temperature described in step b controls to control at 6.0-8.0 at 30-50 DEG C, pH
Doazo reaction described in step c, step e carries out under all needing the effect of Sodium Nitrite and hydrochloric acid, and temperature controls to carry out under control 1.0-2.0 at 0-20 DEG C, pH;
Described in steps d one even temperature of reaction controls to control to carry out under 0.5-3.0 at 5-25 DEG C, pH;
Carry out under the effect of described in step f two even reaction needed sodium bicarbonate or soda ash, temperature of reaction controls to control to carry out under 3.0-7.0 at 5-25 DEG C, pH;
Further, the de-ester reaction described in step g is that synthetic dyestuff is warmed up to 50-70 DEG C, by soda ash powder adjust ph at 8.0-9.0, carries out alkaline purification reaction, after de-ester terminal arrives, adds hydrochloric acid readjustment joint pH to 5.0-6.5.
Another kind of red reactive dyes, it is mixed by above-mentioned red reactive dyes and auxiliary agent and forms; Above-mentioned auxiliary agent is selected from a kind of or two or more arbitrarily mixture in Sodium sulfate anhydrous.min(99), Sodium hexametaphosphate 99, condensation compound of methyl naphthalene sulfonic acid and formaldehyde, naphthalene sulfonic acidformaldehyde condensation product; Further, above-mentioned auxiliary agent is Sodium sulfate anhydrous.min(99).
Compared with prior art, beneficial effect of the present invention is as follows:
One, through type of the present invention (1) select or mixing and obtain red reactive dyes, be suitable for the dyeing of cellulosic fibre.Be CN201410269736.9 with the patent No., name is called that the Chinese invention patent disclosed in a kind of active deep red look dye well its preparation method is compared, the amino of the present invention to the J acid structure of dyestuff carries out sulfomethylation, improve easily the washing property of dyestuff, thus improve crock fastness and the washing fastness of dyestuff; And the present invention carries out protection to amino can prevent dye oxidation, thus can improve light fastness and the heat-resistant stability of dyestuff.
Two, red reactive dyes of the present invention also has excellent colouring synchronism, high dye uptake and degree of fixation, high level-dyeing property, also particularly suitable and cotton fiber dyeing washing fastness, crock fastness, light fastness, heat-resistant stability being had to high request.The premium propertiess such as the dyeing and weaving thing thermo-sensitivity obtained is stable, sun-proof, washable, rub resistance.
Three, present invention employs J acid structure to this Dyestuff synthesis, its enhancing, depth etc. will be got well compared with the active red dye of the sour structure of H.
Four, in order to improve the water-soluble of dyestuff better, the printing and dyeing such as level-dyeing property effect, above-mentioned dyestuff of the present invention can also add dissimilar auxiliary agent, carry out auxiliary agent improvement, after above-mentioned dyestuff with the addition of different auxiliary agent, it is after printed fabrics, also in dye uptake, dye diffusion rate and alkaline resistance properties etc., has better effect.
Embodiment
The invention will be further described to synthesize object lesson below, but not therefore for limiting scope of the present invention, for convenience of description, form with sodium salt represents by dye composition, but its actual form is likely metal base, be more likely metal-salt, especially free acid.
With specific embodiment, technical scheme of the present invention is described below, but protection scope of the present invention is not limited thereto:
Embodiment 1: a kind of red reactive dyes, is made up of the compound of simple formula (1-1) structure:
(1-1) its synthetic method step of compound of structure is as follows:
1, condensation reaction: add end water 100g in beaker, control temperature, at 25-45 DEG C, adds 10g Sodium Pyrosulfite and is stirred to complete clearly molten, the formaldehyde solution of 9g is added slowly, survey pH after adding at 5.0-9.0, then intensification 50-70 DEG C, insulation is protected pH value and is continued stirring reaction 1-2 hour.Condensation reaction formula is such as formula shown in (a):
Na
2S
2O
5+2HCHO+H
2O→2HOCH
2SO
3Na
Formula (a)
2, sulfomethylation: above-mentioned reaction solution is cooled to 30-50 DEG C, again the 2-amino-5-naphthols-7-sulfonic acid of 26g and J acid are dropped into, add 12g sodium bicarbonate and raise pH to 6.0-8.0, be incubated 30-50 DEG C of reaction to sour any residual aqueous phase≤2.0% of J for terminal arrives, then be cooled to less than 20 DEG C for subsequent use.Sulfomethylation is such as formula shown in (b):
3, doazo reaction: 53g sulfonation para-ester is joined in 100g water and 50g trash ice solution and carry out making beating 1 hour.Then 10g hydrochloric acid (30%) is added, stir after 1 minute, by molten clearly 30% sodium nitrite solution 24g to be added drop-wise to 20 minutes in the sulfonation para-ester of having pulled an oar and to carry out diazotization reaction, control temperature 8-10 DEG C in dropping process, pH value control 1.0-1.2.And make the micro-indigo plant of starch potassium iodide paper, the micro-indigo plant of congo-red test paper.After sodium nitrite solution dropwises, keep temperature 8-10 DEG C, pH value control 1.0-1.2 stirring reaction 30 minutes again, then balance excessive Sodium Nitrite with 0.5g thionamic acid.Shown in following (c) formula of doazo reaction equation:
4. an even reaction: by the sulphur methyl J acid of having lowered the temperature in step 2, solution 10-30 minutes is added drop-wise in Balanced sulfonation para-ester diazonium salt, control temperature 8-10 DEG C, carries out an even reaction, pH value is 0.8-1.5, and stirring reaction 2-3 is little of an even terminal.Shown in one even reaction equation following (d):
5. doazo reaction: 29.5g para-ester is joined in 100g water and 50g trash ice solution and carry out making beating 1 hour.Then 12g hydrochloric acid (30%) is added, stir after 1 minute, by molten clearly 30% sodium nitrite solution 24g to be added drop-wise to 20 minutes in the para-ester of having pulled an oar and to carry out diazotization reaction, control temperature 8-10 DEG C in dropping process, pH value control 1.0-1.2.And make the micro-indigo plant of starch potassium iodide paper, the micro-indigo plant of congo-red test paper.After sodium nitrite solution dropwises, keep temperature 8-10 DEG C, pH value control 1-1.2 stirring reaction 30 minutes again, then balance excessive Sodium Nitrite with 0.5g thionamic acid.Shown in following (e) formula of doazo reaction equation:
6. two even reactions: para-ester diazonium thing join one even in carry out two even reactions, regulate pH at 5.0-6.0 with 20g sodium bicarbonate, control temperature is at 10-15 DEG C, pH value is at 5.0-6.0, it is two even reaction ends that reaction disappears to diazonium salt, obtain two even reactants, shown in two even reaction equations following (f):
Embodiment 2: a kind of red reactive dyes, is made up of the compound of simple formula (1-2) structure:
(1-2) its synthetic method step of compound of structure is as follows:
1, condensation reaction: add end water 100g in beaker, control temperature, at 25-45 DEG C, adds 10g Sodium Pyrosulfite and is stirred to complete clearly molten, the formaldehyde solution of 9g is added slowly, survey pH after adding at 5.0-9.0, then intensification 50-70 DEG C, insulation is protected pH value and is continued stirring reaction 1-2 hour.Condensation reaction formula is such as formula shown in (a):
Na
2S
2O
5+2HCHO+H
2O→2HOCH
2SO
3Na
Formula (a)
2, sulfomethylation: above-mentioned reaction solution is cooled to 30-50 DEG C, then 26gJ acid dropped into, adds 12g sodium bicarbonate and raises pH to 6.0-8.0, be incubated 30-50 DEG C of reaction to sour any residual aqueous phase≤2.0% of J for terminal arrives, then be cooled to less than 20 DEG C for subsequent use.Sulfomethylation is such as formula shown in (b):
3, doazo reaction: 53g sulfonation para-ester is joined in 100g water and 50g trash ice solution and carry out making beating 1 hour.Then 10g hydrochloric acid (30%) is added, stir after 1 minute, by molten clearly 30% sodium nitrite solution 24g to be added drop-wise to 20 minutes in the sulfonation para-ester of having pulled an oar and to carry out diazotization reaction, control temperature 8-10 DEG C in dropping process, pH value control 1.0-1.2.And make the micro-indigo plant of starch potassium iodide paper, the micro-indigo plant of congo-red test paper.After sodium nitrite solution dropwises, keep temperature 8-10 DEG C, pH value control 1-1.2 stirring reaction 30 minutes again, then balance excessive Sodium Nitrite with 0.5g thionamic acid.Shown in following (c) formula of doazo reaction equation:
4. an even reaction: be added drop-wise in Balanced sulfonation para-ester diazonium salt by the sulphur methyl J acid solution 10-30 minutes of having lowered the temperature, 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 of an even terminal.Shown in one even reaction equation following (d):
5. doazo reaction: 33.5g O-methoxy para-ester is joined in 100g water and 50g trash ice solution and carry out making beating 1 hour.Then 12g hydrochloric acid (30%) is added, stir after 1 minute, by molten clearly 30% sodium nitrite solution 24g to be added drop-wise to 20 minutes in the O-methoxy para-ester of having pulled an oar and to carry out diazotization reaction, control temperature 8-10 DEG C in dropping process, pH value control 1.0-1.2.And make the micro-indigo plant of starch potassium iodide paper, the micro-indigo plant of congo-red test paper.After sodium nitrite solution dropwises, keep temperature 8-10 DEG C, pH value control 1-1.2 stirring reaction 30 minutes again, then balance excessive Sodium Nitrite with 0.5g thionamic acid.Shown in following (e) formula of doazo reaction equation:
6. two even reactions: O-methoxy para-ester diazonium thing join one even in carry out two even reactions, regulate pH at 5.0-6.0 with 22g sodium bicarbonate, control temperature is at 10-15 DEG C, pH value is at 5.0-6.0, it is two even reaction ends that reaction disappears to diazonium salt, obtain two even reactants, shown in two even reaction equations following (f):
Embodiment 3: a kind of red reactive dyes, is made up of the compound of simple formula (1-3) structure:
(1-3) its synthetic method step of compound of structure is as follows:
1, condensation reaction: add end water 100g in beaker, control temperature, at 25-45 DEG C, adds 10g Sodium Pyrosulfite and is stirred to complete clearly molten, the formaldehyde solution of 9g is added slowly, survey pH after adding at 5.0-9.0, then intensification 50-70 DEG C, insulation is protected pH value and is continued stirring reaction 1-2 hour.Condensation reaction formula is such as formula shown in (a):
Na
2S
2O5+
2HCHO+H
2O→2HOCH
2SO
3Na
Formula (a)
2, sulfomethylation: above-mentioned reaction solution is cooled to 30-50 DEG C, then 26gJ acid dropped into, adds 12g sodium bicarbonate and raises pH to 6.0-8.0, be incubated 30-50 DEG C of reaction to sour any residual aqueous phase≤2.0% of J for terminal arrives, then be cooled to less than 20 DEG C for subsequent use.Sulfomethylation is such as formula shown in (b):
3, doazo reaction: 53g sulfonation para-ester is joined in 100g water and 50g trash ice solution and carry out making beating 1 hour.Then 10g hydrochloric acid (30%) is added, stir after 1 minute, by molten clearly 30% sodium nitrite solution 24g to be added drop-wise to 20 minutes in the sulfonation para-ester of having pulled an oar and to carry out diazotization reaction, control temperature 8-10 DEG C in dropping process, pH value control 1.0-1.2.And make the micro-indigo plant of starch potassium iodide paper, the micro-indigo plant of congo-red test paper.After sodium nitrite solution dropwises, keep temperature 8-10 DEG C, pH value control 1-1.2 stirring reaction 30 minutes again, then balance excessive Sodium Nitrite with 0.5g thionamic acid.Shown in following (c) formula of doazo reaction equation:
4. an even reaction: be added drop-wise in Balanced sulfonation para-ester diazonium salt by the sulphur methyl J acid solution 10-30 minutes of having lowered the temperature, 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 of an even terminal.Shown in one even reaction equation following (d):
5. doazo reaction: 37.0g gram of Li Xiding para-ester is joined in 100g water and 50g trash ice solution and carry out making beating 1 hour.Then 12g hydrochloric acid (30%) is added, stir after 1 minute, by molten clearly 30% sodium nitrite solution 24g to be added drop-wise to 20 minutes in gram Li Xiding para-ester of having pulled an oar and to carry out diazotization reaction, control temperature 8-10 DEG C in dropping process, pH value control 1.0-1.2.And make the micro-indigo plant of starch potassium iodide paper, the micro-indigo plant of congo-red test paper.After sodium nitrite solution dropwises, keep temperature 8-10 DEG C, pH value control 1-1.2 stirring reaction 30 minutes again, then balance excessive Sodium Nitrite with 0.5g thionamic acid.Shown in following (e) formula of doazo reaction equation:
6. two even reactions: a gram Li Xiding para-ester diazonium thing join one even in carry out two even reactions, with 21
gsodium bicarbonate regulates pH at 5.0-6.0, and control temperature is at 10-15 DEG C, and pH value is at 5.0-6.0, and reacting to diazonium salt disappearance is two even reaction ends, obtains two even reactants, shown in two even reaction equations following (F):
Embodiment 4: a kind of red reactive dyes, is made up of the compound of simple formula (1-4) structure:
(1-4) its synthetic method step of compound of structure is as follows:
1, condensation reaction: add end water 100g in beaker, control temperature, at 25-45 DEG C, adds 10g Sodium Pyrosulfite and is stirred to complete clearly molten, the formaldehyde solution of 9g is added slowly, survey pH after adding at 5.0-9.0, then intensification 50-70 DEG C, insulation is protected pH value and is continued stirring reaction 1-2 hour.Condensation reaction formula is such as formula shown in (a):
Na
2S
2O
5+2HCHO+H
2O→2HOCH
2SO
3Na
Formula (a)
2, sulfomethylation: above-mentioned reaction solution is cooled to 30-50 DEG C, then 26gJ acid dropped into, adds 12g sodium bicarbonate and raises pH to 6.0-8.0, be incubated 30-50 DEG C of reaction to sour any residual aqueous phase≤2.0% of J for terminal arrives, then be cooled to less than 20 DEG C for subsequent use.Sulfomethylation is such as formula shown in (b):
3, doazo reaction: 53g sulfonation para-ester is joined in 100g water and 50g trash ice solution and carry out making beating 1 hour.Then 10g hydrochloric acid (30%) is added, stir after 1 minute, by molten clearly 30% sodium nitrite solution 24g to be added drop-wise to 20 minutes in the sulfonation para-ester of having pulled an oar and to carry out diazotization reaction, control temperature 8-10 DEG C in dropping process, pH value control 1.0-1.2.And make the micro-indigo plant of starch potassium iodide paper, the micro-indigo plant of congo-red test paper.After sodium nitrite solution dropwises, keep temperature 8-10 DEG C, pH value control 1-1.2 stirring reaction 30 minutes again, then balance excessive Sodium Nitrite with 0.5g thionamic acid.Shown in following (c) formula of doazo reaction equation:
4. an even reaction: be added drop-wise in Balanced sulfonation para-ester diazonium salt by the sulphur methyl J acid solution 10-30 minutes of having lowered the temperature, 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 of an even terminal.Shown in one even reaction equation following (d):
5. doazo reaction: 39.5g bi-methoxy para-ester is joined in 100g water and 50g trash ice solution and carry out making beating 1 hour.Then 12g hydrochloric acid (30%) is added, stir after 1 minute, by molten clearly 30% sodium nitrite solution 24g to be added drop-wise to 20 minutes in the bi-methoxy para-ester of having pulled an oar and to carry out diazotization reaction, control temperature 8-10 DEG C in dropping process, pH value control 1.0-1.2.And make the micro-indigo plant of starch potassium iodide paper, the micro-indigo plant of congo-red test paper.After sodium nitrite solution dropwises, keep temperature 8-10 DEG C, pH value control 1-1.2 stirring reaction 30 minutes again, then balance excessive Sodium Nitrite with 0.5g thionamic acid.Shown in following (e) formula of doazo reaction equation:
6. two even reactions: bi-methoxy para-ester diazonium thing join one even in carry out two even reactions, regulate pH at 5.0-6.0 with 21g sodium bicarbonate, control temperature is at 10-15 DEG C, pH value is at 5.0-6.0, it is two even reaction ends that reaction disappears to diazonium salt, obtain two even reactants, shown in two even reaction equations following (F):
Embodiment 5: a kind of red reactive dyes, is made up of the compound of simple formula (1-5) structure:
Formula (1-5) its preparation method adopts following raw material: Sodium Pyrosulfite, formaldehyde, sodium bicarbonate,
Its preparation process and embodiment 1,2,3,4 identical.
Embodiment 6: a kind of red reactive dyes, is made up of the compound of simple formula (1-6) structure:
Formula (1-6) its preparation method adopts following raw material: Sodium Pyrosulfite, formaldehyde, sodium bicarbonate,
Its preparation process and embodiment 1,2,3,4 identical.
Embodiment 7: a kind of red reactive dyes, is made up of the compound of simple formula (1-7) structure:
Formula (1-7) its preparation method adopts following raw material: Sodium Pyrosulfite, formaldehyde, sodium bicarbonate,
Its preparation process and embodiment 1,2,3,4 identical.
Embodiment 8: a kind of red reactive dyes, is made up of the compound of simple formula (1-8) structure:
Formula (1-8) its preparation method adopts following raw material: Sodium Pyrosulfite, formaldehyde, sodium bicarbonate,
Its preparation process and embodiment 1,2,3,4 identical.
With the difference of embodiment 1, embodiment 9: a kind of red reactive dyes, is that its preparation process f terminates to carry out skimming treatment further afterwards: be warmed up to 50-70 DEG C at above-mentioned product, regulates pH8.0-9.0, react 1 hour, carry out alkaline purification reaction with soda ash powder.After degreasing terminal arrives, add hydrochloric acid readjustment joint pH to 5.0-6.5, magma spraying dry can obtain red granules dyestuff.Reaction equation is as shown in the formula shown in (g):
Embodiment 10: a kind of red reactive dyes, is made up of the compound of simple formula (1-10) structure:
Its preparation process is identical with embodiment 9.
Embodiment 11: a kind of red reactive dyes, is made up of the compound of simple formula (1-11) structure:
Its preparation process is identical with embodiment 9.
Embodiment 12: a kind of red reactive dyes, is made up of the compound of simple formula (1-12) structure:
Its preparation process is identical with embodiment 9.
Embodiment 13: a kind of red reactive dyes, is made up of the compound of simple formula (1-13) structure:
Its preparation process is identical with embodiment 9.
Embodiment 14: a kind of red reactive dyes, is made up of the compound of simple formula (1-14) structure:
Its preparation process is identical with embodiment 9.
Embodiment 15: a kind of red reactive dyes, is made up of the compound of simple formula (1-15) structure:
Its preparation process is identical with embodiment 9.
Embodiment 16: a kind of red reactive dyes, is made up of the compound of simple formula (1-16) structure:
Its preparation process is identical with embodiment 9.
Embodiment 17: a kind of red reactive dyes, by formula (1-1) the structural compounds 80g in embodiment 1, formula (1-2) structural compounds 10g in embodiment 2, mix in embodiment 16 Chinese style (1-16) structural compounds 10g tempering tank, or spraying dry after common dissolving.
Embodiment 18: a kind of red reactive dyes, by embodiment 3 Chinese style (1-3) structural compounds 5g, embodiment 4 Chinese style (1-4) structural compounds 50g, embodiment 5 Chinese style (1-5) structural compounds 5g, the mixture of embodiment 6 Chinese style (1-6) structural compounds 40g mixes in tempering tank with 10g Sodium sulfate anhydrous.min(99), or spraying dry after common dissolving.
Embodiment 19: a kind of red reactive dyes, by embodiment 1 Chinese style (1-1) structural compounds 50g, embodiment 2 Chinese style (1-2) structural compounds 20g, embodiment 10 Chinese style (1-10) structural compounds 10g, the mixture of embodiment 7 Chinese style (1-7) structural compounds 20g mixes in tempering tank with 20g Sodium sulfate anhydrous.min(99), or spraying dry after common dissolving.
Embodiment 20: a kind of red reactive dyes, by embodiment 1 Chinese style (1-1) structural compounds 20g, the mixture of embodiment 2 Chinese style (1-2) structural compounds 80g mixes with Sodium sulfate anhydrous.min(99) 50g and mixes in tempering tank, or spraying dry after common dissolving.
Embodiment 21: a kind of red reactive dyes, by embodiment 5 Chinese style (1-5) structural compounds 50g, embodiment 12 Chinese style (1-12) structural compounds 50g and Sodium hexametaphosphate 99 15g mixes in tempering tank, or spraying dry after common dissolving.
Embodiment 22: a kind of red reactive dyes, by embodiment 6 Chinese style (1-6) structural compounds 30g, mix in embodiment 11 Chinese style (1-11) structural compounds 70g and condensation compound of methyl naphthalene sulfonic acid and formaldehyde 20g tempering tank, or spraying dry after common dissolving.
Embodiment 23: a kind of red reactive dyes, is to change the reaction raw materials sodium bicarbonate in preparation process 4 into saleratus with the difference of embodiment 1.
The part Dyeing Example of above-mentioned red reactive dyes:
Respectively taking the above-mentioned dyestuff of 1g (1-1)---the dye monomer compound that (1-16) is obtained or its two kinds or two or more mixture (embodiment 12-17) are placed in dye cup, dyestuff weighs 2% with fabric and dyes, be in the dye bath of 1:20 containing 60g/L Sodium sulfate anhydrous.min(99), bath raio, adsorb 30min at 60 DEG C, add soda ash (consumption 15-20g/L) fixation 45min.Dyeing and weaving thing through washing, soaping, dry.The red cotton obtained has the redness of homogeneity, satisfied Exposure to Sunlight and fastness to rubbing, and specific performance is in table 1.
Table 1
Detect according to great many of experiments and show that the red reactive dyes of red reactive dyes of the present invention structure sourer than traditional J has excellent application performance, concrete correlation data is in table 2.
Table 2
| Sequence number | Dry fastness | Fastness to wet rubbing | Light fastness | Resistance to hot pressing 200 DEG C |
| Dyestuff 1 of the present invention | 4-5 | 3-4 | 4 | 3-4 |
| Dyestuff 2 of the present invention | 4-5 | 3-4 | 4-5 | 3-4 |
| Dyestuff 3 of the present invention | 4-5 | 3-4 | 4-5 | 4 |
| Dyestuff 4 of the present invention | 4-5 | 3-4 | 4-5 | 4 |
| Dyestuff 5 of the present invention | 4 | 3-4 | 4 | 4 |
| Dyestuff 6 of the present invention | 4-5 | 3-4 | 4-5 | 4 |
| Dyestuff 7 of the present invention | 4-5 | 3-4 | 4-5 | 3-4 |
| Dyestuff 8 of the present invention | 4-5 | 3-4 | 4-5 | 4 |
| Dyestuff 9 of the present invention | 4-5 | 3-4 | 4-5 | 4 |
| Dyestuff 10 of the present invention | 4 | 3-4 | 4 | 4 |
| Dyestuff 11 of the present invention | 4-5 | 3-4 | 4-5 | 4 |
| Dyestuff 12 of the present invention | 4-5 | 3-4 | 4 | 3-4 |
| Dyestuff 15 of the present invention | 4-5 | 3-4 | 4-5 | 3-4 |
| Dyestuff 16 of the present invention | 4-5 | 3-4 | 4-5 | 4 |
| Dyestuff 17 of the present invention | 4-5 | 3-4 | 4-5 | 4 |
| Dyestuff 18 of the present invention | 4-5 | 3-4 | 4-5 | 4 |
| Dyestuff 19 of the present invention | 4-5 | 3-4 | 4-5 | 4 |
| Dyestuff 20 of the present invention | 4 | 3-4 | 4 | 4 |
| Dyestuff 21 of the present invention | 4-5 | 3-4 | 4-5 | 4 |
| Dyestuff 22 of the present invention | 4-5 | 3-4 | 4 | 3-4 |
| Dyestuff 23 of the present invention | 4-5 | 3-4 | 4-5 | 4 |
| The non-sulfomethylation red of J acid | 3-4 | 2-3 | 3 | 2-3 |
Finally, it is also to be noted that enumerate above be only specific embodiments of the invention son.Obviously, the invention is not restricted to above examples of implementation, many distortion can also be had.All distortion that those of ordinary skill in the art can directly derive from content disclosed by the invention or associate, all should think protection scope of the present invention.
Claims (9)
1. a red reactive dyes, is characterized in that: it comprises any one compound in the formula of being selected from (1) general formula, or in formula (1) general formula any two or more compound according to the composite mixture of arbitrary proportion;
In its Chinese style (1):
R
1, R
2, R
3, R
4separately
independentground representative-H ,-CH
3,-OCH
3or-SO
3m;
Y
1and Y
2separately
independentground representative-CH=CH
2or-C
2h
4oSO
3m;
M represents hydrogen or basic metal.
2. a kind of red reactive dyes according to claim 1, is characterized in that:
Y
1and Y
2separately
independentground representative :-C
2h
4oSO
3m;
M represents-Na ,-K or-Li.
3. a kind of red reactive dyes according to claim 1, is characterized in that:
Y
1representative :-CH=CH
2; Or Y
2representative :-CH=CH
2; Or Y
1and Y
2all represent :-CH=CH
2;
M represents-Na ,-K or-Li.
4. a kind of red reactive dyes according to claim 1, is characterized in that: the red reactive dyes shown in formula (1) is the mixture of following formula (1-1) to a kind of or any several concrete structure formula in formula (1-16):
。
5. a preparation method for red reactive dyes as claimed in claim 1, is characterized in that: adopt following raw material: Sodium Pyrosulfite, formaldehyde, formula I, formula II and formula III.
Wherein in formula I, formula II and formula III:
R
1, R
2, R
3, R
4separately
independentground representative-H ,-CH
3,-OCH
3or-SO
3m;
Y
3and Y
4separately
independentground representative-C
2h
4oSO
3m;
M represents hydrogen or basic metal.
The preparation process of process comprises as follows:
A. condensation reaction: Sodium Pyrosulfite and formaldehyde are carried out condensation reaction, synthesis sulphur methyl salt;
Na
2S
2O
5+2HCHO+H
2O→2HOCH
2SO
3Na
B. sulfomethylation: formula I 2-amino-5-naphthols-7-sulfonic acid and a are walked completely reacted sulphur methyl salt carry out sulfomethylation under the effect of alkali, synthesizes the sulphur methyl J acid of following structural formula;
C. doazo reaction: formula III is carried out diazotization reaction under the effect of Sodium Nitrite and hydrochloric acid;
D. an even reaction: the diazotization reaction product of above-mentioned formula III and b walk the sulphur methyl J acid of synthesizing to carry out an idol and react;
E. doazo reaction: formula II is carried out diazotization reaction under the effect of Sodium Nitrite and hydrochloric acid;
F. two even reactions: the sulphur methyl J acid one even thing that the diazotization reaction product of above-mentioned formula II and d walks Reactive Synthesis carries out two and occasionally reacts, and reacts and terminates rear acquisition such as formula the red reactive dyes shown in (A);
Formula (A):
Namely the Y in formula (A)
3and Y
4as Y in formula (1)
1and Y
2separately
independentground representative :-C
2h
4oSO
3m; A class situation;
Y in the formula (1) described in claim 1
1or Y
2wherein any one representative-CH=CH
2time, or Y
1or Y
2all representative-CH=CH
2time, described preparation process also comprises:
G. de-ester reaction, is warmed up to certain temperature by described f step by synthetic formula (A) dyestuff, then carries out alkaline purification reaction acquisition formula (B):
In formula, Y
1or Y
2wherein any one representative-CH=CH
2, or Y
1or Y
2all representative-CH=CH
2.
6. the preparation method of a kind of red reactive dyes according to claim 5, is characterized in that:
Setting-up point described in step a controls to control at 5.0-9.0 at 50-70 DEG C, pH.
Sulfomethylation temperature described in step b controls to control at 6.0-8.0 at 30-50 DEG C, pH
Doazo reaction described in step c, step e carries out under all needing the effect of Sodium Nitrite and hydrochloric acid, and temperature controls to carry out under control 1.0-2.0 at 0-20 DEG C, pH;
Described in steps d one even temperature of reaction controls to control to carry out under 0.5-3.0 at 5-25 DEG C, pH;
Carry out under the effect of described in step f two even reaction needed sodium bicarbonate or soda ash, temperature of reaction controls to control to carry out under 3.0-7.0 at 5-25 DEG C, pH.
7. the preparation method of a kind of red reactive dyes according to claim 5 or 6, is characterized in that:
De-ester reaction described in step g is that synthetic dyestuff is warmed up to 50-70 DEG C, by soda ash powder adjust ph at 8.0-9.0, carries out alkaline purification reaction, after de-ester terminal arrives, adds hydrochloric acid readjustment joint pH to 5.0-6.5.
8. a red reactive dyes, is characterized in that: mixed by red reactive dyes according to claim 1 and auxiliary agent and form; Described auxiliary agent is selected from a kind of or two or more arbitrarily mixture in Sodium sulfate anhydrous.min(99), Sodium hexametaphosphate 99, condensation compound of methyl naphthalene sulfonic acid and formaldehyde, naphthalene sulfonic acidformaldehyde condensation product.
9. a kind of red reactive dyes according to claim 8, is characterized in that: described auxiliary agent is Sodium sulfate anhydrous.min(99).
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510214052.3A CN104861739A (en) | 2015-04-29 | 2015-04-29 | Red reactive dye and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510214052.3A CN104861739A (en) | 2015-04-29 | 2015-04-29 | Red reactive dye and preparation method thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN104861739A true CN104861739A (en) | 2015-08-26 |
Family
ID=53907946
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201510214052.3A Pending CN104861739A (en) | 2015-04-29 | 2015-04-29 | Red reactive dye and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN104861739A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106634045A (en) * | 2016-12-08 | 2017-05-10 | 浙江亿得化工有限公司 | Dark red reactive dye and preparation method thereof |
| 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 |
Citations (15)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6011140A (en) * | 1996-01-11 | 2000-01-04 | Basf Aktiengesellschaft | Reactive azo dyes with an aminonaphthalenesulfonic acid coupling component and intermediates therefor |
| CN1594445A (en) * | 2003-08-16 | 2005-03-16 | 德意志戴斯达纺织品及染料两合公司 | Dye mixtures of fiber-reactive azo dyes, their preparation and their use |
| CN1643079A (en) * | 2002-03-22 | 2005-07-20 | 德意志戴斯达纺织品及染料两合公司 | Dye mixtures of fiber-reactive azo dyes, their preparation and use |
| CN1730566A (en) * | 2005-08-30 | 2006-02-08 | 大连理工大学 | Alkali resistant black active dye suitable for batch cold process |
| CN1730565A (en) * | 2005-08-30 | 2006-02-08 | 大连理工大学 | Black and active dye |
| CN1912014A (en) * | 2006-08-15 | 2007-02-14 | 大连华成中瑞科技有限公司 | Dark black active dyestuff having high colour fixing rate |
| CN1977001A (en) * | 2004-09-02 | 2007-06-06 | 德意志戴斯达纺织品及染料两合公司 | Dye mixtures of fibre-reactive azo dyes production and use thereof |
| TW200825142A (en) * | 2006-12-05 | 2008-06-16 | Everlight Chem Ind Corp | Reactive red dye composition and application thereof |
| CN101283054A (en) * | 2005-10-05 | 2008-10-08 | 德意志戴斯达纺织品及染料两合公司 | Azo reactive dyes and mixtures of fiber-reactive azo dyes, their preparation and their use |
| CN101473000A (en) * | 2006-06-20 | 2009-07-01 | 德意志戴斯达纺织品及染料两合公司 | Dye mixtures of fibre-reactive azo dyes, production and use thereof |
| DE102009047183A1 (en) * | 2008-12-19 | 2010-07-15 | Basf Se | Dye mixture, useful for coloring leather, comprises a first anionic dye, a second anionic dye, and third anionic dye, where the first and third anionic dye are azo dyes, and the second anionic dye is the azo dye or napthalene-azo dye |
| CN102321391A (en) * | 2011-09-07 | 2012-01-18 | 上海雅运纺织化工股份有限公司 | Three primary color reactive dye composition, and dyeing application of three primary color reactive dye composition in fiber |
| CN102344693A (en) * | 2011-08-17 | 2012-02-08 | 无锡润新染料有限公司 | Novel composite active cardinal dye and manufacturing method thereof |
| WO2013021352A2 (en) * | 2011-08-10 | 2013-02-14 | Colourtex Industries Limited | Black mixtures of fibre reactive azo reactive dyestuffs |
| CN103571231A (en) * | 2013-11-07 | 2014-02-12 | 褚平忠 | Dark colored reactive dye with high fixation rate |
-
2015
- 2015-04-29 CN CN201510214052.3A patent/CN104861739A/en active Pending
Patent Citations (15)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6011140A (en) * | 1996-01-11 | 2000-01-04 | Basf Aktiengesellschaft | Reactive azo dyes with an aminonaphthalenesulfonic acid coupling component and intermediates therefor |
| CN1643079A (en) * | 2002-03-22 | 2005-07-20 | 德意志戴斯达纺织品及染料两合公司 | Dye mixtures of fiber-reactive azo dyes, their preparation and use |
| CN1594445A (en) * | 2003-08-16 | 2005-03-16 | 德意志戴斯达纺织品及染料两合公司 | Dye mixtures of fiber-reactive azo dyes, their preparation and their use |
| CN1977001A (en) * | 2004-09-02 | 2007-06-06 | 德意志戴斯达纺织品及染料两合公司 | Dye mixtures of fibre-reactive azo dyes production and use thereof |
| CN1730566A (en) * | 2005-08-30 | 2006-02-08 | 大连理工大学 | Alkali resistant black active dye suitable for batch cold process |
| CN1730565A (en) * | 2005-08-30 | 2006-02-08 | 大连理工大学 | Black and active dye |
| CN101283054A (en) * | 2005-10-05 | 2008-10-08 | 德意志戴斯达纺织品及染料两合公司 | Azo reactive dyes and mixtures of fiber-reactive azo dyes, their preparation and their use |
| CN101473000A (en) * | 2006-06-20 | 2009-07-01 | 德意志戴斯达纺织品及染料两合公司 | Dye mixtures of fibre-reactive azo dyes, production and use thereof |
| CN1912014A (en) * | 2006-08-15 | 2007-02-14 | 大连华成中瑞科技有限公司 | Dark black active dyestuff having high colour fixing rate |
| TW200825142A (en) * | 2006-12-05 | 2008-06-16 | Everlight Chem Ind Corp | Reactive red dye composition and application thereof |
| DE102009047183A1 (en) * | 2008-12-19 | 2010-07-15 | Basf Se | Dye mixture, useful for coloring leather, comprises a first anionic dye, a second anionic dye, and third anionic dye, where the first and third anionic dye are azo dyes, and the second anionic dye is the azo dye or napthalene-azo dye |
| WO2013021352A2 (en) * | 2011-08-10 | 2013-02-14 | Colourtex Industries Limited | Black mixtures of fibre reactive azo reactive dyestuffs |
| CN102344693A (en) * | 2011-08-17 | 2012-02-08 | 无锡润新染料有限公司 | Novel composite active cardinal dye and manufacturing method thereof |
| CN102321391A (en) * | 2011-09-07 | 2012-01-18 | 上海雅运纺织化工股份有限公司 | Three primary color reactive dye composition, and dyeing application of three primary color reactive dye composition in fiber |
| CN103571231A (en) * | 2013-11-07 | 2014-02-12 | 褚平忠 | Dark colored reactive dye with high fixation rate |
Non-Patent Citations (1)
| Title |
|---|
| 王专等: "新型双偶氮红色活性染料的结构与性能关系研究", 《染料与染色》 * |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106634045A (en) * | 2016-12-08 | 2017-05-10 | 浙江亿得化工有限公司 | Dark red reactive dye and preparation method thereof |
| 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 |
| CN112409819B (en) * | 2020-10-26 | 2022-02-15 | 苏州澳缘盛新材料科技有限公司 | Reactive dye red jade and application thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN1296438C (en) | Black and active dye | |
| CN104987750A (en) | Low-alkaline or alkali-free active golden yellow dye and preparation method thereof | |
| CN100528972C (en) | Composite active dye | |
| CN104861739A (en) | Red reactive dye and preparation method thereof | |
| CN101565559B (en) | Navy reactive dye mixture and preparation and application thereof | |
| CN105778561A (en) | Black active dye composition and preparation method and use thereof | |
| CN106634045A (en) | Dark red reactive dye and preparation method thereof | |
| CN103013176A (en) | High-performance green reactive dye mixture and application thereof | |
| CN111100478B (en) | Preparation method and application of blue dye with three active groups | |
| CN104830097A (en) | Yellowish-brown reactive dye and preparation method thereof | |
| CN104194394A (en) | Black reactive dye composition as well as preparation method and application thereof | |
| CN105038312B (en) | A kind of red reactive dyes compound and its preparation and application | |
| CN101705019B (en) | Red reactive dye for wool and preparation method thereof | |
| CN102206428B (en) | Novel responsive dye possessing N-alkylamino radical | |
| CN101255282B (en) | Reactive dye compound and uses thereof | |
| CN102504594B (en) | Reactive red dye composition | |
| CN103351645A (en) | Reactive blue dye and preparation method thereof | |
| CN101704770B (en) | Method for preparing purple reactive dye | |
| CN104893357A (en) | Yellow reactive dye and preparation method thereof | |
| CN104194395A (en) | Reactive red dye composition, reactive red dye as well as preparation method and application of active red dye | |
| CN105440736A (en) | Composite yellow reactive dye for wool and preparation method thereof | |
| CN104693838A (en) | Green reactive dye and preparation method thereof | |
| CN104312202A (en) | Low-alkaline or alkali-free active dark red dye and preparation method thereof | |
| CN104371357A (en) | Low-alkali or alkali-free active bright-red dye and preparation method thereof | |
| CN102391675A (en) | Azo reactive dye and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| EXSB | Decision made by sipo to initiate substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20150826 |
|
| RJ01 | Rejection of invention patent application after publication |