CN104830097A - Yellowish-brown reactive dye and preparation method thereof - Google Patents
Yellowish-brown reactive dye and preparation method thereof Download PDFInfo
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Abstract
A yellowish-brown reactive dye and a preparation method thereof. The invention relates to a yellowish-brown reactive dye and a preparation method thereof. The yellowish-brown reactive dye includes one compound selected from a general formula (1), or a mixture compounded by more than two compounds in the general formula (1) in any proportion. R1, R2, R3, R4, R5 and R6 in the formula (1) independently represent -H, -CH3, -OCH3 and -SO3M; Y1 and Y2 independently represent -CH=CH2 and -C2H4OSO3M; and M represents hydrogen or alkali metal. The yellowish-brown reactive dye has excellent coloration synchronization, high dye uptake and fixation rate, good levelness, and excellent solarization and friction fastness.
Description
Technical field
The invention belongs to the reactive dyestuff field in new material technology, particularly relate to class yellowish brown reactive dyestuffs, 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.
Traditional yellowish brown reactive dyestuffs, general is all based on composite, often adopt three looks composite, a kind of red one indigo plant adding a kind of Huang a small amount of is again come composite, as the patent No. a kind of composite active palm dye that is CN201210488565.X disclosed in Chinese invention patent specification sheets; For another example the patent No. a kind of composite active palm dye etc. disclosed in Chinese invention patent specification sheets that is CN201010221183.1.When composite, compatibleness for dyestuff when the completely inconsistent dyestuff of more than three kinds or three kinds structures is composite is maximum test, because the otherness of precursor structure is comparatively large, the completely inconsistent dyestuff of more than three kinds and three kinds structures is composite really accomplishes that complete compatibility is very difficult.Yellowish-brown is belong to responsive look dyestuff, Ye Shi printing and dyeing mill feels the color of having a headache most, because compatibleness is bad in production process, different dyes also differs comparatively large to fiber affinity, easily causes look flower, causes dyeing percentage of A-class goods to only have about 50%, need repeatedly strip and repair look, cause dyestuff to waste greatly, cost is high, simultaneously also contaminate environment.
Summary of the invention
First invention order of the present invention is that providing a kind of has excellent colouring synchronism, dye uptake and degree of fixation high, good level-dyeing property, the yellowish brown reactive dyestuffs that Exposure to Sunlight, crock fastness are excellent.
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 yellowish brown reactive dyestuffs.
Based on the yellowish brown reactive dyestuffs that first goal of the invention provides, the 3rd goal of the invention of the present invention is also the yellowish brown reactive dyestuffs providing another kind of auxiliary agent to improve.
For first goal of the invention, the technical solution used in the present invention is:
A kind of yellowish brown reactive dyestuffs, 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
4, R
5, R
6separately
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.
As preferred version of the present invention: above-mentioned Y
1and Y
2separately
independentground representative :-C
2h
4oSO
3m; M represents :-Na or-K.
As preferred version of the present invention: Y
1representative :-CH=CH
2; Or Y
2representative :-CH=CH
2; Or Y
1and Y
2all represent :-CH=CH
2;
M represents :-Na or-K.
Further, the yellowish brown reactive dyestuffs shown in formula (1) are the mixture of following formula (1-1) to a kind of or any several concrete structure formula in formula (1-20):
For second goal of the invention, the present invention adopts following scheme:
Adopt following raw material:
Wherein in formula I, formula II, formula III and formula IV:
R
1, R
2, R
3, R
4, R
5, R
6separately
independentground representative-H ,-CH
3,-OCH
3or-SO
3m;
Y
3and Y
4representative-C
2h
4oSO
3m;
M represents hydrogen or basic metal;
The preparation process of process comprises as follows:
A. doazo reaction: formula I is carried out diazotization reaction under the effect of Sodium Nitrite and hydrochloric acid;
B. one
even reaction: the diazotization reaction product of above-mentioned formula I and formula IV carry out one
even reaction;
C. doazo reaction: formula III is carried out diazotization reaction under the effect of Sodium Nitrite and hydrochloric acid;
D. two
even reaction: the diazotization reaction product of above-mentioned formula III and an even thing carry out two
even reaction;
E. doazo reaction: formula II is carried out diazotization reaction under the effect of Sodium Nitrite and hydrochloric acid;
F. three
even reaction: the diazotization reaction product of above-mentioned formula II and two even things carry out three
even reaction, reaction terminates rear acquisition such as formula the yellowish brown reactive dyestuffs 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.
Preferred version as above-mentioned preparation method:
Doazo reaction described in above-mentioned steps a, 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 step b one
even reactiontemperature controls to control to carry out under 0.5-3.0 at 5-25 DEG C, pH;
Described in steps d two
even reactioncarry out under needing the effect of 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;
Described in step f three
even reactioncarry out under needing the effect of sodium bicarbonate or soda ash, temperature of reaction controls to control to carry out under 5.0-8.0 at 5-25 DEG C, pH;
Further, the de-ester reaction described in above-mentioned steps 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.
For the 3rd goal of the invention, another kind of yellowish brown reactive dyestuffs of the present invention, it is mixed by above-mentioned yellowish brown reactive dyestuffs 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; As preferably, 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 yellowish brown reactive dyestuffs, be suitable for the dyeing of cellulosic fibre, its with the patent No. for the composite active palm dye disclosed in CN201210488565.X with CN201010221183.1 is compared, the present invention can monomer structure be main, even time composite, also be the yellowish brown reactive dyestuffs that precursor structure duplicates very much, due to the precursor structure that it adopts similarity high, compatibleness is very good, and above-mentioned two patents, be all form so that three looks composite.Due to above-mentioned principle, yellowish brown reactive dyestuffs of the present invention also have excellent colouring synchronism, dye uptake and degree of fixation high, good level-dyeing property, Exposure to Sunlight, crock fastness are excellent, therefore particularly suitable and cotton fiber dyeing washing fastness, crock fastness, light fastness 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.
Two, in order to improve the water-soluble of dyestuff better, the printing and dyeing such as level-dyeing property effect, above-mentioned dyestuff can also add dissimilar auxiliary agent.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 yellowish brown reactive dyestuffs, 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, doazo reaction: 24g P-nethoxyaniline ortho-sulfonic acid is joined in 100g water and 50g trash ice solution and carry out making beating 1 hour.Then 15g hydrochloric acid (30%) is added, stir after 1 minute, by molten clearly 30% sodium nitrite solution 26g to be added drop-wise to 20 minutes in the P-nethoxyaniline ortho-sulfonic acid 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.Doazo reaction equation is as shown in the formula shown in (a):
2. one
even reaction: 12g mphenylenediamine is joined in 80g water, and makes it complete clearly molten with adding 2.5g hydrochloric acid.Then molten clear mphenylenediamine solution 5 minutes are added drop-wise in Balanced P-nethoxyaniline ortho-sulfonic acid diazonium salt, control temperature 8-10 DEG C, regulate pH=2-3 with 5g sodium bicarbonate, first carry out one
even reaction, the even terminal of stirring reaction to.One
even reactionequation is as shown in the formula shown in (b):
3. doazo reaction: 65g is joined in 100g water and 50g trash ice solution (beta-sulfuric ester ethyl sulfonyl) aniline ortho-sulfonic acid and carries out making beating 1 hour.Then 10g hydrochloric acid (30%) is added, stir after 1 minute, by molten clearly 30% sodium nitrite solution 26g with 20 minutes be added drop-wise to pulled an oar carry out diazotization reaction in (beta-sulfuric ester ethyl sulfonyl) aniline ortho-sulfonic acid, 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.Doazo reaction equation is as shown in the formula shown in (c):
4. two
even reaction: (beta-sulfuric ester ethyl sulfonyl) aniline ortho-sulfonic acid diazonium thing is joined in an idol and carries out two
even reaction, with 15g sodium bicarbonate regulate pH at 4.5-5.5, control temperature at 10-15 DEG C, pH value at 4.5-5.5, react to diazonium salt disappear be two
even reactionterminal, obtains two
even reactionthing, two
even reactionshown in equation following (d):
5. doazo reaction: 65g is joined in 100g water and 50g trash ice solution (beta-sulfuric ester ethyl sulfonyl) aniline ortho-sulfonic acid and carries out making beating 1 hour.Then 10g hydrochloric acid (30%) is added, stir after 1 minute, by molten clearly 30% sodium nitrite solution 26g with 20 minutes be added drop-wise to pulled an oar carry out diazotization reaction in (beta-sulfuric ester ethyl sulfonyl) aniline ortho-sulfonic acid, 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.Doazo reaction equation is as shown in the formula shown in (e):
6. three
even reaction: (beta-sulfuric ester ethyl sulfonyl) aniline ortho-sulfonic acid diazonium thing is joined in two idols and carries out three
even reaction, with 16g sodium bicarbonate regulate pH at 6-7, control temperature at 10-15 DEG C, pH value at 6-7, react to diazonium salt disappear be three
even reactionterminal, obtain (1-1) dyestuff in reactive dyestuffs formula (1), gained magma is all sprayed dry, obtains yellowish brown particle dye 180g.Three
even reactionequation is as shown in the formula shown in (f).
Embodiment 2: a kind of yellowish brown reactive dyestuffs, 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, doazo reaction: 20g open-chain crown ether ortho-sulfonic acid is joined in 100g water and 50g trash ice solution and carry out making beating 1 hour.Then 15g hydrochloric acid (30%) is added, stir after 1 minute, by molten clearly 30% sodium nitrite solution 26g to be added drop-wise to 20 minutes in the open-chain crown ether ortho-sulfonic acid 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.Doazo reaction equation is as shown in the formula shown in (a):
2. one
even reaction: 12g mphenylenediamine is joined in 80g water, and makes it complete clearly molten with adding 2.5g hydrochloric acid.Then molten clear mphenylenediamine solution 5 minutes are added drop-wise in Balanced open-chain crown ether ortho-sulfonic acid diazonium salt, control temperature 8-10 DEG C, regulate pH=2-3 with 5g sodium bicarbonate, first carry out one
even reaction, the even terminal of stirring reaction to.One
even reactionequation is as shown in the formula shown in (b):
3. doazo reaction: 65g is joined in 100g water and 50g trash ice solution (beta-sulfuric ester ethyl sulfonyl) aniline ortho-sulfonic acid and carries out making beating 1 hour.Then 10g hydrochloric acid (30%) is added, stir after 1 minute, by molten clearly 30% sodium nitrite solution 26g with 20 minutes be added drop-wise to pulled an oar carry out diazotization reaction in (beta-sulfuric ester ethyl sulfonyl) aniline ortho-sulfonic acid, 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.Doazo reaction equation is as shown in the formula shown in (c):
4. two
even reaction: (beta-sulfuric ester ethyl sulfonyl) aniline ortho-sulfonic acid diazonium thing is joined in an idol and carries out two
even reaction, with 15g sodium bicarbonate regulate pH at 4.5-5.5, control temperature at 10-15 DEG C, pH value at 4.5-5.5, react to diazonium salt disappear be two
even reactionterminal, obtains two
even reactionthing, two
even reactionequation is as shown in the formula shown in (d):
5. doazo reaction: 65g is joined in 100g water and 50g trash ice solution (beta-sulfuric ester ethyl sulfonyl) aniline ortho-sulfonic acid and carries out making beating 1 hour.Then 10g hydrochloric acid (30%) is added, stir after 1 minute, by molten clearly 30% sodium nitrite solution 26g with 20 minutes be added drop-wise to pulled an oar carry out diazotization reaction in (beta-sulfuric ester ethyl sulfonyl) aniline ortho-sulfonic acid, 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.Doazo reaction equation is as shown in the formula shown in (e):
6. three
even reaction: (beta-sulfuric ester ethyl sulfonyl) aniline ortho-sulfonic acid diazonium thing is joined in two idols and carries out three
even reaction, with 16g sodium bicarbonate regulate pH at 6-7, control temperature at 10-15 DEG C, pH value at 6-7, react to diazonium salt disappear be three
even reactionterminal, obtain (1-2) dyestuff in reactive dyestuffs formula (1), gained magma is all sprayed dry, obtains yellowish brown particle dye 175g.Three
even reactionequation is as shown in the formula shown in (f).
Embodiment 3: a kind of yellowish brown reactive dyestuffs, 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, doazo reaction: 24g P-nethoxyaniline ortho-sulfonic acid is joined in 100g water and 50g trash ice solution and carry out making beating 1 hour.Then 15g hydrochloric acid (30%) is added, stir after 1 minute, by molten clearly 30% sodium nitrite solution 26g to be added drop-wise to 20 minutes in the P-nethoxyaniline ortho-sulfonic acid 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 (A) formula of doazo reaction equation:
2. one
even reaction: 12g mphenylenediamine is joined in 80g water, and makes it complete clearly molten with adding 2.5g hydrochloric acid.Then molten clear mphenylenediamine solution 5 minutes are added drop-wise in Balanced P-nethoxyaniline ortho-sulfonic acid diazonium salt, control temperature 8-10 DEG C, regulate pH=2-3 with 5g sodium bicarbonate, first carry out one
even reaction, the even terminal of stirring reaction to.One
even reactionshown in equation following (B):
3. doazo reaction: 32g is joined in 100g water and 50g trash ice solution (beta-sulfuric ester ethyl sulfonyl) aniline and carries out making beating 1 hour.Then 10g hydrochloric acid (30%) is added, stir after 1 minute, by molten clearly 30% sodium nitrite solution 26g with 20 minutes be added drop-wise to pulled an oar carry out diazotization reaction in (beta-sulfuric ester ethyl sulfonyl) aniline, 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.Doazo reaction equation is as shown in the formula shown in (c):
4. two
even reaction: (beta-sulfuric ester ethyl sulfonyl) aniline diazonium thing is joined in an idol and carries out two
even reaction, with 15g sodium bicarbonate regulate pH at 4.5-5.5, control temperature at 10-15 DEG C, pH value at 4.5-5.5, react to diazonium salt disappear be two
even reactionterminal, obtains two
even reactionthing, two
even reactionshown in equation following (d):
5. doazo reaction: 32g is joined in 100g water and 50g trash ice solution (beta-sulfuric ester ethyl sulfonyl) aniline and carries out making beating 1 hour.Then 10g hydrochloric acid (30%) is added, stir after 1 minute, by molten clearly 30% sodium nitrite solution 26g with 20 minutes be added drop-wise to pulled an oar carry out diazotization reaction in (beta-sulfuric ester ethyl sulfonyl) aniline, 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.Doazo reaction equation is as shown in the formula shown in (e) formula:
6. three
even reaction: (beta-sulfuric ester ethyl sulfonyl) aniline diazonium thing is joined in two idols and carries out three
even reaction, with 16g sodium bicarbonate regulate pH at 6-7, control temperature at 10-15 DEG C, pH value at 6-7, react to diazonium salt disappear be three
even reactionterminal, obtain (1-2) dyestuff in reactive dyestuffs formula (1), gained magma is all sprayed dry, obtains yellowish brown particle dye 170g.Three
even reactionequation is as shown in the formula shown in (f).
Embodiment 4: a kind of yellowish brown reactive dyestuffs, is made up of the compound of simple formula (1-4) structure:
Formula (1-4) its preparation method adopts following raw material:
Raw material in alternative embodiment 1, its preparation process repeats embodiment 1.
Embodiment 5: a kind of yellowish brown reactive dyestuffs, is made up of the compound of simple formula (1-5) structure:
Formula (1-5) its preparation method adopts following raw material:
Raw material in alternative embodiment 1, its preparation process repeats embodiment 1.
Embodiment 6: a kind of yellowish brown reactive dyestuffs, is made up of the compound of simple formula (1-6) structure:
Formula (1-6) its preparation method adopts following raw material:
Raw material in alternative embodiment 1, its preparation process repeats embodiment 1.
Embodiment 7: a kind of yellowish brown reactive dyestuffs, is made up of the compound of simple formula (1-7) structure:
Formula (1-7) its preparation method adopts following raw material:
Raw material in alternative embodiment 1, its preparation process repeats embodiment 1.
Embodiment 8: a kind of yellowish brown reactive dyestuffs, is made up of the compound of simple formula (1-8) structure:
Formula (1-8) its preparation method adopts following raw material:
Raw material in alternative embodiment 1, its preparation process repeats embodiment 1.
Embodiment 9: a kind of yellowish brown reactive dyestuffs, is made up of the compound of simple formula (1-9) structure:
Formula (1-9) its preparation method adopts following raw material:
Raw material in alternative embodiment 1, its preparation process repeats embodiment 1.
Embodiment 10: a kind of yellowish brown reactive dyestuffs, is made up of the compound of simple formula (1-10) structure:
Formula (1-10) its preparation method adopts following raw material:
Raw material in alternative embodiment 1, its preparation process repeats embodiment 1.
Embodiment 11: a kind of yellowish brown reactive dyestuffs, formula (1-11) structure is as follows:
Be that its preparation process f terminates to carry out de-ester process further afterwards with the difference of embodiment 1: be warmed up to 50-70 DEG C at above-mentioned product, regulate pH8.0-9.0 with soda ash powder, react 1 hour, carry out alkaline purification reaction.After de-ester terminal arrives, add hydrochloric acid readjustment joint pH to 5.0-6.5, magma spraying dry can obtain yellowish brown particle dye.Reaction equation is as shown in the formula shown in (g):
Certainly, the present embodiment also comprise de-ester completely time, the situation of above-mentioned formula (1-11) and embodiment 1 mixture.
Embodiment 12: a kind of yellowish brown reactive dyestuffs, formula (1-12) structure is as follows:
On the basis of embodiment 2, the de-ester process repeated in embodiment 11 obtains; The present embodiment also comprise de-ester completely time, the situation of above-mentioned formula (1-12) and embodiment 2 mixture.
Embodiment 13: a kind of yellowish brown reactive dyestuffs, formula (1-13) structure is as follows:
On the basis of embodiment 3, the de-ester process repeated in embodiment 11 obtains; The present embodiment also comprise de-ester completely time, the situation of above-mentioned formula (1-13) and embodiment 3 mixture.
Embodiment 14: a kind of yellowish brown reactive dyestuffs, formula (1-14) structure is as follows:
On the basis of embodiment 4, the de-ester process repeated in embodiment 11 obtains; The present embodiment also comprise de-ester completely time, the situation of above-mentioned formula (1-14) and embodiment 4 mixture.
Embodiment 15: a kind of yellowish brown reactive dyestuffs, formula (1-15) structure is as follows:
On the basis of embodiment 5, the de-ester process repeated in embodiment 11 obtains; The present embodiment also comprise de-ester completely time, the situation of above-mentioned formula (1-15) and embodiment 5 mixture.
Embodiment 16: a kind of yellowish brown reactive dyestuffs, formula (1-16) structure is as follows:
On the basis of embodiment 6, the de-ester process repeated in embodiment 11 obtains; The present embodiment also comprise de-ester completely time, the situation of above-mentioned formula (1-16) and embodiment 6 mixture.
Embodiment 17: a kind of yellowish brown reactive dyestuffs, formula (1-17) structure is as follows:
On the basis of embodiment 7, the de-ester process repeated in embodiment 11 obtains; The present embodiment also comprise de-ester completely time, the situation of above-mentioned formula (1-17) and embodiment 7 mixture.
Embodiment 18: a kind of yellowish brown reactive dyestuffs, formula (1-18) structure is as follows:
On the basis of embodiment 8, the de-ester process repeated in embodiment 11 obtains; The present embodiment also comprise de-ester completely time, the situation of above-mentioned formula (1-18) and embodiment 8 mixture.
Embodiment 19: a kind of yellowish brown reactive dyestuffs, formula (1-19) structure is as follows:
On the basis of embodiment 9, the de-ester process repeated in embodiment 11 obtains; The present embodiment also comprise de-ester completely time, the situation of above-mentioned formula (1-19) and embodiment 9 mixture.
Embodiment 20: a kind of yellowish brown reactive dyestuffs, formula (1-20) structure is as follows:
On the basis of embodiment 10, the de-ester process repeated in embodiment 11 obtains; The present embodiment also comprise de-ester completely time, the situation of above-mentioned formula (1-20) and embodiment 10 mixture.
Embodiment 21: a kind of yellowish brown reactive dyestuffs, by formula (1-1) the structural compounds 70g in embodiment 1, formula (1-2) structural compounds 5g in embodiment 2, mix in embodiment 8 Chinese style (1-8) structural compounds 25g tempering tank, or spraying dry after common dissolving.
Embodiment 22: a kind of yellowish brown reactive dyestuffs, 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 23: a kind of yellowish brown reactive dyestuffs, 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 24: a kind of yellowish brown reactive dyestuffs, 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 25: a kind of yellowish brown reactive dyestuffs, by embodiment 5 Chinese style (1-5) structural compounds 50g, embodiment 7 Chinese style (1-7) structural compounds 50g and Sodium hexametaphosphate 99 15g mixes in tempering tank, or spraying dry after common dissolving.
Embodiment 26: a kind of yellowish brown reactive dyestuffs, by embodiment 6 Chinese style (1-6) structural compounds 30g, mix in embodiment 8 Chinese style (1-8) structural compounds 70g and condensation compound of methyl naphthalene sulfonic acid and formaldehyde 20g tempering tank, or spraying dry after common dissolving.
Embodiment 27: a kind of yellowish brown reactive dyestuffs, 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 yellowish brown reactive dyestuffs:
Respectively taking the above-mentioned dyestuff of 1g (1-1)---the dye monomer compound that (1-20) is obtained or its two kinds or two or more mixture (embodiment 21,24,25,26) 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 yellowish brown cotton obtained has the yellowish brown of homogeneity, satisfied Exposure to Sunlight and fastness to rubbing, and specific performance is shown in
table 1.
table 1
Detect according to great many of experiments and show that yellowish brown reactive dyestuffs of the present invention have excellent application performance than traditional composite yellowish brown reactive dyestuffs, concrete correlation data is shown in
table 2.
table 2
| Sequence number | First-time qualification rate | Fastness to wet rubbing | Light fastness | Compatibleness |
| Dyestuff 1 of the present invention | 98％ | 3-4 | 4 | Good |
| Dyestuff 2 of the present invention | 99％ | 3-4 | 4-5 | Good |
| Dyestuff 3 of the present invention | 95％ | 3-4 | 4-5 | Good |
| Dyestuff 4 of the present invention | 95％ | 3-4 | 4-5 | Good |
| Dyestuff 5 of the present invention | 96％ | 3-4 | 4-5 | Good |
| Dyestuff 6 of the present invention | 95％ | 3-4 | 4 | Good |
| Dyestuff 7 of the present invention | 97％ | 3-4 | 4-5 | Good |
| Dyestuff 8 of the present invention | 95％ | 3-4 | 4-5 | Good |
| Dyestuff 9 of the present invention | 95％ | 3-4 | 4-5 | Good |
| Dyestuff 10 of the present invention | 95％ | 3-4 | 4 | Good |
| Dyestuff 11 of the present invention | 99％ | 3-4 | 4-5 | Good |
| Dyestuff 12 of the present invention | 98％ | 3-4 | 4 | Good |
| Dyestuff 13 of the present invention | 96％ | 3-4 | 4-5 | Good |
| Dyestuff 14 of the present invention | 96％ | 3-4 | 4-5 | Good |
| Dyestuff 15 of the present invention | 95％ | 3-4 | 4 | Good |
| Dyestuff 16 of the present invention | 96％ | 3-4 | 4-5 | Good |
| Dyestuff 17 of the present invention | 95％ | 3-4 | 4-5 | Good |
| Dyestuff 18 of the present invention | 96％ | 3-4 | 4 | Good |
| Dyestuff 19 of the present invention | 98％ | 3-4 | 4-5 | Good |
| Dyestuff 20 of the present invention | 97％ | 3-4 | 4-5 | Good |
| Dyestuff 21 of the present invention | 95％ | 3-4 | 4 | Good |
| Dyestuff 24 of the present invention | 97％ | 3-4 | 4-5 | Good |
| Dyestuff 25 of the present invention | 95％ | 3-4 | 4-5 | Good |
| Dyestuff 26 of the present invention | 95％ | 3-4 | 4-5 | Good |
| Sample 1 is reddish brown | 40％ | 2-3 | 3-4 | Difference |
| Sample 2 is yellowish-brown | 45％ | 3 | 3-4 | Difference |
| Sample 3 palm fibre | 50％ | 2-3 | 4 | Generally |
| Sample 4 palm fibre | 35％ | 3 | 3-4 | Generally |
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. yellowish brown reactive dyestuffs, 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
4, R
5, R
6represent independently of one another :-H ,-CH
3,-OCH
3or-SO
3m;
Y
1and Y
2represent independently of one another :-CH=CH
2or-C
2h
4oSO
3m;
M represents: hydrogen or basic metal.
2. a kind of yellowish brown reactive dyestuffs according to claim 1, is characterized in that:
Y
1and Y
2represent independently of one another :-C
2h
4oSO
3m;
M represents :-Na or-K.
3. a kind of yellowish brown reactive dyestuffs 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 or-K.
4. a kind of yellowish brown reactive dyestuffs according to claim 1, is characterized in that: the yellowish brown reactive dyestuffs shown in formula (1) are the mixture of following formula (1-1) to a kind of or any several concrete structure formula in formula (1-20):
。
5. a preparation method for yellowish brown reactive dyestuffs as claimed in claim 1, is characterized in that:
Adopt following raw material:
Wherein in formula I, formula II, formula III and formula IV:
R
1, R
2, R
3, R
4, R
5, R
6represent-H ,-CH independently of one another
3,-OCH
3or-SO
3m;
Y
3and Y
4representative-C
2h
4oSO
3m;
M represents hydrogen or basic metal;
The preparation process of process comprises as follows:
A. doazo reaction: formula I is carried out diazotization reaction under the effect of Sodium Nitrite and hydrochloric acid;
B. an even reaction: the diazotization reaction product of above-mentioned formula I and formula IV carry out and occasionally react;
C. doazo reaction: formula III is carried out diazotization reaction under the effect of Sodium Nitrite and hydrochloric acid;
D. two even reactions: the diazotization reaction product of above-mentioned formula III and an even thing carry out two and occasionally react;
E. doazo reaction: formula II is carried out diazotization reaction under the effect of Sodium Nitrite and hydrochloric acid;
F. three even reactions: the diazotization reaction product of above-mentioned formula II and two even things carry out three and occasionally react, and reaction terminates rear acquisition such as formula the yellowish brown reactive dyestuffs 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.
6. the preparation method of a kind of yellowish brown reactive dyestuffs according to claim 5, is characterized in that:
Doazo reaction described in step a, 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 step b 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 steps d 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;
Carry out under the effect of described in step f three even reaction needed sodium bicarbonate or soda ash, temperature of reaction controls to control to carry out under 5.0-8.0 at 5-25 DEG C, pH.
7. the preparation method of a kind of yellowish brown reactive dyestuffs 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. yellowish brown reactive dyestuffs, is characterized in that: mixed by yellowish brown reactive dyestuffs 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 yellowish brown reactive dyestuffs according to claim 8, is characterized in that: described auxiliary agent is Sodium sulfate anhydrous.min(99).
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