CN102876079A - Black reactive dye and preparation method thereof - Google Patents
Black reactive dye and preparation method thereof Download PDFInfo
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- CN102876079A CN102876079A CN2012103527953A CN201210352795A CN102876079A CN 102876079 A CN102876079 A CN 102876079A CN 2012103527953 A CN2012103527953 A CN 2012103527953A CN 201210352795 A CN201210352795 A CN 201210352795A CN 102876079 A CN102876079 A CN 102876079A
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- 238000002360 preparation method Methods 0.000 title claims abstract description 25
- 239000000985 reactive dye Substances 0.000 title abstract 5
- 238000000034 method Methods 0.000 claims abstract description 6
- 238000006243 chemical reaction Methods 0.000 claims description 39
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 33
- 230000008878 coupling Effects 0.000 claims description 30
- 238000010168 coupling process Methods 0.000 claims description 30
- 238000005859 coupling reaction Methods 0.000 claims description 30
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 24
- 125000000664 diazo group Chemical group [N-]=[N+]=[*] 0.000 claims description 20
- 239000007788 liquid Substances 0.000 claims description 20
- LPXPTNMVRIOKMN-UHFFFAOYSA-M sodium nitrite Chemical compound [Na+].[O-]N=O LPXPTNMVRIOKMN-UHFFFAOYSA-M 0.000 claims description 20
- 238000003756 stirring Methods 0.000 claims description 17
- FDDDEECHVMSUSB-UHFFFAOYSA-N sulfanilamide Chemical compound NC1=CC=C(S(N)(=O)=O)C=C1 FDDDEECHVMSUSB-UHFFFAOYSA-N 0.000 claims description 16
- 229940124530 sulfonamide Drugs 0.000 claims description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 15
- 238000006193 diazotization reaction Methods 0.000 claims description 14
- 238000012360 testing method Methods 0.000 claims description 12
- 235000010288 sodium nitrite Nutrition 0.000 claims description 10
- 150000001875 compounds Chemical class 0.000 claims description 9
- 238000012546 transfer Methods 0.000 claims description 8
- 230000007062 hydrolysis Effects 0.000 claims description 7
- 238000006460 hydrolysis reaction Methods 0.000 claims description 7
- IOVCWXUNBOPUCH-UHFFFAOYSA-N Nitrous acid Chemical compound ON=O IOVCWXUNBOPUCH-UHFFFAOYSA-N 0.000 claims description 6
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 6
- 239000002253 acid Substances 0.000 claims description 6
- IQFVPQOLBLOTPF-HKXUKFGYSA-L congo red Chemical compound [Na+].[Na+].C1=CC=CC2=C(N)C(/N=N/C3=CC=C(C=C3)C3=CC=C(C=C3)/N=N/C3=C(C4=CC=CC=C4C(=C3)S([O-])(=O)=O)N)=CC(S([O-])(=O)=O)=C21 IQFVPQOLBLOTPF-HKXUKFGYSA-L 0.000 claims description 6
- 239000010813 municipal solid waste Substances 0.000 claims description 5
- 230000035484 reaction time Effects 0.000 claims description 3
- 239000011734 sodium Substances 0.000 claims description 3
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 3
- 235000017550 sodium carbonate Nutrition 0.000 claims description 3
- 238000001914 filtration Methods 0.000 claims description 2
- 238000012423 maintenance Methods 0.000 claims description 2
- APRRQJCCBSJQOQ-UHFFFAOYSA-N 4-amino-5-hydroxynaphthalene-2,7-disulfonic acid Chemical compound OS(=O)(=O)C1=CC(O)=C2C(N)=CC(S(O)(=O)=O)=CC2=C1 APRRQJCCBSJQOQ-UHFFFAOYSA-N 0.000 claims 8
- 239000004677 Nylon Substances 0.000 abstract description 7
- 238000004043 dyeing Methods 0.000 abstract description 7
- 229920001778 nylon Polymers 0.000 abstract description 7
- 239000004744 fabric Substances 0.000 abstract description 3
- 229910052755 nonmetal Inorganic materials 0.000 abstract description 2
- 238000010668 complexation reaction Methods 0.000 abstract 1
- 239000000975 dye Substances 0.000 description 29
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 24
- 238000009413 insulation Methods 0.000 description 16
- 239000012065 filter cake Substances 0.000 description 14
- QPILZZVXGUNELN-UHFFFAOYSA-M sodium;4-amino-5-hydroxynaphthalene-2,7-disulfonate;hydron Chemical compound [Na+].OS(=O)(=O)C1=CC(O)=C2C(N)=CC(S([O-])(=O)=O)=CC2=C1 QPILZZVXGUNELN-UHFFFAOYSA-M 0.000 description 13
- 238000010792 warming Methods 0.000 description 13
- 229910052757 nitrogen Inorganic materials 0.000 description 12
- NVBFHJWHLNUMCV-UHFFFAOYSA-N sulfamide Chemical compound NS(N)(=O)=O NVBFHJWHLNUMCV-UHFFFAOYSA-N 0.000 description 12
- 239000000047 product Substances 0.000 description 9
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 description 6
- 238000004458 analytical method Methods 0.000 description 6
- DPDMMXDBJGCCQC-UHFFFAOYSA-N [Na].[Cl] Chemical compound [Na].[Cl] DPDMMXDBJGCCQC-UHFFFAOYSA-N 0.000 description 5
- 238000001035 drying Methods 0.000 description 5
- FIXVWFINKCQNFG-UHFFFAOYSA-M sodium;4-[(4-aminophenyl)diazenyl]benzenesulfonate Chemical compound [Na+].C1=CC(N)=CC=C1N=NC1=CC=C(S([O-])(=O)=O)C=C1 FIXVWFINKCQNFG-UHFFFAOYSA-M 0.000 description 5
- 238000005660 chlorination reaction Methods 0.000 description 4
- 159000000000 sodium salts Chemical class 0.000 description 4
- 230000007613 environmental effect Effects 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 238000007670 refining Methods 0.000 description 3
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 description 2
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 2
- 206010013786 Dry skin Diseases 0.000 description 2
- ODFJOVXVLFUVNQ-UHFFFAOYSA-N acetarsol Chemical compound CC(=O)NC1=CC([As](O)(O)=O)=CC=C1O ODFJOVXVLFUVNQ-UHFFFAOYSA-N 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 238000009833 condensation Methods 0.000 description 2
- 230000005494 condensation Effects 0.000 description 2
- 230000032050 esterification Effects 0.000 description 2
- 238000005886 esterification reaction Methods 0.000 description 2
- XTHPWXDJESJLNJ-UHFFFAOYSA-N sulfurochloridic acid Chemical compound OS(Cl)(=O)=O XTHPWXDJESJLNJ-UHFFFAOYSA-N 0.000 description 2
- FYSNRJHAOHDILO-UHFFFAOYSA-N thionyl chloride Chemical compound ClS(Cl)=O FYSNRJHAOHDILO-UHFFFAOYSA-N 0.000 description 2
- QPQKUYVSJWQSDY-CCEZHUSRSA-N 4-(phenylazo)aniline Chemical compound C1=CC(N)=CC=C1\N=N\C1=CC=CC=C1 QPQKUYVSJWQSDY-CCEZHUSRSA-N 0.000 description 1
- 0 CCCC(C)[C@](CC[C@@](C)N=NC)N=N[C@](C1)[C@@](*)CC(C[C@@]([C@@]2N=NC)S)=C1C2N Chemical compound CCCC(C)[C@](CC[C@@](C)N=NC)N=N[C@](C1)[C@@](*)CC(C[C@@]([C@@]2N=NC)S)=C1C2N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000000536 complexating effect Effects 0.000 description 1
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- 238000012545 processing Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
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Abstract
The invention relates to a black reactive dye and a preparation method thereof. The black reactive dye has the structural formula as follows: FORMULA. The invention further provides the preparation method of the black reactive dye. The black reactive dye prepared by the preparation method has the advantages of high applicability, non-metal complexation, no damage to human health and environment, especial applicability for nylon fabric dyeing, high color fixation and fastness, and good reproducibility and stability in a dyeing process.
Description
Technical field
The present invention relates to a kind of reactive dyestuffs, especially a kind of black and active dye that is applicable to dyeing nylon and preparation method thereof.
Background technology
Along with updating of nylon fabrics performance, its consumption is increasing, but its dyeing course, especially dye black, what basically use now is metallized dye, because the existence of heavy metal, that manufacturing processed or use procedure all will affect environmental and human health impacts, along with the progress of society, people's environmental consciousness is more and more stronger, and the environmental friendliness type dye becomes present development trend.Therefore be badly in need of a kind of excellent performance, black and active dye free from environmental pollution.
Summary of the invention
The objective of the invention is to overcome the deficiency of existing metallized dye, a kind of black and active dye that is applicable to nylon material dyeing and preparation method thereof is provided.
The technical solution used in the present invention is:
A kind of black and active dye, its structural formula be as shown in the formula (I):
R
1A kind of in the following substituting group;-H ,-NO
2,-OCH
3Or-SO
3Na.
The present invention also provides the preparation method of above-mentioned black and active dye, and the method comprises following steps:
(a) structure formula II compound diazotization:
Xiang Shuizhong adds the formula II compound, adds ice and hydrochloric acid, adds sodium nitrite solution again, and diazotization gets the first diazo liquid;
R
2A kind of in the following substituting group;-H ,-NO
2,-OCH
3Or-SO
3H;
(b) H acid solution preparation
Xiang Shuizhong adds H acid and stirs, and accent pH is 6-7, gets the H acid solution;
(c) a step coupling
Step (b) gained H acid solution is joined in step (a) gained the first diazo liquid, react to get a step coupling solution;
(d) P-aminoazobenzene-4-(N-ethylsulfuric acid ester group) sulphonamide diazotization
Xiang Shuizhong adds P-aminoazobenzene-4-(N-ethylsulfuric acid ester group) sulphonamide, adds ice and hydrochloric acid, adds sodium nitrite solution again, and diazotization gets the second diazo liquid;
(e) two step couplings:
Step (d) is obtained the second diazo liquid join in the step coupling solution that step (c) obtains, react and to get two step coupling solutions;
(f) hydrolysis:
The two step coupling solutions that step (e) is obtained are hydrolyzed at pH=8-12, get hydrolyzed solution, namely make structural formula (I) black and active dye.
Further, also comprise the steps:
(g) refining: as in step (f) gained hydrolyzed solution, to add sodium-chlor, make dyestuff separate out and filter, collect the dyestuff filter cake.
(h) drying: the dyestuff filter cake is dried, pulverized, get the finished product black and active dye.
Further, the preparation method of black and active dye of the present invention comprises following steps:
(a) structure formula II compound diazotization:
R
2A kind of in the following substituting group;-H ,-NO
2,-OCH
3Or-SO
3H;
Add water to retort, then add structure formula II compound, after stirring, add trash ice and 30wt % hydrochloric acid soln, add again the 30wt% sodium nitrite solution, finish reaction 1-3 hour, be blue after the maintenance congo-red test paper soaks, be blue after the KI test paper soaks; React complete and remove unreacted nitrous acid with thionamic acid, get the first diazo liquid, for subsequent use;
(b) H acid solution preparation:
Add entry to retort, then add H acid, transfer pH=6-7 with the 30wt% sodium hydroxide solution, complete after molten the H acid solution, for subsequent use.
(c) a step coupling:
The first diazo liquid of step (a) preparation is put into retort, add again the H acid solution of step (b) preparation, temperature 7-10 ℃, stirring reaction 2-5 hour, get a step coupling solution, for subsequent use.
(d) P-aminoazobenzene-4-(N-ethylsulfuric acid ester group) sulphonamide diazotization
Add water to retort, then add P-aminoazobenzene-4-(N-ethylsulfuric acid ester group) sulphonamide, after stirring, add trash ice and 30wt% hydrochloric acid soln, add again the 30wt% sodium nitrite solution, finish and react again 1-4 hour, be blue after keeping congo-red test paper to soak, be blue after the KI test paper soaks, react complete and remove unreacted nitrous acid with thionamic acid, get the second diazo liquid, for subsequent use.
(e) two step couplings:
With the second diazo liquid that step (d) obtains, join in the step coupling solution of step (c) acquisition, stir, transfer pH=5-8 with yellow soda ash, temperature 15-30 ℃ was reacted 3-6 hour, reacted complete filtration, got two step coupling solutions, for subsequent use.
(f) hydrolysis:
Two step of (e) step gained coupling solution is transferred pH=8-12 with the 30wt% sodium hydroxide solution, the reaction that is hydrolyzed, reaction times 4-8 hour, get hydrolyzed solution, namely get structural formula (I) black and active dye.
(g) refining:
(f) step gained hydrolyzed solution is added sodium-chlor according to the ratio that every 100ml adds 10-30g, treat that dyestuff separates out fully, filter, collect filter cake, weigh, analysis content, for subsequent use.
(h) drying:
(g) step filter cake is dried, pulverized, weigh, get the finished product black and active dye.
The invention still further relates to a kind of dye composite, this dye composite comprises one or more structures of said structure formula (I).
The present invention also provides the application of above-mentioned reactive dyestuffs in dyeing nylon.
H acid of the present invention is 1-amino-8-naphthol-3, the abbreviation of 6-disulfonate sodium, and its structural formula is as follows:
Para-ester: formal name used at school is that its structural formula is as follows to (beta-sulfuric ester ethyl sulfonyl) aniline:
P-aminoazobenzene-4-(N-ethylsulfuric acid ester group) sulphonamide has another name called P-aminoazobenzene-4-sulfonamido ethylsulfuric acid ester, and structural formula is as follows:
This P-aminoazobenzene-4-(N-ethylsulfuric acid ester group) preparation method of sulphonamide comprises the steps:
(a) P-aminoazobenzene-4-sulfonic acid acidylate
P-aminoazobenzene-4-sulfonic acid is added to the water, is warming up to 80 ℃, transfer pH=7.5～8.5 with 30% sodium hydroxide solution, material is dissolved fully, be cooled to 35 ℃, slowly drip acetic anhydride, approximately finished in 15～20 minutes, control pH=5～6.5 are in 40 ℃～50 ℃, insulation reaction 2～3 hours, take P-aminoazobenzene-4-sulfonic acid completely dissolve as reaction end, be cooled to 15～20 ℃, add the chlorination sodium salt and analyse, filter, filter cake is dried;
(b) chlorosulphonation
Step (a) gained dry product is joined in the reaction vessel, add chlorsulfonic acid by weight 1:5～10,1～1.5 hour time spent was warming up to 128～130 ℃, insulation reaction 4 hours, be cooled to 60 ℃, under this temperature, dripped sulfur oxychloride in 1.5～2 hours, finish rear insulation reaction 2 hours, be warming up to 90～95 ℃, insulation reaction 30 minutes, be warming up to again 105～110 ℃, insulation reaction 30 minutes is cooled to 15～20 ℃, dilutes with frozen water, flush cake gets acetparaminosalol nitrogen benzide-4-SULPHURYL CHLORIDE;
(c) condensation
Step (b) gained acetparaminosalol nitrogen benzide-4-SULPHURYL CHLORIDE is joined in the reactor, be warming up to 35 ℃～45 ℃, 30 minutes times spent added Monoethanolamine MEA BASF, kept pH=7.5～9, insulation reaction 5～8 hours, take acetparaminosalol nitrogen benzide-4-SULPHURYL CHLORIDE completely dissolve as reaction end, after reaction is finished, be cooled to 20 ℃, adding the chlorination sodium salt analyses, filter, collect filter cake, get the amino sulfone of acetparaminosalol nitrogen benzide-4-beta-hydroxyethyl;
(d) hydrolysis
The amino sulfone of step (c) products therefrom acetparaminosalol nitrogen benzide-4-beta-hydroxyethyl is joined in the reaction vessel, add water and stir, add again 96% sodium hydroxide, 1～1.5 hour time spent, be warming up to 100 ℃, insulation reaction 1-2 hour, thin layer plate launched take the amino sulfone completely dissolve of kharophen nitrogen benzide-4-beta-hydroxyethyl as reaction end, be cooled to 20 ℃, hydrochloric acid soln with 30% is adjusted pH=6～6.5, filters, and collects filter cake, dry, get the amino sulfone of P-aminoazobenzene-4-beta-hydroxyethyl;
(e) esterification
The amino sulfone of step (d) product P-aminoazobenzene-4-beta-hydroxyethyl is joined in the four-hole bottle, oleum by weight 1:7～10 addings 103%～105%, heat up 35～45 ℃, insulation reaction 4～6 hours, take the amino sulfone completely dissolve of P-aminoazobenzene-4-beta-hydroxyethyl as terminal point, after finishing, reaction dilutes flush cake with frozen water, filter cake gets P-aminoazobenzene-4-(N-ethylsulfuric acid ester group 70 ℃ of dryings) sulphonamide.
The beneficial effect that the present invention has:
The black and active dye suitability that the present invention makes is strong, and nonmetal complexing can not be detrimental to health and environment, especially is fit to dye nylon fabrics, high fixation, high fastness, and dyeing course has good circulation ratio and stability.
Embodiment
The following examples just to the explanation of technical scheme of the present invention, do not form any restriction to technical scheme of the present invention and protection domain.
Embodiment 1:
P-aminoazobenzene-4-(N-ethylsulfuric acid ester group) sulphonamide, structural formula is as follows:
This P-aminoazobenzene-4-(N-ethylsulfuric acid ester group) preparation method of sulphonamide comprises the steps:
(a) P-aminoazobenzene-4-sulfonic acid acidylate
100% P-aminoazobenzene of measuring-4-sulfonic acid 27.7g is added in the 500ml beaker, add water 250ml, be warming up to 80 ℃, transfer pH=7.5～8 with 30% sodium hydroxide solution, material is dissolved fully, be cooled to 35 ℃, slowly drip acetic anhydride, approximately finished in 15～20 minutes, control pH=5～6.5 are in 40 ℃～50 ℃, insulation reaction, take P-aminoazobenzene-4-sulfonic acid completely dissolve as reaction end, be down to 15～20 ℃, get solution A, adding the chlorination sodium salt analyses again, wherein the ratio of sodium-chlor and solution A is 0.15g:1mL, filters, and filter cake is dried;
(b) chlorosulphonation
Step (a) gained dry product 30g is joined in the 500ml four-hole bottle, add chlorsulfonic acid 210g, 1 hour time spent, be warming up to 128～130 ℃, insulation reaction 4 hours is cooled to 60 ℃, under this temperature, drip sulfur oxychloride in 1.5 hours, finish rear insulation reaction 2 hours, be warming up to 90～95 ℃ of insulation reaction 30 minutes, be warming up to again 105～110 ℃, insulation reaction 30 minutes is cooled to 15～20 ℃, dilutes with frozen water, flush cake gets acetparaminosalol nitrogen benzide-4-SULPHURYL CHLORIDE;
(c) condensation
The acetparaminosalol nitrogen benzide of step (b) gained-4-SULPHURYL CHLORIDE is joined in the 1000ml beaker, be warming up to 35 ℃～45 ℃, 30 minutes times spent added Monoethanolamine MEA BASF, keep pH=7.5～8, insulation reaction, take acetparaminosalol nitrogen benzide-4-SULPHURYL CHLORIDE completely dissolve as reaction end, after reaction is finished, be cooled to 20 ℃, get solution B, add again the chlorination sodium salt and analyse, wherein the ratio of sodium-chlor and solution B is 0.15g:1mL, filter, collect filter cake, get the amino sulfone of acetparaminosalol nitrogen benzide-4-beta-hydroxyethyl;
(d) hydrolysis
The amino sulfone of step (c) products therefrom acetparaminosalol nitrogen benzide-4-beta-hydroxyethyl is joined in the 1000ml beaker, adding 400ml water stirs, if by volume mass ratio 4%(volume mass is 100ml than 4% volume that refers to solution, the add-on of 96% sodium hydroxide is 4g) add-on adds 96% sodium hydroxide 16g, 1 hour time spent was warming up to 100 ℃, the insulation reaction thin layer plate launches take the amino sulfone completely dissolve of kharophen nitrogen benzide-4-beta-hydroxyethyl as reaction end, be cooled to 20 ℃, adjust pH=6～6.5 with 30% hydrochloric acid soln, filter, collect filter cake, dry, get the amino sulfone of P-aminoazobenzene-4-beta-hydroxyethyl;
(e) esterification
The amino sulfone 40g of step (d) product P-aminoazobenzene-4-beta-hydroxyethyl is joined in the four-hole bottle, the oleum 280g of adding 103%, heat up 35～45 ℃, insulation reaction, take the amino sulfone completely dissolve of P-aminoazobenzene-4-beta-hydroxyethyl as terminal point, after finishing, reaction dilutes flush cake with frozen water, filter cake gets P-aminoazobenzene-4-(N-ethylsulfuric acid ester group 70 ℃ of dryings) sulphonamide.
Embodiment 2:
A kind of preparation method of black and active dye comprises the steps:
(a) para-ester diazotization:
In 200ml water, add para-ester 28.1 g, add 100g ice and 30 wt % hydrochloric acid soln 15g, add 30 wt % sodium nitrite solutions, 24 g, under 0-5 ℃ of temperature, stir 3h, be blue after keeping congo-red test paper to soak, be blue after the KI test paper soaks, remove excessive nitrous acid with thionamic acid, obtain the first diazo liquid, for subsequent use.
(b) H acid solution preparation:
Add 34g H acid in the 200ml water and stir, transfer pH=6.9 with 30 wt % sodium hydroxide solutions, complete must the H acid solution after molten, for subsequent use.
(c) a step coupling:
The H acid solution that step (b) is made joins in the first diazo liquid of step (a) preparation fast, and temperature 7-10 ℃ of stirring reaction 3 hours gets a step coupling solution, and be for subsequent use.
(d) P-aminoazobenzene-4-(N-ethylsulfuric acid ester group) sulphonamide diazotization:
In 300g water, add 38.5g P-aminoazobenzene-4-(N-ethylsulfuric acid ester group) sulphonamide, add trash ice 20g, 30 wt % hydrochloric acid soln 25g, with at the uniform velocity adding 30 wt % sodium nitrite solution 25g in 4 hours, finish at temperature 0-5 ℃ and kept stirring reaction 4 hours, be blue after keeping congo-red test paper to soak, be little blueness after the KI test paper soaks, reaction is finished and to be removed residue nitrous acid with thionamic acid and get the second diazo liquid, and is for subsequent use.
(e) two step couplings:
Step (d) is obtained the second diazo liquid, join step (c) and obtain to stir in the step coupling solution, transfer pH=6.7 with yellow soda ash, be warming up to 25 ℃, reacted 6 hours, reaction is complete filters, and gets two step coupling solutions,
(f) hydrolysis:
Two step of step (e) gained coupling solution temperature is controlled at 50 ℃, regulates pH=9.5 with the 30wt% sodium hydroxide solution, the reaction that is hydrolyzed, 4 hours reaction times, get hydrolyzed solution, namely get such as the formula III black and active dye,
(g) refining:
(f) step gained hydrolyzed solution is added sodium-chlor according to the ratio that every 100ml adds 20g, treat that dyestuff separates out fully, filter, collect filter cake, weigh, analysis content, for subsequent use.
(h) drying:
(g) step filter cake is dried, pulverized, weigh, get the finished product black and active dye.
It is as follows that the black and active dye of embodiment 2 preparation dyes the application performance of nylon:
Compound of the present invention and preparation method thereof is described by specific embodiment.Those skilled in the art can use for reference the links such as content appropriate change raw material of the present invention, processing condition and realize corresponding other purpose, its relevant change does not all break away from content of the present invention, all similar replacements and change will become apparent to those skilled in the art that and all be deemed to be included within the scope of the present invention.
Claims (3)
1. black and active dye is characterized in that: its structural formula as shown in the formula (I):
R
1A kind of in the following substituting group;-H ,-NO
2,-OCH
3Or-SO
3Na.
2. the preparation method of the described black and active dye of claim 1, it is characterized in that: the method comprises following steps:
(a) structure formula II compound diazotization:
Xiang Shuizhong adds the formula II compound, adds ice and hydrochloric acid, adds sodium nitrite solution again, and diazotization gets the first diazo liquid;
R
2A kind of in the following substituting group;-H ,-NO
2,-OCH
3Or-SO
3H;
(b) H acid solution preparation
Xiang Shuizhong adds H acid and stirs, and accent pH is 6-7, gets the H acid solution;
(c) a step coupling
Step (b) gained H acid solution is joined in step (a) gained the first diazo liquid, react to get a step coupling solution;
(d) P-aminoazobenzene-4-(N-ethylsulfuric acid ester group) sulphonamide diazotization
Xiang Shuizhong adds P-aminoazobenzene-4-(N-ethylsulfuric acid ester group) sulphonamide, adds ice and hydrochloric acid, adds sodium nitrite solution again, and diazotization gets the second diazo liquid;
(e) two step couplings:
Step (d) is obtained the second diazo liquid join in the step coupling solution that step (c) obtains, react and to get two step coupling solutions;
(f) hydrolysis:
The two step coupling solutions that step (e) is obtained are hydrolyzed at pH=8-12, get hydrolyzed solution, namely make structural formula (I) black and active dye.
3. method according to claim 2, it is characterized in that: the method comprises following steps:
(a) structure formula II compound diazotization:
R
2A kind of in the following substituting group;-H ,-NO
2,-OCH
3Or-SO
3H;
Add water to retort, then add structure formula II compound, after stirring, add trash ice and 30wt % hydrochloric acid soln, add again the 30wt% sodium nitrite solution, finish reaction 1-3 hour, be blue after the maintenance congo-red test paper soaks, be blue after the KI test paper soaks; React complete and remove unreacted nitrous acid with thionamic acid, get the first diazo liquid, for subsequent use;
(b) H acid solution preparation:
Add entry to retort, then add H acid, transfer pH=6-7 with the 30wt% sodium hydroxide solution, complete after molten the H acid solution, for subsequent use.
(c) a step coupling:
The first diazo liquid of step (a) preparation is put into retort, add again the H acid solution of step (b) preparation, temperature 7-10 ℃, stirring reaction 2-5 hour, get a step coupling solution, for subsequent use.
(d) P-aminoazobenzene-4-(N-ethylsulfuric acid ester group) sulphonamide diazotization
Add water to retort, then add P-aminoazobenzene-4-(N-ethylsulfuric acid ester group) sulphonamide, after stirring, add trash ice and 30wt% hydrochloric acid soln, add again the 30wt% sodium nitrite solution, finish and react again 1-4 hour, be blue after keeping congo-red test paper to soak, be blue after the KI test paper soaks, react complete and remove unreacted nitrous acid with thionamic acid, get the second diazo liquid, for subsequent use.
(e) two step couplings:
With the second diazo liquid that step (d) obtains, join in the step coupling solution of step (c) acquisition, stir, transfer pH=5-8 with yellow soda ash, temperature 15-30 ℃ was reacted 3-6 hour, reacted complete filtration, got two step coupling solutions, for subsequent use.
(f) hydrolysis:
Two step of (e) step gained coupling solution is transferred pH=8-12 with the 30wt% sodium hydroxide solution, the reaction that is hydrolyzed, reaction times 4-8 hour, get hydrolyzed solution, namely get structural formula (I) black and active dye.
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| US4638054A (en) * | 1983-11-10 | 1987-01-20 | Bayer Aktiengesellschaft | Aminonaphthol bisazo reactive dyes |
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