CN101418132A - Purple reactive dyes for wool and preparation method thereof - Google Patents
Purple reactive dyes for wool and preparation method thereof Download PDFInfo
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- CN101418132A CN101418132A CNA2008101529229A CN200810152922A CN101418132A CN 101418132 A CN101418132 A CN 101418132A CN A2008101529229 A CNA2008101529229 A CN A2008101529229A CN 200810152922 A CN200810152922 A CN 200810152922A CN 101418132 A CN101418132 A CN 101418132A
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- soda ash
- purple
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- 238000002360 preparation method Methods 0.000 title claims abstract description 27
- 210000002268 wool Anatomy 0.000 title claims abstract description 26
- 239000000985 reactive dye Substances 0.000 title abstract description 6
- 238000005859 coupling reaction Methods 0.000 claims abstract description 17
- 238000001035 drying Methods 0.000 claims abstract description 12
- 238000009833 condensation Methods 0.000 claims abstract description 5
- 230000005494 condensation Effects 0.000 claims abstract description 5
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 78
- 239000000243 solution Substances 0.000 claims description 72
- 238000003756 stirring Methods 0.000 claims description 60
- 238000006243 chemical reaction Methods 0.000 claims description 58
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 50
- NLKNQRATVPKPDG-UHFFFAOYSA-M potassium iodide Chemical compound [K+].[I-] NLKNQRATVPKPDG-UHFFFAOYSA-M 0.000 claims description 50
- 235000017550 sodium carbonate Nutrition 0.000 claims description 39
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 39
- 238000012360 testing method Methods 0.000 claims description 36
- LPXPTNMVRIOKMN-UHFFFAOYSA-M sodium nitrite Chemical compound [Na+].[O-]N=O LPXPTNMVRIOKMN-UHFFFAOYSA-M 0.000 claims description 34
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 32
- 239000000463 material Substances 0.000 claims description 28
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 27
- 238000012546 transfer Methods 0.000 claims description 24
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 claims description 20
- 239000007788 liquid Substances 0.000 claims description 20
- -1 2-4Thiazolinyl Chemical group 0.000 claims description 19
- 239000012065 filter cake Substances 0.000 claims description 19
- 208000006278 hypochromic anemia Diseases 0.000 claims description 17
- 235000010288 sodium nitrite Nutrition 0.000 claims description 17
- 229920002472 Starch Polymers 0.000 claims description 16
- 235000019698 starch Nutrition 0.000 claims description 16
- 239000008107 starch Substances 0.000 claims description 16
- ZMCHBSMFKQYNKA-UHFFFAOYSA-N 2-aminobenzenesulfonic acid Chemical compound NC1=CC=CC=C1S(O)(=O)=O ZMCHBSMFKQYNKA-UHFFFAOYSA-N 0.000 claims description 15
- 239000002253 acid Substances 0.000 claims description 15
- 238000000034 method Methods 0.000 claims description 14
- 239000000047 product Substances 0.000 claims description 13
- 238000006193 diazotization reaction Methods 0.000 claims description 10
- 239000011259 mixed solution Substances 0.000 claims description 10
- 238000000746 purification Methods 0.000 claims description 10
- 235000017557 sodium bicarbonate Nutrition 0.000 claims description 10
- 229910000030 sodium bicarbonate Inorganic materials 0.000 claims description 10
- 238000005507 spraying Methods 0.000 claims description 10
- 206010014080 Ecchymosis Diseases 0.000 claims description 8
- 241001062009 Indigofera Species 0.000 claims description 8
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 8
- 239000004411 aluminium Substances 0.000 claims description 8
- 229910052782 aluminium Inorganic materials 0.000 claims description 8
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 8
- 238000010009 beating Methods 0.000 claims description 8
- 238000006482 condensation reaction Methods 0.000 claims description 8
- 238000001816 cooling Methods 0.000 claims description 8
- 238000001514 detection method Methods 0.000 claims description 8
- 238000001914 filtration Methods 0.000 claims description 8
- 230000008569 process Effects 0.000 claims description 8
- 239000011435 rock Substances 0.000 claims description 8
- 239000000741 silica gel Substances 0.000 claims description 8
- 229910002027 silica gel Inorganic materials 0.000 claims description 8
- 238000010792 warming Methods 0.000 claims description 8
- 239000011230 binding agent Substances 0.000 claims description 6
- 238000005352 clarification Methods 0.000 claims description 6
- HBZVNWNSRNTWPS-UHFFFAOYSA-N 6-amino-4-hydroxynaphthalene-2-sulfonic acid Chemical compound C1=C(S(O)(=O)=O)C=C(O)C2=CC(N)=CC=C21 HBZVNWNSRNTWPS-UHFFFAOYSA-N 0.000 claims description 5
- 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 claims description 4
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 4
- 238000004090 dissolution Methods 0.000 claims description 4
- 229910052708 sodium Inorganic materials 0.000 claims description 4
- 239000011734 sodium Substances 0.000 claims description 4
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims description 3
- 229910052794 bromium Inorganic materials 0.000 claims description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 3
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims description 3
- 229920002554 vinyl polymer Polymers 0.000 claims description 3
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims description 2
- 229910052728 basic metal Inorganic materials 0.000 claims description 2
- 150000003818 basic metals Chemical class 0.000 claims description 2
- 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 2
- 229910052736 halogen Inorganic materials 0.000 claims description 2
- 150000002367 halogens Chemical class 0.000 claims description 2
- 238000009413 insulation Methods 0.000 claims description 2
- 238000002791 soaking Methods 0.000 claims description 2
- 239000011780 sodium chloride Substances 0.000 claims description 2
- 239000000975 dye Substances 0.000 abstract description 34
- 238000005516 engineering process Methods 0.000 abstract description 10
- 230000008878 coupling Effects 0.000 abstract description 7
- 238000010168 coupling process Methods 0.000 abstract description 7
- 230000007613 environmental effect Effects 0.000 abstract description 3
- 230000009257 reactivity Effects 0.000 abstract description 2
- 239000002699 waste material Substances 0.000 abstract description 2
- 239000002351 wastewater Substances 0.000 abstract description 2
- 239000012752 auxiliary agent Substances 0.000 abstract 2
- 238000007792 addition Methods 0.000 abstract 1
- 238000002156 mixing Methods 0.000 abstract 1
- 238000004806 packaging method and process Methods 0.000 abstract 1
- 239000002994 raw material Substances 0.000 abstract 1
- 238000004043 dyeing Methods 0.000 description 8
- ZYSOYLBBCYWEMB-UHFFFAOYSA-N 7-aminonaphthalen-1-ol Chemical class C1=CC=C(O)C2=CC(N)=CC=C21 ZYSOYLBBCYWEMB-UHFFFAOYSA-N 0.000 description 6
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 6
- 210000003298 dental enamel Anatomy 0.000 description 6
- 239000012954 diazonium Substances 0.000 description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-O diazynium Chemical compound [NH+]#N IJGRMHOSHXDMSA-UHFFFAOYSA-O 0.000 description 6
- 238000005259 measurement Methods 0.000 description 6
- 150000003839 salts Chemical class 0.000 description 6
- 238000005070 sampling Methods 0.000 description 6
- 230000008859 change Effects 0.000 description 2
- DPDMMXDBJGCCQC-UHFFFAOYSA-N [Na].[Cl] Chemical compound [Na].[Cl] DPDMMXDBJGCCQC-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 125000001246 bromo group Chemical group Br* 0.000 description 1
- 210000000085 cashmere Anatomy 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000983 mordant dye Substances 0.000 description 1
Images
Abstract
The invention discloses purple wool reactive dye and a preparation method thereof, wherein 4-amido-2-aniline-2-sulfonic acid, 2-amido-8-hydroxy-naphthalene-6-sulfonic acid, 2, 3- propionyl chloride dibromide are taken as main raw materials, and the purple wool reactive dye is prepared by nitridation, condensation, coupling, addition of an auxiliary agent, improvement of the concentration of the dye, adjustment of the chromatic light, adjustment of the strength, drying and packaging. The purple wool reactive dye obtained has high reactivity, superior solubility, colorful chromatic light, good lightfastness performance and high exhaustion rate and fixation rate. By adoption of the auxiliary agent and the pre-mixing technology, waste water and waste residue can be prevented from being generated, so that the purple wool reactive dye greatly promotes environmental protection.
Description
Technical field
The present invention relates to a kind of reactive dye for wool and preparation method thereof, especially purple active dye for wool and preparation method thereof.
Background technology
Now general dyeing wool, cashmere, used dyestuff are matching stain, acid mordant dye and metallized dye.Because with the material that these kinds of dyes are dyed, fastness is all not good enough, coloured light is not really gorgeous, but also can cause trouble to environmental protection.Enter 21 century, because the restriction of environmental ecology is more and more higher for the requirement of dye uptake, degree of fixation and dyeing waste-water.Matching stain can not satisfy development of times again.
Summary of the invention
Technical problem to be solved by this invention is, reduces the environmental pollution of dyestuff, the product solubility height, and also bright in colour, the application performance excellence, easy to use, suitability is strong.
In order to solve the problems of the technologies described above, the invention provides a kind of purple active dye for wool, described dyestuff has solved the above-mentioned problems in the prior art.
In addition, the present invention also provides a kind of its preparation method of described reactive dyestuffs.
Purple active dye for wool of the present invention has following general structure:
Wherein
R＝——COR
2XR
2X ——COR
3X ——R
2SO
2R
3
In a kind of.
Wherein,
R
2Identical or different and the expression C
1-6Alkyl, preferred C
1-4Alkyl, methyl more preferably;
R
3Identical or different and the expression C
2-6Thiazolinyl, preferred C
2-4Thiazolinyl, vinyl more preferably;
Identical or different and the expression halogen of X is preferably bromine;
Identical in M and the general formula, expression basic metal is preferably sodium.
Preferably, R
2Identical and be methyl, R
3Identical and be vinyl, X is identical and be bromine, and M is identical and be sodium.This moment, described dyestuff was:
The preparation method of purple active dye for wool of the present invention comprises the steps:
A. condensation reaction: in retort, add 2-amino-8-hydroxyl naphthalene-6-sulfonic acid, regulate (soda ash with 96% is transferred) pH=7～7.5, stirring and dissolving, clarification.Make C%=8-12 in the solution.The temperature of adjusting solution is 5～12 ℃, adjusts C%=10-11 in the solution, and with 2,3-two bromo propionyl chloros add, and keep pH=5.5～7.5 simultaneously, stirring reaction 1-3 hour in 1.5～2 hours.5～12 ℃ of temperature of reaction are used the aluminium base silica gel thin-layer plate endpoint detection of TLC at last.Obtain condensation solution.
Among the step a,
Preferably use soda ash, the soda ash of more preferably using 96%wt with pH regulator to 7-7.5.
Preferably the temperature with direct ice and chuck circulating water adjustment solution is 5-12 ℃.
Preferably pH is maintained 5.5-7.5 with sodium bicarbonate.
B, diazotization reaction
In retort, add 4-amino-2 aniline-2 sulfonic acid.Stir downward modulation pH=7～7.5.Material is dissolved fully.Add then and dissolved 30% sodium nitrite solution, stir, it is standby to obtain mixed solution.
In another retort, add 30% hydrochloric acid.Controlled temperature is 8～15 ℃ under stirring, and 1～1.5 hour time spent added above-mentioned mixed solution.Use the spot of pH test paper and starch potassium iodide paper test soln in the reinforced process.The pH test paper was under the condition of purple and the little indigo plant of starch potassium iodide paper reaction 1-3 hour.Use the thionamic acid ecchymose removing at last, obtain diazotization reaction solution, standby.
Among the step b,
Preferably pH is adjusted to 7-7.5 with 96% soda ash.
C. coupled reaction: follow acid binding agent to join in the condensation solution that step a obtains the reaction soln that obtains among the step b,, under 15-30 ℃, react acquisition coupled reaction look liquid 6-7 hour at pH=6-8.
Preferably, control pH value of solution=6～8,15～25 ℃ of holding temperatures were reacted 30 minutes.Be warming up to 25～30 ℃, insulation reaction is 6 hours again;
D. alkaline purification: c step look liquid temp is reduced to 6-10 ℃, transfer pH=11.8～12.5～10 ℃ of holding temperatures are kept pH=11.8～12, react 0.5-2 hour.Transfer pH=6～6.5 at last.Obtain alkaline purification look liquid, standby.
Preferably, the sodium hydroxide solution with 30% is adjusted to 11.8-12 with pH,
Preferably, with 30% hydrochloric acid soln pH is adjusted to 6-6.5.
E. saltout: with the look liquid of steps d by volume 8%～10% add NaCl, treat that material is separated out after, filter to obtain filter cake.
Preferably adopt press filtration to obtain filter cake.
F. filter cake making beating and spraying drying obtain the purple active dye for wool finished product.
It is pointed out that other drying means commonly used also can be used for the present invention, to obtain the dyestuff finished product except that filter cake being carried out spraying drying obtaining the purple active dye for wool finished product.
In preparation method of the present invention, described step a is preferably: add 2-amino-8-hydroxyl naphthalene-6-sulfonic acid in water, stir down and transfer pH=7～7.5 with 96% yellow soda ash, material dissolution, clarification, C%=10 in the solution～12, direct cooling on the rocks, adjust volume C%=10, adjust temperature to 5～12 ℃, in 1.5～2 hours with 2,3-two bromo propionyl chloros add, stirring reaction 2 hours, 5～12 ℃ of temperature of reaction, reaction pH=6～6.5.
In preparation method of the present invention, described step b is preferably: add 4-amino-2-aniline-2-sulfonic acid in water, stir down and regulate pH=7～7 with 96% yellow soda ash.5 make material dissolution, clarification, C%=10 in the solution～12; In solution, add quantitative Sodium Nitrite, in 1～1.5 hour, will appeal drips of solution and be added in the frozen water that contains quantitative hydrochloric acid stirring reaction, 8～15 ℃ of temperature of reaction, guarantee to be after congo-red test paper soaks blue at reaction soln, and the KI test paper is little blueness after soaking, reacted 2 hours.
In preparation method of the present invention, the employed acid binding agent of step a is preferably sodium bicarbonate.
In preparation method of the present invention, the employed acid binding agent of step c is preferably 15% soda ash solution.
The invention has the beneficial effects as follows: the resulting purple active dye for wool of the present invention has higher reactivity, and good solubleness has very bright-coloured beautiful coloured light; The light fastness performance is fabulous, has very high exhaustion rate and degree of fixation.No waste residue produces in the production process, and environment protection has been played very big promoter action.
Description of drawings
Fig. 1 is preparation technology's schema of purple active dye for wool of the present invention.
Embodiment:
Embodiment 1
1, allocation sheet:
The material name weight molecule is than folding hundred consumptions (Kg) charging capacitys (kilomol)
2-amino-8-hydroxyl naphthalene-6-
239 1 143.3 0.6
Sulfonic acid
2,3-two bromo propionyl chloros 250.5 1.07 160.8 0.6
4-amino-2 aniline-2 sulfonic acid 264 1 158.4 0.6
Hydrochloric acid 36.5 3 65.7 0.6
Sodium Nitrite 69 1.05 43.47 0.6
2, dyestuff preparation technology of the present invention operates as follows:
A, condensation reaction
Put into 1500 liters in end water in retort, add 143.4 kilograms of 2-amino-8-hydroxyl naphthalenes of 100%-6-sulfonic acid, the soda ash with 96% is transferred pH=7～7.5, and stirring and dissolving makes material molten entirely, clarifies.C%=12 in the solution, the temperature of adjusting solution with direct ice and chuck circulating water is 5～7 ℃, adjusts C%=10 in the solution, with 2,3-two bromo propionyl chloros add, and keep pH=5.5～6.5 with sodium bicarbonate simultaneously, stirring reaction 2 hours in 1.5～2 hours.5～7 ℃ of temperature of reaction, reaction pH=6～6.5.Use the aluminium base silica gel thin-layer plate endpoint detection of TLC at last.
B, diazotization reaction
In 10000 liters enamel pot, add 2500 liters in water, add 158.4 kilograms of 100% 4-amino-2 aniline-2 sulfonic acid again.Stir down and transfer pH=7～7.5 with 96% soda ash.Stir down and transfer pH=7～7.5 with 96% soda ash.Material is dissolved fully.Add then and dissolved 30% quantitative sodium nitrite solution, the back that stirs is standby.
In another retort of 10000 liters, add 600 liters in water, 219 kilograms of 30% hydrochloric acid.Controlled temperature is 8～11 ℃ under stirring, and 1～1.5 hour time spent added above-mentioned mixed solution.At any time use the spot of pH test paper and starch potassium iodide paper test soln in the reinforced process.In temperature is 8～11 ℃, and the pH test paper was under the condition of purple and the little indigo plant of starch potassium iodide paper reaction 2 hours.Use the thionamic acid ecchymose removing at last, standby.V=3600～3800 liter
C, coupled reaction
Diazonium liquid is followed 96% soda ash, under the condition of pH=6～7, join in the condensated liquid, stir and be warming up to 25 ℃ after 30 minutes, keep pH=6～7.Reacted 6 hours.Use the UV test curve, watch reaction end, standby.The V=6300 liter.
D, alkaline purification
Cooling on the rocks is reduced to 8 ℃ with the temperature of coupling solution, and the sodium hydroxide solution with 30% is transferred pH=11.8～12.5～8 ℃ of holding temperatures are kept pH=11.8～12 and reacted 1 hour, transfer pH=6.5 with 30% hydrochloric acid soln at last, and are standby.
E, saltout
Accurate measurement volumes, and according to 8～10% minutes 3 times of volume refined salt is joined in the reaction solution.Stirred 1 hour, press filtration, filter cake is weighed, and surveys to contain admittedly sampling, dyeing.
F, filter cake making beating dissolving, spraying drying.
Get 540 kilograms of dry product finished product dyestuffs
The dyestuff of dry gained is packed by the specification of 25 kilograms in every case.Warehouse-in is deposited.
Preparation purple active dye for wool norm quota of consumption table of the present invention:
| Material name | Unit consumption, Kg/T |
| 2-amino-8-hydroxyl naphthalene-6-sulfonic acid | 262.9 |
| 2,3～two bromo propionyl chloros | 293.6 |
| 4-amino-2 aniline-2 sulfonic acid | 290.6 |
| Hydrochloric acid | 120.5 |
| Sodium Nitrite | 79.76 |
| Sodium hydroxide | 366.9 |
| Yellow soda ash | 587 |
| Sodium-chlor | 1467.8 |
Preparation purple active dye for wool application performance table of the present invention
Embodiment 2
1, allocation sheet:
The material name weight molecule is than folding hundred consumptions (Kg) charging capacitys (kilomol)
2-amino-8-hydroxyl naphthalene-6-
239 1 143.3 0.6
Sulfonic acid
2,3～two bromo propionyl chloros 250.5 1.07 160.8 0.6
4-amino-2 aniline-2 sulfonic acid 264 1 158.4 0.6
Hydrochloric acid 36.5 3 65.7 0.6
Sodium Nitrite 69 1.05 43.47 0.6
2, dyestuff preparation technology of the present invention operates as follows:
A, condensation reaction
Put into 1500 liters in end water in retort, add 143.4 kilograms of 2-amino-8-hydroxyl naphthalenes of 100%-6-sulfonic acid, the soda ash with 96% is transferred pH=7～7.5, and stirring and dissolving makes material molten entirely, clarifies.C%=12 in the solution, the temperature of adjusting solution with direct ice and chuck circulating water is 7～8 ℃, adjusts C%=10 in the solution, with 2,3-two bromo propionyl chloros add, and keep pH=5.5～6.5 with sodium bicarbonate simultaneously, stirring reaction 2 hours in 1.5～2 hours.7～8 ℃ of temperature of reaction, reaction pH=5.5～6.5.Use the aluminium base silica gel thin-layer plate endpoint detection of TLC at last.
B, diazotization reaction
In 10000 liters enamel pot, add 2500 liters in water, add 158.4 kilograms of 100%4-amino-2 aniline-2 sulfonic acid again.Stir down and transfer pH=7～7.5 with 96% soda ash.Stir down and transfer pH=7～7.5 with 96% soda ash.Material is dissolved fully.Add then and dissolved 30% quantitative sodium nitrite solution, the back that stirs is standby.
In another retort of 10000 liters, add 600 liters in water, 219 kilograms of 30% hydrochloric acid.Controlled temperature is 8～11 ℃ under stirring, and 1～1.5 hour time spent added above-mentioned mixed solution.At any time use the spot of pH test paper and starch potassium iodide paper test soln in the reinforced process.In temperature is 8～11 ℃, and the pH test paper was under the condition of purple and the little indigo plant of starch potassium iodide paper reaction 2 hours.Use the thionamic acid ecchymose removing at last, standby.V=3600～3800 liter
C, coupled reaction
Diazonium liquid is followed 96% soda ash, under the condition of pH=6～7, join in the condensated liquid, stir and be warming up to 25 ℃ after 30 minutes, keep pH=6～7.Reacted 6 hours.Use the UV test curve, watch reaction end, standby.The V=6300 liter.
D, alkaline purification
Cooling on the rocks is reduced to 8 ℃ with the temperature of coupling solution, and the sodium hydroxide solution with 30% is transferred pH=11.8～12.5～8 ℃ of holding temperatures are kept pH=11.8～12 and reacted 1 hour, transfer pH=6.5 with 30% hydrochloric acid soln at last, and are standby.
E, saltout
Accurate measurement volumes, and according to 8～10% minutes 3 times of volume refined salt is joined in the reaction solution.Stirred 1 hour, press filtration, filter cake is weighed, and surveys to contain admittedly sampling, dyeing.
F, filter cake making beating dissolving, spraying drying.Get 543 kilograms of dry product dyestuffs
The dyestuff of dry gained is packed by the specification of 25 kilograms in every case.Warehouse-in is deposited.
Embodiment 3
1, allocation sheet:
The material name weight molecule is than folding hundred consumptions (Kg) charging capacitys (kilomol)
2-amino-8-hydroxyl naphthalene-6-
239 1 143.3 0.6
Sulfonic acid
2,3～two bromo propionyl chloros 250.5 1.07 160.8 0.6
4-amino-2 aniline-2 sulfonic acid 264 1 158.4 0.6
Hydrochloric acid 36.5 3 65.7 0.6
Sodium Nitrite 69 1.05 43.47 0.6
2, dyestuff preparation technology of the present invention operates as follows:
A, condensation reaction
Put into 1500 liters in end water in retort, add 143.4 kilograms of 2-amino-8-hydroxyl naphthalenes of 100%-6-sulfonic acid, the soda ash with 96% is transferred pH=7～7.5, and stirring and dissolving makes material molten entirely, clarifies.C%=12 in the solution, the temperature of adjusting solution with direct ice and chuck circulating water is 8～10 ℃, adjusts C%=10 in the solution, with 2,3-two bromo propionyl chloros add, and keep pH=5.5～6.5 with sodium bicarbonate simultaneously, stirring reaction 2 hours in 1.5～2 hours.8～10 ℃ of temperature of reaction, reaction pH=5.5～6.5.Use the aluminium base silica gel thin-layer plate endpoint detection of TLC at last.
B, diazotization reaction
In 10000 liters enamel pot, add 2500 liters in water, add 158.4 kilograms of 100%4-amino-2 aniline-2 sulfonic acid again.Stir down and transfer pH=7～7.5 with 96% soda ash.Stir down and transfer pH=7～7.5 with 96% soda ash.Material is dissolved fully.Add then and dissolved 30% quantitative sodium nitrite solution, the back that stirs is standby.
In another retort of 10000 liters, add 600 liters in water, 219 kilograms of 30% hydrochloric acid.Controlled temperature is 8～11 ℃ under stirring, and 1～1.5 hour time spent added above-mentioned mixed solution.At any time use the spot of pH test paper and starch potassium iodide paper test soln in the reinforced process.In temperature is 8～11 ℃, and the pH test paper was under the condition of purple and the little indigo plant of starch potassium iodide paper reaction 2 hours.Use the thionamic acid ecchymose removing at last, standby.V=3600～3800 liter
C, coupled reaction
Diazonium liquid is followed 96% soda ash, under the condition of pH=6～7, join in the condensated liquid, stir and be warming up to 25 ℃ after 30 minutes, keep pH=6～7.Reacted 6 hours.Use the UV test curve, watch reaction end, standby.The V=6300 liter.
D, alkaline purification
Cooling on the rocks is reduced to 8 ℃ with the temperature of coupling solution, and the sodium hydroxide solution with 30% is transferred pH=11.8～12.5～8 ℃ of holding temperatures are kept pH=11.8～12 and reacted 1 hour, transfer pH=6.5 with 30% hydrochloric acid soln at last, and are standby.
E, saltout
Accurate measurement volumes, and according to 8～10% minutes 3 times of volume refined salt is joined in the reaction solution.Stirred 1 hour, press filtration, filter cake is weighed, and surveys to contain admittedly sampling, dyeing.
F, filter cake making beating dissolving, spraying drying.Getting 545 kilograms of dyestuffs with dry gained of dry product dyestuff packs by the specification of 25 kilograms in every case.Warehouse-in is deposited.
Embodiment 4
1, allocation sheet:
The material name weight molecule is than folding hundred consumptions (Kg) charging capacitys (kilomol)
2-amino-8-hydroxyl naphthalene-6-
239 1 143.3 0.6
Sulfonic acid
2,3～two bromo propionyl chloros 250.5 1.07 160.8 0.6
4-amino-2 aniline-2 sulfonic acid 264 1 158.4 0.6
Hydrochloric acid 36.5 3 65.7 0.6
Sodium Nitrite 69 1.05 43.47 0.6
2, dyestuff preparation technology of the present invention operates as follows:
A, condensation reaction
Put into 1500 liters in end water in retort, add 143.4 kilograms of 2-amino-8-hydroxyl naphthalenes of 100%-6-sulfonic acid, the soda ash with 96% is transferred pH=7～7.5, and stirring and dissolving makes material molten entirely, clarifies.C%=12 in the solution, the temperature of adjusting solution with direct ice and chuck circulating water is 9～11 ℃, adjusts C%=10 in the solution, with 2,3-two bromo propionyl chloros add, and keep pH=6.5～7.5 with sodium bicarbonate simultaneously, stirring reaction 2 hours in 1.5～2 hours.9～11 ℃ of temperature of reaction, reaction pH=6.5～7.5.Use the aluminium base silica gel thin-layer plate endpoint detection of TLC at last.
B, diazotization reaction
In 10000 liters enamel pot, add 2500 liters in water, add 158.4 kilograms of 100%4-amino-2 aniline-2 sulfonic acid again.Stir down and transfer pH=7～7.5 with 96% soda ash.Stir down and transfer pH=7～7.5 with 96% soda ash.Material is dissolved fully.Add then and dissolved 30% quantitative sodium nitrite solution, the back that stirs is standby.
In another retort of 10000 liters, add 600 liters in water, 219 kilograms of 30% hydrochloric acid.Controlled temperature is 11～15 ℃ under stirring, and 1～1.5 hour time spent added above-mentioned mixed solution.At any time use the spot of pH test paper and starch potassium iodide paper test soln in the reinforced process.In temperature is 11～15 ℃, and the pH test paper was under the condition of purple and the little indigo plant of starch potassium iodide paper reaction 2 hours.Use the thionamic acid ecchymose removing at last, standby.V=3600～3800 liter
C, coupled reaction
Diazonium liquid is followed 96% soda ash, under the condition of pH=7～8, join in the condensated liquid, stir and be warming up to 25 ℃ after 30 minutes, keep pH=7～8.Reacted 6 hours.Use the UV test curve, watch reaction end, standby.The V=6300 liter.
D, alkaline purification
Cooling on the rocks is reduced to 8 ℃ with the temperature of coupling solution, and the sodium hydroxide solution with 30% is transferred pH=11.8～12.5～8 ℃ of holding temperatures are kept pH=11.8～12 and reacted 1 hour, transfer pH=6.5 with 30% hydrochloric acid soln at last, and are standby.
E, saltout
Accurate measurement volumes, and according to 8～10% minutes 3 times of volume refined salt is joined in the reaction solution.Stirred 1 hour, press filtration, filter cake is weighed, and surveys to contain admittedly sampling, dyeing.
F, filter cake making beating dissolving, spraying drying.
Get 540 kilograms of dry product dyestuffs
The dyestuff of dry gained is packed by the specification of 25 kilograms in every case.Warehouse-in is deposited.
Embodiment 5
1, allocation sheet:
The material name weight molecule is than folding hundred consumptions (Kg) charging capacitys (kilomol)
2-amino-8-hydroxyl naphthalene-6-
239 1 143.3 0.6
Sulfonic acid
2,3～two bromo propionyl chloros 250.5 1.07 160.8 0.6
4-amino-2 aniline-2 sulfonic acid 264 1 158.4 0.6
Hydrochloric acid 36.5 3 65.7 0.6
Sodium Nitrite 69 1.05 43.47 0.6
2, dyestuff preparation technology of the present invention operates as follows:
A, condensation reaction
Put into 1500 liters in end water in retort, add 143.4 kilograms of 2-amino-8-hydroxyl naphthalenes of 100%-6-sulfonic acid, the soda ash with 96% is transferred pH=7～7.5, and stirring and dissolving makes material molten entirely, clarifies.C%=12 in the solution, the temperature of adjusting solution with direct ice and chuck circulating water is 10～11 ℃, adjusts C%=10 in the solution, in 1.5～2 hours with 2,3-two bromo propionyl chloros add, and keep pH=6.5～7.5 with sodium bicarbonate simultaneously, stirring reaction 2 hours.10～11 ℃ of temperature of reaction, reaction pH=6.5～7.5.Use the aluminium base silica gel thin-layer plate endpoint detection of TLC at last.
B, diazotization reaction
In 10000 liters enamel pot, add 2500 liters in water, add 158.4 kilograms of 100%4-amino-2 aniline-2 sulfonic acid again.Stir down and transfer pH=7～7.5 with 96% soda ash.Stir down and transfer pH=7～7.5 with 96% soda ash.Material is dissolved fully.Add then and dissolved 30% quantitative sodium nitrite solution, the back that stirs is standby.
In another retort of 10000 liters, add 600 liters in water, 219 kilograms of 30% hydrochloric acid.Controlled temperature is 11～15 ℃ under stirring, and 1～1.5 hour time spent added above-mentioned mixed solution.At any time use the spot of pH test paper and starch potassium iodide paper test soln in the reinforced process.In temperature is 11～15 ℃, and the pH test paper was under the condition of purple and the little indigo plant of starch potassium iodide paper reaction 2 hours.Use the thionamic acid ecchymose removing at last, standby.V=3600～3800 liter
C, coupled reaction
Diazonium liquid is followed 96% soda ash, under the condition of pH=7～8, join in the condensated liquid, stir and be warming up to 25 ℃ after 30 minutes, keep pH=7～8.Reacted 6 hours.Use the UV test curve, watch reaction end, standby.The V=6300 liter.
D, alkaline purification
Cooling on the rocks is reduced to 8 ℃ with the temperature of coupling solution, and the sodium hydroxide solution with 30% is transferred pH=11.8～12.5～8 ℃ of holding temperatures are kept pH=11.8～12 and reacted 1 hour, transfer pH=6.5 with 30% hydrochloric acid soln at last, and are standby.
E, saltout
Accurate measurement volumes, and according to 8～10% minutes 3 times of volume refined salt is joined in the reaction solution.Stirred 1 hour, press filtration, filter cake is weighed, and surveys to contain admittedly sampling, dyeing.
F, filter cake making beating dissolving, spraying drying.
Get 545 kilograms of finished product dyestuffs
The dyestuff of dry gained is packed by the specification of 25 kilograms in every case.Warehouse-in is deposited.
Embodiment 6
1, allocation sheet:
The material name weight molecule is than folding hundred consumptions (Kg) charging capacitys (kilomol)
2-amino-8-hydroxyl naphthalene-6-
239 1 143.3 0.6
Sulfonic acid
2,3～two bromo propionyl chloros 250.5 1.07 160.8 0.6
4-amino-2 aniline-2 sulfonic acid 264 1 158.4 0.6
Hydrochloric acid 36.5 3 65.7 0.6
Sodium Nitrite 69 1.05 43.47 0.6
2, dyestuff preparation technology of the present invention operates as follows:
A, condensation reaction
Put into 1500 liters in end water in retort, add 143.4 kilograms of 2-amino-8-hydroxyl naphthalenes of 100%-6-sulfonic acid, the soda ash with 96% is transferred pH=7～7.5, and stirring and dissolving makes material molten entirely, clarifies.C%=12 in the solution, the temperature of adjusting solution with direct ice and chuck circulating water is 11～12 ℃, adjusts C%=10 in the solution, in 1.5～2 hours with 2,3-two bromo propionyl chloros add, and keep pH=5.5～6.5 with sodium bicarbonate simultaneously, stirring reaction 2 hours.11～12 ℃ of temperature of reaction, reaction pH=6.5～7.5.Use the aluminium base silica gel thin-layer plate endpoint detection of TLC at last.
B, diazotization reaction
In 10000 liters enamel pot, add 2500 liters in water, add 158.4 kilograms of 100%4-amino-2 aniline-2 sulfonic acid again.Stir down and transfer pH=7～7.5 with 96% soda ash.Stir down and transfer pH=7～7.5 with 96% soda ash.Material is dissolved fully.Add then and dissolved 30% quantitative sodium nitrite solution, the back that stirs is standby.
In another retort of 10000 liters, add 600 liters in water, 219 kilograms of 30% hydrochloric acid.Controlled temperature is 11～15 ℃ under stirring, and 1～1.5 hour time spent added above-mentioned mixed solution.At any time use the spot of pH test paper and starch potassium iodide paper test soln in the reinforced process.In temperature is 11～15 ℃, and the pH test paper was under the condition of purple and the little indigo plant of starch potassium iodide paper reaction 2 hours.Use the thionamic acid ecchymose removing at last, standby.V=3600～3800 liter
C, coupled reaction
Diazonium liquid is followed 96% soda ash, under the condition of pH=7～8, join in the condensated liquid, stir and be warming up to 25 ℃ after 30 minutes, keep pH=7～8.Reacted 6 hours.Use the UV test curve, watch reaction end, standby.The V=6300 liter.
D, alkaline purification
Cooling on the rocks is reduced to 8 ℃ with the temperature of coupling solution, and the sodium hydroxide solution with 30% is transferred pH=11.8～12.5～8 ℃ of holding temperatures are kept pH=11.8～12 and reacted 1 hour, transfer pH=6.5 with 30% hydrochloric acid soln at last, and are standby.
E, saltout
Accurate measurement volumes, and according to 8～10% minutes 3 times of volume refined salt is joined in the reaction solution.Stirred 1 hour, press filtration, filter cake is weighed, and surveys to contain admittedly sampling, dyeing.
F, filter cake making beating dissolving, spraying drying.Get 537 kilograms of finished product dyestuffs
The dyestuff of dry gained is packed by the specification of 25 kilograms in every case.Warehouse-in is deposited.
Example 1,2,3,4,5,6 gained finished product dyestuffs are 540 kilograms, 543 kilograms, and 545 kilograms, 540 kilograms, 545 kilograms and 537 kilograms.After testing, example 1,2,3,4,5,6 must be measured almost and maintain an equal level.Compare with the standard of being formulated in the test, coloured light is basically identical also.
Because the present invention adopts spraying drying, adopt with prior art that to dry resulting dyestuff crystal formation different, so the solubleness of the purple active dye for wool of preparation method of the present invention preparation is big, coloured light is bright, favorable reproducibility, to colour purity just.
Below in conjunction with the embodiments the present invention is described in more detail; but those of ordinary skills should be understood that; under the prerequisite that does not break away from spirit of the present invention; can make various changes or change to the present invention; but these changes or change fall within protection scope of the present invention equally, and protection scope of the present invention is as the criterion with appending claims.
Claims (14)
1, a kind of purple active dye for wool has following general structure:
Wherein
R＝——COR
2XR
2X ——COR
3X ——R
2SO
2R
3
In a kind of.
Wherein,
R
2Identical or different and the expression C
1-6Alkyl;
R
3Identical or different and the expression C
2-6Thiazolinyl;
Identical or different and the expression halogen of X;
Identical in M and the general formula, expression basic metal.
2, reactive dyestuffs according to claim 1, wherein,
R
2Identical or different and be expressed as C
1-4Alkyl,
R
3Identical or different and the expression C
2-4Thiazolinyl,
Identical in M and the general formula, and be sodium.
3, reactive dyestuffs as claimed in claim 1 or 2, wherein,
R
2Identical and be methyl, R
3Identical and be vinyl, X is identical and be bromine, and M is identical and be sodium, and its structural formula is as follows:
4, the preparation method of the purple active dye for wool of one of a kind of claim 1-3 comprises the steps:
A. condensation reaction: in retort, add 2-amino-8-hydroxyl naphthalene-6-sulfonic acid, regulate (soda ash with 96% is transferred) pH=7～7.5, stirring and dissolving, clarification makes C%=8-12 in the solution, and the temperature of adjusting solution is 5～12 ℃, adjust C%=10-11 in the solution, with 2,3-two bromo propionyl chloros add, and keep pH=5.5～7.5 simultaneously in 1.5～2 hours, stirring reaction 1-3 hour, 5～12 ℃ of temperature of reaction are used the aluminium base silica gel thin-layer plate endpoint detection of TLC at last, obtain condensation solution;
B, diazotization reaction
In retort, add 4-amino-2 aniline-2 sulfonic acid.Stir downward modulation pH=7～7.5, material is dissolved fully, add then and dissolved 30% sodium nitrite solution, stir, it is standby to obtain mixed solution;
In another retort, add 30% hydrochloric acid, controlled temperature is 8～15 ℃ under stirring, 1～1.5 hour time spent added above-mentioned mixed solution, use the spot of pH test paper and starch potassium iodide paper test soln in the reinforced process, the pH test paper was under the condition of purple and the little indigo plant of starch potassium iodide paper reaction 1-3 hour, use the thionamic acid ecchymose removing at last, obtain diazotization reaction solution, standby;
C. coupled reaction: follow acid binding agent to join in the condensation solution that step a obtains the reaction soln that obtains among the step b,, under 15-30 ℃, react acquisition coupled reaction look liquid 6-7 hour at pH=6-8;
D. alkaline purification: c step look liquid temp is reduced to 6-10 ℃, transfer pH=11.8～12,5～10 ℃ of holding temperatures are kept pH=11.8～12, react 0.5-2 hour, transfer pH=6～6.5 at last, obtain alkaline purification look liquid, and are standby;
E. saltout: with the look liquid of steps d by volume 8%～10% add NaCl, treat that material is separated out after, filter to obtain filter cake;
F. filter cake making beating and spraying drying obtain the purple active dye for wool finished product.
5, method as claimed in claim 4, among the step a,
With soda ash with pH regulator to 7-7.5,
The temperature of adjusting solution with direct ice and chuck circulating water is 5-12 ℃,
With sodium bicarbonate pH is maintained 5.5-7.5.
6, as claim 4 or 5 described methods, in step a, the soda ash with 96% with pH regulator to 7-7.5.
7, as the described method of one of claim 4-6, wherein, in step b, the soda ash with 96% is adjusted to 7-7.5 with pH.
8, as the described method of one of claim 4-7, in step c, control pH value of solution=6～8,15～25 ℃ of holding temperatures were reacted 30 minutes.Be warming up to 25～30 ℃, insulation reaction is 6 hours again.
9, as the described method of one of claim 4-8, in steps d, the sodium hydroxide solution with 30% is adjusted to 11.8-12 with pH, and the hydrochloric acid soln with 30% is adjusted to 6-6.5 with pH.
10,, adopt press filtration to obtain filter cake as the described method of one of claim 4-9.
11, the preparation method of purple active dye for wool as claimed in claim 4 is characterized in that, described step a is: add 2-amino-8-hydroxyl naphthalene-6-sulfonic acid in water, stir down and transfer pH=7～7.5, material dissolution, clarification with 96% yellow soda ash, C%=10 in the solution～12, volume C%=10 is adjusted in direct cooling on the rocks, adjust temperature to 5～12 ℃, with 2,3-two bromo propionyl chloros add, stirring reaction 2 hours in 1.5～2 hours, 5～12 ℃ of temperature of reaction, reaction pH=6～6.5.
12, the preparation method of purple active dye for wool according to claim 4, it is characterized in that described step b is: in water, add 4-amino-2-aniline-2-sulfonic acid, regulate pH=7～7.5 with 96% yellow soda ash under stirring and make material dissolution, clarification, C%=10 in the solution～12; In solution, add quantitative Sodium Nitrite, in 1～1.5 hour, will appeal drips of solution and be added in the frozen water that contains quantitative hydrochloric acid stirring reaction, 8～15 ℃ of temperature of reaction, guarantee to be after congo-red test paper soaks blue at reaction soln, and the KI test paper is little blueness after soaking, reacted 2 hours.
13, the preparation method of purple active dye for wool according to claim 4 is characterized in that, the employed acid binding agent of described step a is a sodium bicarbonate.
14, the preparation method of purple active dye for wool according to claim 4 is characterized in that, the employed acid binding agent of described c step is 15% soda ash solution.
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|---|---|---|---|
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103554983A (en) * | 2013-10-31 | 2014-02-05 | 天津德凯化工股份有限公司 | Purple reactive dye and preparation method thereof |
| CN106118119A (en) * | 2016-07-01 | 2016-11-16 | 烟台利盈化工科技有限公司 | Warm type disperse purple dye, its compounding mixture and preparation method thereof in resistance to highly basic |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| ES387743A1 (en) * | 1970-01-30 | 1974-07-01 | Ciba Geigy | Monoazo dyestuffs their manufacture and use |
| EP0419413A1 (en) * | 1989-09-22 | 1991-03-27 | Ciba-Geigy Ag | Dyeing or printing process of blended fibres containing cellulose fibres and silk |
| CN1918245B (en) * | 2004-02-13 | 2010-11-03 | 西巴特殊化学品控股有限公司 | Mixtures of reactive dyes and their use |
-
2008
- 2008-11-11 CN CN 200810152922 patent/CN101418132B/en active Active
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103554983A (en) * | 2013-10-31 | 2014-02-05 | 天津德凯化工股份有限公司 | Purple reactive dye and preparation method thereof |
| CN106118119A (en) * | 2016-07-01 | 2016-11-16 | 烟台利盈化工科技有限公司 | Warm type disperse purple dye, its compounding mixture and preparation method thereof in resistance to highly basic |
| CN106118119B (en) * | 2016-07-01 | 2018-02-27 | 烟台澳土复合材料有限公司 | Warm type disperse purple dye, its compounding mixture and preparation method thereof in resistance to highly basic |
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