CN101705014A - Orange reactive dye for wool and preparation method thereof - Google Patents
Orange reactive dye for wool and preparation method thereof Download PDFInfo
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- CN101705014A CN101705014A CN200910228201A CN200910228201A CN101705014A CN 101705014 A CN101705014 A CN 101705014A CN 200910228201 A CN200910228201 A CN 200910228201A CN 200910228201 A CN200910228201 A CN 200910228201A CN 101705014 A CN101705014 A CN 101705014A
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- 210000002268 wool Anatomy 0.000 title claims abstract description 15
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- 239000000985 reactive dye Substances 0.000 title claims abstract description 14
- 150000001875 compounds Chemical class 0.000 claims abstract description 18
- 239000000975 dye Substances 0.000 claims abstract description 11
- 125000003545 alkoxy group Chemical group 0.000 claims abstract description 10
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 10
- 239000000243 solution Substances 0.000 claims description 95
- 239000007788 liquid Substances 0.000 claims description 64
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 48
- KYARBIJYVGJZLB-UHFFFAOYSA-N 7-amino-4-hydroxy-2-naphthalenesulfonic acid Chemical compound OC1=CC(S(O)(=O)=O)=CC2=CC(N)=CC=C21 KYARBIJYVGJZLB-UHFFFAOYSA-N 0.000 claims description 44
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 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 30
- 238000005859 coupling reaction Methods 0.000 claims description 28
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 24
- 239000012954 diazonium Substances 0.000 claims description 24
- IJGRMHOSHXDMSA-UHFFFAOYSA-O diazynium Chemical compound [NH+]#N IJGRMHOSHXDMSA-UHFFFAOYSA-O 0.000 claims description 24
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 20
- 238000001035 drying Methods 0.000 claims description 20
- 235000010288 sodium nitrite Nutrition 0.000 claims description 17
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 claims description 16
- 238000004090 dissolution Methods 0.000 claims description 16
- 150000002148 esters Chemical class 0.000 claims description 14
- 239000002253 acid Substances 0.000 claims description 13
- -1 bromo propionyl chloros Chemical compound 0.000 claims description 13
- IOVCWXUNBOPUCH-UHFFFAOYSA-N Nitrous acid Chemical compound ON=O IOVCWXUNBOPUCH-UHFFFAOYSA-N 0.000 claims description 12
- 238000006243 chemical reaction Methods 0.000 claims description 12
- 238000006482 condensation reaction Methods 0.000 claims description 12
- 238000006193 diazotization reaction Methods 0.000 claims description 12
- 208000006278 hypochromic anemia Diseases 0.000 claims description 12
- 239000011259 mixed solution Substances 0.000 claims description 12
- 238000006386 neutralization reaction Methods 0.000 claims description 12
- 239000007921 spray Substances 0.000 claims description 12
- 239000000463 material Substances 0.000 claims description 11
- 238000005352 clarification Methods 0.000 claims description 10
- 235000017550 sodium carbonate Nutrition 0.000 claims description 10
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 10
- 238000000034 method Methods 0.000 claims description 9
- 238000003756 stirring Methods 0.000 claims description 9
- 239000012295 chemical reaction liquid Substances 0.000 claims description 8
- 230000008878 coupling Effects 0.000 claims description 8
- 238000010168 coupling process Methods 0.000 claims description 8
- 235000017557 sodium bicarbonate Nutrition 0.000 claims description 8
- 229910000030 sodium bicarbonate Inorganic materials 0.000 claims description 8
- 238000005507 spraying Methods 0.000 claims description 8
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 claims description 4
- 229910052728 basic metal Inorganic materials 0.000 claims description 4
- 150000003818 basic metals Chemical class 0.000 claims description 4
- 238000006277 sulfonation reaction Methods 0.000 claims description 4
- 229910052751 metal Inorganic materials 0.000 claims description 2
- 239000002184 metal Substances 0.000 claims description 2
- 239000011734 sodium Substances 0.000 claims description 2
- 239000002994 raw material Substances 0.000 abstract description 5
- 238000003912 environmental pollution Methods 0.000 abstract description 3
- 229910052783 alkali metal Inorganic materials 0.000 abstract 1
- 150000001340 alkali metals Chemical class 0.000 abstract 1
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 14
- 239000001048 orange dye Substances 0.000 description 6
- KRRUJXFCUPBUCQ-UHFFFAOYSA-N 1,3,2,4-dioxadithietane 2,2,4,4-tetraoxide Chemical compound S1(=O)(=O)OS(=O)(=O)O1 KRRUJXFCUPBUCQ-UHFFFAOYSA-N 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 238000004043 dyeing Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 150000003457 sulfones Chemical class 0.000 description 2
- QLRBNEZOQPLERN-UHFFFAOYSA-N (sulfonylamino)benzene Chemical compound O=S(=O)=NC1=CC=CC=C1 QLRBNEZOQPLERN-UHFFFAOYSA-N 0.000 description 1
- ZMCHBSMFKQYNKA-UHFFFAOYSA-N 2-aminobenzenesulfonic acid Chemical compound NC1=CC=CC=C1S(O)(=O)=O ZMCHBSMFKQYNKA-UHFFFAOYSA-N 0.000 description 1
- IOVCWXUNBOPUCH-UHFFFAOYSA-M Nitrite anion Chemical compound [O-]N=O IOVCWXUNBOPUCH-UHFFFAOYSA-M 0.000 description 1
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 210000000085 cashmere Anatomy 0.000 description 1
- AFOSIXZFDONLBT-UHFFFAOYSA-N divinyl sulfone Chemical compound C=CS(=O)(=O)C=C AFOSIXZFDONLBT-UHFFFAOYSA-N 0.000 description 1
- 239000002932 luster Substances 0.000 description 1
- 239000000983 mordant dye Substances 0.000 description 1
- WXWCDTXEKCVRRO-UHFFFAOYSA-N para-Cresidine Chemical compound COC1=CC=C(C)C=C1N WXWCDTXEKCVRRO-UHFFFAOYSA-N 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Paper (AREA)
Abstract
The invention discloses an orange reactive dye for wool and a preparation method thereof. The orange reactive dye for the wool is a compound having a general formula (I) structure as follows, wherein R1 is H, alkyl, alkoxy or SO3M; R2 is H, alkyl or alkoxy; R3 is COCHBrCH2Br; Z is SO2C2H4OSO3M; and M is H or alkali metal. The usage and the preparation for the dye can reduce environmental pollution; and the orange reactive dye for wool is characterized by low cost of raw materials, high product solubility, bright color, excellent application performance, convenient use and strong applicability.
Description
Technical field
The present invention relates to a kind of reactive dye for wool and preparation method thereof, particularly relate to a kind of orange reactive 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.
Technical problem to be solved by this invention is, provides one can reduce environmental pollution, and the desired raw material cost is low, the product solubility height, and also bright in colour, the application performance excellence, easy to use, orange reactive dye for wool that suitability is strong and preparation method thereof.
Summary of the invention
In order to solve the problems of the technologies described above, the invention provides a kind of orange reactive dye for wool, this orange reactive dye for wool is the compound with following general formula (I) structure:
Wherein:
R
1Be H, alkyl, alkoxyl group or SO
3M;
R
2Be H, alkyl or alkoxyl group;
R
3Be COCHBrCH
2Br;
Z is SO
2C
2H
4OSO
3M;
M is H or basic metal;
Preferably, wherein alkyl is CH
3Or CH
2CH
3, alkoxyl group is OCH
3Or OCH
2CH
3, M is a basic metal;
More preferably, alkyl is CH
3, alkoxyl group is OCH
3, M is the Na metal;
The preparation method of the dye composition of said structure formula (I) comprises the steps:
The dissolving of a, J acid
Transferring the pH of J acid solution with sodium hydroxide solution is 6.5-7.0, and the mass/volume concentration of adjusting solution is 7.5%, gets the J acid solution;
B, condensation reaction
Adjusting J acid solution mass/volume concentration is 6%, keeps pH=6～6.5 with sodium bicarbonate, 5～10 ℃ of temperature, and 40～60 minutes times spent, add 2,3-two bromo propionyl chloros and acetone mixed solution reacted 1-3 hour, got condensated liquid.
C, diazotization reaction
In water, the regulator solution temperature is less than 0 ℃ with the compound dissolution of following general formula (II), and the pH that keeps solution with hydrochloric acid adds Sodium Nitrite fast less than 2, keeps 0～5 ℃ of reaction of temperature 1-3 hour, eliminates excessive nitrous acid with thionamic acid, diazonium liquid,
R wherein
1, R
2With the implication of Z with top definition.
D, coupled reaction
The diazonium liquid that the c step is obtained joins in the condensated liquid that the b step obtains, holding temperature 10-30 ℃, keep pH=5-8, reacted 3-5 hour coupling solution.
E, neutralization reaction
Coupling solution is adjusted to pH=6-6.5 with hydrochloric acid soln, stirred 10-20 minute.
F, drying
With dry formula (I) compound that gets of the solution spray of e step.
Preferably, the preparation method of the dye composition of said structure formula (I) comprises the steps:
The dissolving of a, J acid
With water dissolution J acid, transfer pH=6.5-7 with sodium hydroxide solution then, make material dissolution, clarification, the mass/volume concentration of adjusting solution is 7.5%, gets the J acid solution;
B, condensation reaction
Under 5～7 ℃ of temperature, adjusting J acid solution mass/volume concentration is 6%, keep pH=6～6.5 with sodium bicarbonate, kept 40～60 minutes for 5～10 ℃ in temperature, add 2 then, 3-two bromo propionyl chloros and acetone mixed solution, 5～10 ℃ of holding temperatures and pH value 6～6.5, reacted 1-3 hour, and got condensated liquid.
C, diazotization reaction
The compound dissolution of following general formula (II) in water, is added hydrochloric acid, and the regulator solution temperature is less than 0 ℃, the pH that keeps solution adds Sodium Nitrite fast less than 2, keeps 0～5 ℃ of reaction of temperature 1-3 hour, eliminate excessive nitrous acid with thionamic acid, get diazonium liquid
R wherein
1, R
2With the implication of Z with top definition.
D, coupled reaction
The diazonium liquid that the c step is obtained joins in the condensated liquid that the b step obtains, and transfers pH=7 with yellow soda ash, is warmed up to 10 ℃, holding temperature 10-30 ℃, keep pH=5-8, reacted 3-5 hour coupling solution.
E, neutralization reaction
Coupling solution is adjusted to pH=6-6.5 with hydrochloric acid soln, stirred 10-20 minute.
F, drying
With dry formula (I) compound that gets of the solution spray of e step.
More preferably, the preparation method of the dye composition of said structure formula (I) comprises the steps:
The dissolving of a, J acid
In beaker, add water, add 100%J acid then, stir down and transfer pH=6.5-7, make material dissolution with 30% sodium hydroxide solution, clarification, the volume of adjustment solution, the mass/volume concentration that makes solution is 7.5% J acid solution.
B, condensation reaction
Adjust J acid solution temperature to 5～7 ℃ with direct ice and water, adjusting liquor capacity concentration is 6%, keep pH=6～6.5 with sodium bicarbonate then, with 5～10 ℃ of direct ice holding temperatures, 40～60 minutes times spent are with 2 of suitable moles mass, 3-two bromo propionyl chloros and acetone mixed solution add, 5～10 ℃ of holding temperatures and pH value 6～6.5 were reacted 1-3 hour, got condensated liquid.
C, diazotization reaction
In beaker, add water, add the compound of following structural formula (II) then, stirred 10-20 minute.30% hydrochloric acid soln is added, adjust solution temperature less than 0 ℃ with direct ice, adjusting mass/volume concentration is 5.5%, under reaction soln guarantees that the pH value is less than 2 condition, 30% nitrite natrium solution of suitable moles mass is added 0～5 ℃ of holding temperature fast, reacted 1-3 hour, eliminate excessive nitrous acid with thionamic acid, get diazonium liquid
R wherein
1, R
2With the implication of Z with top definition.
D, coupled reaction
The diazonium liquid that the c step is obtained join the b step to condensated liquid in, transfer pH=7 with yellow soda ash, be warmed up to 10 ℃, holding temperature 10-30 ℃, keep pH=5-8, reacted 3-5 hour.
E, neutralization reaction
Coupled reaction liquid is adjusted to pH=6-6.5 with 30% hydrochloric acid soln, stirred 10-20 minute.
F, drying
The look liquid of e step is joined in the feed liquid preheater, adjust the spray tower inlet temperature and carry out spraying drying, obtain product.
J acid is the abbreviation of 2-amino-5-naphthols-7-sulfonic acid or 6-amino-1-naphthols-3-sulfonic acid.Its structural formula is as follows:
Preferably, the compound of said structure formula (II) is position ester, a Ke Lixiding para-ester between para-ester, a position ester, O-methoxy, sulfonation para-ester or 2,5-dimethoxy para-ester.
Particularly, the compound of said structure formula (II) is respectively:
Para-ester claims again (beta-sulfuric ester ethyl sulfonyl) aniline, the vinyl sulfone(Remzaol sulfuric ester, and 4-sulfovinic acid sulfuryl aniline, right-beta-hydroxy second sulfone aniline sulfuric ester or right-beta-hydroxy second sulfone aniline sulfuric ester, its structural formula is as follows:
Between the position ester be between the abbreviation of (beta-sulfuric ester ethyl sulfonyl base) aniline, its structural formula is as follows:
By name the 2-methoxyl group-5-β-its structural formula of ethyl sulfuryl sulfate ester aniline is as follows for the chemistry of position ester between O-methoxy:
The CAS number of boarding of Ke Lixiding para-ester (Para Cresidine Base) is 21635-69-8.
The chemistry of sulfonation para-ester is called 4-β-ethyl sulfuryl sulfate ester aniline-2-sulfonic acid, and its structural formula is as follows:
2, the chemistry of 5-dimethoxy para-ester is called 2,5-dimethoxy-4 '-β-ethyl sulfuryl sulfate ester aniline, and the CAS number of boarding is 26672-24-2, structural formula is as follows:
Aforesaid method and hereinafter in the method for embodiment, the unit of mass/volume concentration is grams per milliliter (g/ml) or kg/liter (kg/L).
Used various raw materials all can be bought from the market and obtain in the aforesaid method.
Using and preparing of the compound of the present invention's preparation can reduce environmental pollution, and the desired raw material cost is low, the product solubility height, and lovely luster, the application performance excellence, easy to use, be the strong orange reactive dye for wool of a kind of suitability.
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
The dissolving of a, J acid
In 500 ml beakers, add 200 milliliters in water, add 100%J acid 23.9 grams then, stir down and transfer pH=6.5-7.0 with 30% sodium hydroxide solution, make material dissolution, clarification, the volume of adjusting solution is 319 milliliters, the mass/volume concentration that makes solution is 7.5%, gets the J acid solution.
B, condensation reaction
Adjust J acid solution temperature to 5～7 ℃ with direct ice and water, adjusting solution quality/volumetric concentration is 6%, follow 96% sodium bicarbonate to keep pH=6～6.5 then, with 5～10 ℃ of direct ice holding temperatures, 50 minutes times spent, with 100% 2,3-two bromo propionyl chloros 32.6 gram and the adding of acetone mixed solution, 5～10 ℃ of holding temperatures and pH value 6～6.5, react 2 hours must condensated liquid.
C, diazotization reaction
In 800 ml beakers, add 200 milliliters in water, then 100% para-ester, 28.1 grams are added, stirred 15 minutes.Again 15.8 grams, 30% hydrochloric acid soln is added, adjust solution temperature less than 0 ℃ with direct ice, adjusting mass/volume concentration is 5.5%, under reaction soln guarantees that the pH value is less than 2 condition,, be made into 30% sodium nitrite solution and add fast 100% Sodium Nitrite, 7.04 grams, 0～5 ℃ of holding temperature, reacted 2 hours, and eliminated excessive nitrous acid, get diazonium liquid with thionamic acid
D, coupled reaction
The diazonium liquid that the c step is obtained joins in the condensated liquid that the b step obtains, and transfers pH=7 with 96% yellow soda ash, is warmed up to 20 ℃, and holding temperature 20-30 ℃, keep pH=7-7.5, reacted 4 hours.
E, neutralization reaction
Coupled reaction liquid is adjusted to pH=6-6.5 with 30% hydrochloric acid soln, stirred 15 minutes.
F, drying
The look liquid of e step is joined in the feed liquid preheater, adjust the spray tower inlet temperature and carry out spraying drying.Get the orange dye of following formula structure.
Embodiment 2
The dissolving of a, J acid
In 500 ml beakers, add 200 milliliters in water, add 100%J acid 23.9 grams then, stir down and transfer pH=6.5-7, make material dissolution, clarification with 30% sodium hydroxide solution.The volume of adjusting solution is 319 milliliters.The mass/volume concentration that makes solution is 7.5%
B, condensation reaction
Adjust J acid solution temperature to 5～7 ℃ with direct ice and water, adjusting solution quality/volumetric concentration is 6%, follow 96% sodium bicarbonate to keep pH=6～6.5 then, with 5～10 ℃ of direct ice holding temperatures, 50 minutes times spent, with 100% 2,3-two bromo propionyl chloros 32.6 gram and the adding of acetone mixed solution, 5～10 ℃ of holding temperatures and pH value 6～6.5, react 2 hours must condensated liquid.
C, diazotization reaction
In 800 ml beakers, add 200 milliliters in water, then 100% position ester, 28.1 grams are added, stirred 15 minutes.Again 15.8 grams, 30% hydrochloric acid soln is added.Adjust solution temperature less than 0 ℃ with direct ice, adjusting mass/volume concentration is 5.5%, under reaction soln guarantees that the pH value is less than 2 condition, with 100% Sodium Nitrite, 7.04 grams, is made into 30% sodium nitrite solution and adds fast.0～5 ℃ of holding temperature was reacted 2 hours, eliminated excessive nitrous acid with thionamic acid, got diazonium liquid
D, coupled reaction
The diazonium liquid that the c step is obtained joins in the condensated liquid that the b step obtains, and transfers pH=7 with 96% yellow soda ash, is warmed up to 20 ℃, and holding temperature 20-30 ℃, keep pH=7-7.5, reacted 4 hours.
E, neutralization reaction
Coupled reaction liquid is adjusted to pH=6-6.5 with 30% hydrochloric acid soln, stirred 15 minutes.
F, drying
The look liquid of e step is joined in the feed liquid preheater, adjust the spray tower inlet temperature and carry out spraying drying.Get the orange dye of following formula structure:
Embodiment 3
The dissolving of a, J acid
In 500 ml beakers, add 200 milliliters in water, add 100%J acid 23.9 grams then, stir down and transfer pH=6.5-7, make material dissolution, clarification with 30% sodium hydroxide solution.The volume of adjusting solution is 319 milliliters.The mass/volume concentration that makes solution is 7.5%
B, condensation reaction
Adjust J acid solution temperature to 5～7 ℃ with direct ice and water, adjusting solution quality/volumetric concentration is 6%, follow 96% sodium bicarbonate to keep pH=6～6.5 then, with 5～10 ℃ of direct ice holding temperatures, 50 minutes times spent, with 100% 2,3-two bromo propionyl chloros 32.6 gram and the adding of acetone mixed solution, 5～10 ℃ of holding temperatures and pH value 6～6.5, react 2 hours must condensated liquid.
C, diazotization reaction
In 800 ml beakers, add 200 milliliters in water, then 100%2-methoxyl group-5-β-ethyl sulfuryl sulfate ester aniline 31.1 grams are added, stirred 15 minutes.Again 15.8 grams, 30% hydrochloric acid soln is added.Adjust solution temperature less than 0 ℃ with direct ice, adjusting mass/volume concentration is 5.5%, under reaction soln guarantees that the pH value is less than 2 condition, with 100% Sodium Nitrite, 7.04 grams, is made into 30% sodium nitrite solution and adds fast.0～5 ℃ of holding temperature was reacted 2 hours, eliminated excessive nitrous acid with thionamic acid, got diazonium liquid
D, coupled reaction
The diazonium liquid that the c step is obtained joins in the condensated liquid that the b step obtains, and transfers pH=7 with 96% yellow soda ash, is warmed up to 20 ℃, and holding temperature 20-30 ℃, keep pH=7-7.5, reacted 4 hours.
E, neutralization reaction
Coupled reaction liquid is adjusted to pH=6-6.5 with 30% hydrochloric acid soln, stirred 15 minutes.
F, drying
The look liquid of e step is joined in the feed liquid preheater, adjust the spray tower inlet temperature and carry out spraying drying.Get the orange dye of following formula structure:
Embodiment 4
The dissolving of a, J acid
In 500 ml beakers, add 200 milliliters in water, add 100%J acid 23.9 grams then, stir down and transfer pH=6.5-7, make material dissolution, clarification with 30% sodium hydroxide solution.The volume of adjusting solution is 319 milliliters.The mass/volume concentration that makes solution is 7.5%
B, condensation reaction
Adjust J acid solution temperature to 5～7 ℃ with direct ice and water, adjusting solution quality/volumetric concentration is 6%, follow 96% sodium bicarbonate to keep pH=6～6.5 then, with 5～10 ℃ of direct ice holding temperatures, 50 minutes times spent, with 100% 2,3-two bromo propionyl chloros 32.6 gram and the adding of acetone mixed solution, 5～10 ℃ of holding temperatures and pH value 6～6.5, react 2 hours must condensated liquid.
C, diazotization reaction
In 800 ml beakers, add 200 milliliters in water, then 100% Ke Lixiding para-ester, 32.5 grams are added, stirred 15 minutes.Again 15.8 grams, 30% hydrochloric acid soln is added.Adjust solution temperature less than 0 ℃ with direct ice, adjusting mass/volume concentration is 5.5%, under reaction soln guarantees that the pH value is less than 2 condition, with 100% Sodium Nitrite, 7.04 grams, is made into 30% sodium nitrite solution and adds fast.0～5 ℃ of holding temperature was reacted 2 hours, eliminated excessive nitrous acid with thionamic acid, got diazonium liquid
D, coupled reaction
The diazonium liquid that the c step is obtained joins in the condensated liquid that the b step obtains, and transfers pH=7 with 96% yellow soda ash, is warmed up to 20 ℃, and holding temperature 20-30 ℃, keep pH=7-7.5, reacted 4 hours.
E, neutralization reaction
Coupled reaction liquid is adjusted to pH=6-6.5 with 30% hydrochloric acid soln, stirred 15 minutes.
F, drying
The look liquid of e step is joined in the feed liquid preheater, adjust the spray tower inlet temperature and carry out spraying drying.Get the orange dye of following formula structure:
Embodiment 5
The dissolving of a, J acid
In 500 ml beakers, add 200 milliliters in water, add 100%J acid 23.9 grams then, stir down and transfer pH=6.5-7, make material dissolution, clarification with 30% sodium hydroxide solution.The volume of adjusting solution is 319 milliliters.The mass/volume concentration that makes solution is 7.5%
B, condensation reaction
Adjust J acid solution temperature to 5～7 ℃ with direct ice and water, adjusting solution quality/volumetric concentration is 6%, follow 96% sodium bicarbonate to keep pH=6～6.5 then, with 5～10 ℃ of direct ice holding temperatures, 50 minutes times spent, with 100% 2,3-two bromo propionyl chloros 32.6 gram and the adding of acetone mixed solution, 5～10 ℃ of holding temperatures and pH value 6～6.5, react 2 hours must condensated liquid.
C, diazotization reaction
In 800 ml beakers, add 200 milliliters in water, then 100% sulfonation para-ester, 36.1 grams are added, stirred 15 minutes.Again 15.8 grams, 30% hydrochloric acid soln is added.Adjust solution temperature less than 0 ℃ with direct ice, adjusting mass/volume concentration is 5.5%, under reaction soln guarantees that the pH value is less than 2 condition, with 100% Sodium Nitrite, 7.04 grams, is made into 30% sodium nitrite solution and adds fast.0～5 ℃ of holding temperature was reacted 2 hours, eliminated excessive nitrous acid with thionamic acid, got diazonium liquid
D, coupled reaction
The diazonium liquid that the c step is obtained joins in the condensated liquid that the b step obtains, and transfers pH=7 with 96% yellow soda ash, is warmed up to 20 ℃, and holding temperature 20-30 ℃, keep pH=7-7.5, reacted 4 hours.
E, neutralization reaction
Coupled reaction liquid is adjusted to pH=6-6.5 with 30% hydrochloric acid soln, stirred 15 minutes.
F, drying
The look liquid of e step is joined in the feed liquid preheater, adjust the spray tower inlet temperature and carry out spraying drying.Get the orange dye of following formula structure:
Embodiment 6
The dissolving of a, J acid
In 500 ml beakers, add 200 milliliters in water, add 100%J acid 23.9 grams then, stir down and transfer pH=6.5-7, make material dissolution, clarification with 30% sodium hydroxide solution.The volume of adjusting solution is 319 milliliters.The mass/volume concentration that makes solution is 7.5%
B, condensation reaction
Adjust J acid solution temperature to 5～7 ℃ with direct ice and water, adjusting solution quality/volumetric concentration is 6%, follow 96% sodium bicarbonate to keep pH=6～6.5 then, with 5～10 ℃ of direct ice holding temperatures, 50 minutes times spent, with 100% 2,3-two bromo propionyl chloros 32.6 gram and the adding of acetone mixed solution, 5～10 ℃ of holding temperatures and pH value 6～6.5, react 2 hours must condensated liquid.
C, diazotization reaction
Add 200 milliliters in water in 800 ml beakers, then with 100%2,5-dimethoxy para-ester 34.1 grams add, and stir 15 minutes.Again 15.8 grams, 30% hydrochloric acid soln is added.Adjust solution temperature less than 0 ℃ with direct ice, adjusting mass/volume concentration is 5.5%, under reaction soln guarantees that the pH value is less than 2 condition, with 100% Sodium Nitrite, 7.04 grams, is made into 30% sodium nitrite solution and adds fast.0～5 ℃ of holding temperature was reacted 2 hours, eliminated excessive nitrous acid with thionamic acid, got diazonium liquid
D, coupled reaction
The diazonium liquid that the c step is obtained joins in the condensated liquid that the b step obtains, and transfers pH=7 with 96% yellow soda ash, is warmed up to 20 ℃, and holding temperature 20-30 ℃, keep pH=7-7.5, reacted 4 hours.
E, neutralization reaction
Coupled reaction liquid is adjusted to pH=6-6.5 with 30% hydrochloric acid soln, stirred 15 minutes.
F, drying
The look liquid of e step is joined in the feed liquid preheater, adjust the spray tower inlet temperature and carry out spraying drying.Get the orange dye of following formula structure:
The orange reactive dye for wool application performance of the embodiment of the invention 1 preparation is as shown in the table:
Compound of the present invention and preparation method thereof is described by specific embodiment.Those skilled in the art can use for reference 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 regarded as comprising within the scope of the present invention.
Claims (7)
1. orange reactive dye for wool, this orange reactive dye for wool is the compound with following general formula (I) structure:
Wherein:
R
1Be H, alkyl, alkoxyl group or SO
3M;
R
2Be H, alkyl or alkoxyl group;
R
3Be COCHBrCH
2Br;
Z is SO
2C
2H
4OSO
3M;
M is H or basic metal.
2. dyestuff according to claim 1, wherein alkyl is CH
3Or CH
2CH
3, alkoxyl group is OCH
3Or OCH
2CH
3, M is a basic metal.
3. dyestuff according to claim 1 and 2, wherein alkyl is CH
3, alkoxyl group is OCH
3, M is the Na metal.
4. the preparation method of dyestuff according to claim 1, this method comprises the steps:
The dissolving of a, J acid
Transferring the pH of J acid solution with sodium hydroxide solution is 6.5-7.0, and the mass/volume concentration of adjusting solution is 7.5%, gets the J acid solution;
B, condensation reaction
Adjusting J acid solution mass/volume concentration is 6%, keeps pH=6～6.5 with sodium bicarbonate, 5～10 ℃ of temperature, and 40～60 minutes times spent, add 2,3-two bromo propionyl chloros and acetone mixed solution reacted 1-3 hour, got condensated liquid;
C, diazotization reaction
In water, the regulator solution temperature is less than 0 ℃ with the compound dissolution of following general formula (II), and the pH that keeps solution with hydrochloric acid adds Sodium Nitrite fast less than 2, keeps 0～5 ℃ of reaction of temperature 1-3 hour, eliminates excessive nitrous acid with thionamic acid, diazonium liquid,
R wherein
1, R
2With the implication of Z with the definition in the claim 1;
D, coupled reaction
The diazonium liquid that the c step is obtained joins in the condensated liquid that the b step obtains, holding temperature 10-30 ℃, keep pH=5-8, reacted 3-5 hour coupling solution;
E, neutralization reaction
Coupling solution is adjusted to pH=6-6.5 with hydrochloric acid soln, stirred 10-20 minute;
F, drying
With dry formula (I) compound that gets of the solution spray of e step.
5. method according to claim 4, this method comprises the steps:
The dissolving of a, J acid
With water dissolution J acid, transfer pH=6.5-7 with sodium hydroxide solution then, make material dissolution, clarification, the mass/volume concentration of adjusting solution is 7.5%, gets the J acid solution;
B, condensation reaction
Under 5～7 ℃ of temperature, adjusting J acid solution mass/volume concentration is 6%, keep pH=6～6.5 with sodium bicarbonate, 5～10 ℃ of temperature, 40～60 minutes times spent, add 2,3-two bromo propionyl chloros and acetone mixed solution, 5～10 ℃ of holding temperatures and pH value 6～6.5 were reacted 1-3 hour, got condensated liquid;
C, diazotization reaction
The compound dissolution of following general formula (II) in water, is added hydrochloric acid, and the regulator solution temperature is less than 0 ℃, the pH that keeps solution adds Sodium Nitrite fast less than 2, keeps 0～5 ℃ of reaction of temperature 1-3 hour, eliminate excessive nitrous acid with thionamic acid, get diazonium liquid
R wherein
1, R
2With the implication of Z with the definition in the claim 1;
D, coupled reaction
The diazonium liquid that the c step is obtained joins in the condensated liquid that the b step obtains, and transfers pH=7 with yellow soda ash, is warmed up to 10 ℃, holding temperature 10-30 ℃, keep pH=5-8, reacted 3-5 hour coupling solution;
E, neutralization reaction
Coupling solution is adjusted to pH=6-6.5 with hydrochloric acid soln, stirred 10-20 minute;
F, drying
With dry formula (I) compound that gets of the solution spray of e step.
6. method according to claim 5, this method comprises the steps:
The dissolving of a, J acid
In beaker, add water, add 100%J acid then, stir down and transfer pH=6.5-7, make material dissolution with 30% sodium hydroxide solution, clarification, the volume of adjustment solution, the mass/volume concentration that makes solution is 7.5% J acid solution;
B, condensation reaction
Adjust J acid solution temperature to 5～7 ℃ with direct ice and water, adjusting liquor capacity concentration is 6%, keep pH=6～6.5 with sodium bicarbonate then, with 5～10 ℃ of direct ice holding temperatures, 40～60 minutes times spent are with 2 of suitable moles mass, 3-two bromo propionyl chloros and acetone mixed solution add, 5～10 ℃ of holding temperatures and pH value 6～6.5 were reacted 1-3 hour, got condensated liquid;
C, diazotization reaction
In beaker, add water, add the compound of following structural formula (II) then, stirred 10-20 minute; 30% hydrochloric acid soln is added, adjust solution temperature less than 0 ℃ with direct ice, adjusting mass/volume concentration is 5.5%, under reaction soln guarantees that the pH value is less than 2 condition, 30% sodium nitrite solution of suitable moles mass is added 0～5 ℃ of holding temperature fast, reacted 1-3 hour, eliminate excessive nitrous acid with thionamic acid, get diazonium liquid
R wherein
1, R
2With the implication of Z with the definition in the claim 1;
D, coupled reaction
The diazonium liquid that the c step is obtained joins in the condensated liquid that the b step obtains, and transfers pH=7 with yellow soda ash, is warmed up to 10 ℃, and holding temperature 10-30 ℃, keep pH=5-8, reacted 3-5 hour;
E, neutralization reaction
Coupled reaction liquid is adjusted to pH=6-6.5 with 30% hydrochloric acid soln, stirred 10-20 minute;
F, drying
The look liquid of e step is joined in the feed liquid preheater, adjust the spray tower inlet temperature and carry out spraying drying, obtain product.
7. according to the described method of claim 4-6, wherein the compound of structural formula (II) is position ester, a Ke Lixiding para-ester between para-ester, a position ester, O-methoxy, sulfonation para-ester or 2,5-dimethoxy para-ester.
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|---|---|---|---|
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|---|---|---|---|
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101906256A (en) * | 2010-08-20 | 2010-12-08 | 天津德凯化工股份有限公司 | Orange reactive dye and preparation method thereof |
| CN101942215A (en) * | 2010-08-20 | 2011-01-12 | 天津德凯化工股份有限公司 | Orange reactive dye for wool and preparation method thereof |
| CN102190906A (en) * | 2011-03-26 | 2011-09-21 | 安徽盛源染料有限公司 | Nylon orange active dye and preparation method thereof |
| CN102433022A (en) * | 2011-09-27 | 2012-05-02 | 天津德凯化工股份有限公司 | Maotai-red reactive dye and preparation method thereof |
| CN105504870A (en) * | 2015-11-27 | 2016-04-20 | 天津德凯化工股份有限公司 | Yellow reactive dye and preparation method thereof |
| CN105504869A (en) * | 2015-11-27 | 2016-04-20 | 天津德凯化工股份有限公司 | Yellow reactive dye |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB8530459D0 (en) * | 1985-12-11 | 1986-01-22 | Ciba Geigy Ag | Holograms |
| GB8530454D0 (en) * | 1985-12-11 | 1986-01-22 | Ciba Geigy Ag | Processing holograms |
| EP0419413A1 (en) * | 1989-09-22 | 1991-03-27 | Ciba-Geigy Ag | Dyeing or printing process of blended fibres containing cellulose fibres and silk |
| DE4437262A1 (en) * | 1993-10-22 | 1995-04-27 | Ciba Geigy Ag | Reactive dyes, preparation thereof and use thereof |
-
2009
- 2009-11-16 CN CN 200910228201 patent/CN101705014B/en active Active
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101906256A (en) * | 2010-08-20 | 2010-12-08 | 天津德凯化工股份有限公司 | Orange reactive dye and preparation method thereof |
| CN101942215A (en) * | 2010-08-20 | 2011-01-12 | 天津德凯化工股份有限公司 | Orange reactive dye for wool and preparation method thereof |
| CN102190906A (en) * | 2011-03-26 | 2011-09-21 | 安徽盛源染料有限公司 | Nylon orange active dye and preparation method thereof |
| CN102190906B (en) * | 2011-03-26 | 2013-07-10 | 安徽盛源染料有限公司 | Nylon orange active dye and preparation method thereof |
| CN102433022A (en) * | 2011-09-27 | 2012-05-02 | 天津德凯化工股份有限公司 | Maotai-red reactive dye and preparation method thereof |
| CN102433022B (en) * | 2011-09-27 | 2016-06-08 | 天津德凯化工股份有限公司 | Garnet-red reactive dye and preparation method thereof |
| CN105504870A (en) * | 2015-11-27 | 2016-04-20 | 天津德凯化工股份有限公司 | Yellow reactive dye and preparation method thereof |
| CN105504869A (en) * | 2015-11-27 | 2016-04-20 | 天津德凯化工股份有限公司 | Yellow reactive dye |
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| CN101705014B (en) | 2012-09-05 |
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Address after: 300270 No. 1558 Kaixuan street, Dagang Petrochemical Industrial Park, Binhai New Area, Tianjin Patentee after: Tianjin Dek Chemical Co.,Ltd. Address before: 300163 Tianjin city Dongli District ZhangGuiZhuang road Ji'an Road Patentee before: Tianjin Dek Chemical Co.,Ltd. |
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