CN115678307A - Method based on metal-free acid dye product - Google Patents
Method based on metal-free acid dye product Download PDFInfo
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- CN115678307A CN115678307A CN202211396720.5A CN202211396720A CN115678307A CN 115678307 A CN115678307 A CN 115678307A CN 202211396720 A CN202211396720 A CN 202211396720A CN 115678307 A CN115678307 A CN 115678307A
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- coupling
- reaction
- stirring
- kettle
- acid dye
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- 239000000980 acid dye Substances 0.000 title claims abstract description 25
- 238000000034 method Methods 0.000 title claims abstract description 25
- LPXPTNMVRIOKMN-UHFFFAOYSA-M sodium nitrite Chemical compound [Na+].[O-]N=O LPXPTNMVRIOKMN-UHFFFAOYSA-M 0.000 claims abstract description 40
- 238000005859 coupling reaction Methods 0.000 claims abstract description 37
- 230000008878 coupling Effects 0.000 claims abstract description 30
- 238000010168 coupling process Methods 0.000 claims abstract description 30
- 238000006243 chemical reaction Methods 0.000 claims abstract description 20
- 235000010288 sodium nitrite Nutrition 0.000 claims abstract description 20
- 238000003756 stirring Methods 0.000 claims abstract description 19
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims abstract description 16
- 125000000664 diazo group Chemical group [N-]=[N+]=[*] 0.000 claims abstract description 15
- 239000012954 diazonium Substances 0.000 claims abstract description 15
- 150000001989 diazonium salts Chemical class 0.000 claims abstract description 15
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 12
- JWAZRIHNYRIHIV-UHFFFAOYSA-N 2-naphthol Chemical compound C1=CC=CC2=CC(O)=CC=C21 JWAZRIHNYRIHIV-UHFFFAOYSA-N 0.000 claims abstract description 8
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 claims abstract description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 8
- -1 m-aminophenylsulfonylamino G salt Chemical compound 0.000 claims abstract description 5
- 229950011260 betanaphthol Drugs 0.000 claims abstract description 4
- 239000012295 chemical reaction liquid Substances 0.000 claims abstract description 4
- 239000007788 liquid Substances 0.000 claims abstract description 4
- 235000011121 sodium hydroxide Nutrition 0.000 claims abstract description 4
- 239000000243 solution Substances 0.000 claims description 17
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 claims description 14
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 10
- NLKNQRATVPKPDG-UHFFFAOYSA-M potassium iodide Chemical compound [K+].[I-] NLKNQRATVPKPDG-UHFFFAOYSA-M 0.000 claims description 9
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 claims description 8
- 239000000463 material Substances 0.000 claims description 7
- 235000010265 sodium sulphite Nutrition 0.000 claims description 7
- 239000012670 alkaline solution Substances 0.000 claims description 4
- LNOPIUAQISRISI-UHFFFAOYSA-N n'-hydroxy-2-propan-2-ylsulfonylethanimidamide Chemical compound CC(C)S(=O)(=O)CC(N)=NO LNOPIUAQISRISI-UHFFFAOYSA-N 0.000 claims description 4
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 4
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 claims description 3
- 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 3
- 230000035484 reaction time Effects 0.000 claims description 2
- 239000001632 sodium acetate Substances 0.000 claims description 2
- 235000017281 sodium acetate Nutrition 0.000 claims description 2
- 239000003344 environmental pollutant Substances 0.000 abstract description 8
- 231100000719 pollutant Toxicity 0.000 abstract description 8
- SJEYSFABYSGQBG-UHFFFAOYSA-M Patent blue Chemical compound [Na+].C1=CC(N(CC)CC)=CC=C1C(C=1C(=CC(=CC=1)S([O-])(=O)=O)S([O-])(=O)=O)=C1C=CC(=[N+](CC)CC)C=C1 SJEYSFABYSGQBG-UHFFFAOYSA-M 0.000 abstract description 2
- DGPIGKCOQYBCJH-UHFFFAOYSA-M sodium;acetic acid;hydroxide Chemical compound O.[Na+].CC([O-])=O DGPIGKCOQYBCJH-UHFFFAOYSA-M 0.000 abstract 1
- 239000000975 dye Substances 0.000 description 5
- 235000017550 sodium carbonate Nutrition 0.000 description 3
- 230000002378 acidificating effect Effects 0.000 description 2
- 238000004043 dyeing Methods 0.000 description 2
- 230000002588 toxic effect Effects 0.000 description 2
- 231100000563 toxic property Toxicity 0.000 description 2
- 239000002351 wastewater Substances 0.000 description 2
- 239000002253 acid Substances 0.000 description 1
- PYKYMHQGRFAEBM-UHFFFAOYSA-N anthraquinone Natural products CCC(=O)c1c(O)c2C(=O)C3C(C=CC=C3O)C(=O)c2cc1CC(=O)OC PYKYMHQGRFAEBM-UHFFFAOYSA-N 0.000 description 1
- 150000004056 anthraquinones Chemical class 0.000 description 1
- 239000000987 azo dye Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000006193 diazotization reaction Methods 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 102000004169 proteins and genes Human genes 0.000 description 1
- 108090000623 proteins and genes Proteins 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 210000002268 wool Anatomy 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a method based on a metal-free acid dye product, which relates to the field of acid dyes and comprises the following steps: adding water and hydrochloric acid into a diazo kettle, and adding m-aminophenylsulfonylamino G salt while stirring to generate diazonium salt; step two: adding sodium acetate hydrate and aniline into a coupling kettle, stirring, and transferring the diazonium salt in the step one into the coupling kettle for coupling; step three: adding hydrochloric acid into the reaction liquid after the reaction reaches the end point, and dropwise adding a sodium nitrite solution while stirring; step four: adding water, liquid caustic soda and 2-naphthol into a second coupling kettle, stirring, and transferring the diazonium salt in the third step into the coupling kettle for coupling. The invention has excellent color fastness and bright color light through multiple times of diazo and coupling staggered reaction, and simultaneously fundamentally solves the problems that the acid dye is difficult to degrade in the environment after being used and is easy to generate 'three-cause' pollutants after multiple times of diazo and coupling reaction.
Description
Technical Field
The invention relates to the field of acid dyes, in particular to a method based on a metal-free acid dye product.
Background
The acid dye is a dye containing an acid group in a dye molecule, and comprises azo type, anthraquinone type, triarylmethane type and the like, most of the dye belongs to azo dyes, the acid dye can be combined with amino of protein fiber to form an ionic bond, the application range is wide, and the acid dye can be used under acidic, weakly acidic and neutral conditions.
The acid dye is mainly used for dyeing wool, silk and the like, but the utilization rate is low, a large amount of dye is discharged into the environment along with waste water, and the acid dye waste water has the characteristics of large chroma, poor biodegradability, stable pollutant chemical property, strong oxidation resistance and the like.
Because the structure is difficult to degrade in the environment after being used and is easy to generate the toxic property of 'three causes' pollutant, workers are difficult to effectively treat the pollutant, and meanwhile, the acid dye is used as a water-soluble dye, has bright and level dyeing type complete color system and poor color fastness.
Disclosure of Invention
Based on the above, the invention aims to provide a method based on a metal-free acid dye product, so as to solve the technical problems that the structure is difficult to degrade in the environment after being used, the toxic property of pollutants caused by 'three causes' is easy to generate, and the color fastness is poor.
In order to achieve the purpose, the invention provides the following technical scheme: a process based on metal-free acid dye products comprising the steps of:
the method comprises the following steps: adding water and hydrochloric acid into a diazo kettle, adding m-aminophenylsulfonylamino G salt under stirring, stirring and dissolving at normal temperature, adding crushed ice, adjusting the temperature to be lower than 10 ℃, adding a quantitative sodium nitrite solution inwards, keeping the acidity to be lower than 1.5, and reacting for 60 minutes to the end point after the addition;
step two: firstly, coupling, namely adding sodium acetate and aniline into a coupling kettle, stirring, then transferring the diazonium salt obtained in the first step into the coupling kettle for coupling, controlling the temperature to be less than 20 ℃ in the material transferring process, adjusting the pH to be 3-4 by using sodium carbonate after the diazonium salt is completely transferred, and reacting for 2 hours;
step three: diazo, adding hydrochloric acid into the reaction liquid until the end point of the reaction, dropwise adding a sodium nitrite solution while stirring, keeping the acidity less than 1.5, and keeping the content of sodium nitrite in micro excess, wherein the end point is reached after the addition of the sodium nitrite solution is finished and the reaction time is 60 minutes;
step four: and step two, adding water, caustic soda liquid and 2-naphthol into a second coupling kettle, stirring, transferring the diazonium salt in the step three into the coupling kettle for coupling, controlling the temperature to be less than 20 ℃ in the material transferring process, adjusting the pH to be =8-9 by using soda after all the diazonium salt is transferred, and reacting for 2 hours.
By adopting the technical scheme, the diazo and the coupling are subjected to staggered reaction for multiple times, so that the acid dye has excellent color fastness and bright color light, and meanwhile, after multiple diazo and coupling reactions, the problems that the acid dye is difficult to degrade in the environment after being used and easily generates 'three-cause' pollutants are fundamentally solved.
The invention is further configured that after the reaction in the second step and the fourth step is finished, the end point is determined by detecting no color reaction by using resorcinol alkaline solution.
By adopting the technical scheme, whether the coupling reaction is finished or not can be conveniently judged by workers, and excessive reaction can be prevented.
The invention is further configured that in the feeding process in the step one, the acidity and the excessive sodium sulfite condition are controlled by using Congo red and potassium iodide test paper.
By adopting the technical scheme, the acidity and the addition condition of sodium nitrite in the diazo kettle can be conveniently and timely adjusted by workers in the reaction process.
The invention further provides that in the third step, excessive sodium sulfite is removed by using a small amount of sulfamic acid, and the sodium sulfite is ready for use.
By adopting the technical scheme, after the reaction is finished, redundant sodium sulfite in the reaction kettle is removed through a small amount of sulfamic acid.
The invention is further set that the sodium nitrite solution in the first step is added through trickle flow of the head tank at a constant speed.
By adopting the technical scheme, the phenomenon that the added sodium nitrite solution is excessive is prevented.
In summary, the invention mainly has the following beneficial effects:
the invention has excellent color fastness and bright color light through multiple times of diazo and coupling staggered reaction, and simultaneously fundamentally solves the problems that the acid dye is difficult to degrade in the environment after being used and is easy to generate 'three-cause' pollutants after multiple times of diazo and coupling reaction.
Detailed Description
The technical solutions in the embodiments of the present invention are clearly and completely described below. Are only used for explaining the present invention and should not be construed as limiting the present invention.
The following describes an embodiment of the present invention based on its overall structure.
A process based on metal-free acid dye products comprising the steps of:
the method comprises the following steps: adding water and hydrochloric acid into a diazo kettle, adding m-aminophenylsulfonylamino G salt under stirring, stirring and dissolving the m-aminophenylsulfonylamino G salt at normal temperature, adding crushed ice, adjusting the temperature to be 5, adding a quantitative sodium nitrite solution inwards, keeping the acidity to be 1, reacting for 60 minutes to the end point after the addition, controlling the acidity and the excessive sodium sulfite condition by using Congo red and potassium iodide test paper in the feeding process, so that a worker can timely adjust the acidity and the excessive sodium nitrite adding condition in the diazo kettle in the reaction process, and simultaneously adding the sodium nitrite solution through trickle of an elevated tank at a constant speed to prevent the excessive sodium nitrite solution adding condition;
step two: firstly, coupling, namely adding sodium acetate hydrate and aniline into a coupling kettle, stirring, then transferring the diazonium salt obtained in the step one into the coupling kettle for coupling, controlling the temperature to be 15 ℃ in the material transferring process, adjusting the pH to be =3.5 by using soda ash and reacting for 2 hours after all the diazonium salt is transferred, and detecting that no color reaction is finished by using resorcinol alkaline solution to obtain an end point, so that a worker can conveniently judge whether the coupling reaction is finished or not and prevent the coupling reaction from being over-reacted;
step three: diazo, adding hydrochloric acid into the reaction liquid which is reacted to the end point, dropwise adding a sodium nitrite solution while stirring, keeping the acidity of the solution 1, wherein the sodium nitrite solution is slightly excessive, the reaction is finished for 60 minutes until the end point, and removing excessive sodium nitrite in the reaction solution through a small amount of sulfamic acid after the reaction is finished;
step four: and secondly, adding water, caustic soda liquid and 2-naphthol into a secondary coupling kettle, stirring, transferring the diazonium salt in the third step into the coupling kettle for coupling, controlling the temperature to be 15 ℃ in the material transferring process, adjusting the pH =8.5 by using soda ash after all the diazonium salt is transferred, reacting for 2 hours, detecting that no color development reaction is a terminal point by using resorcinol alkaline solution, so that the terminal point has excellent color fastness and bright color light, and fundamentally solving the problems that the acid dye is difficult to degrade in the environment after being used and easily generates 'three-cause' pollutants after multiple times of diazotization and coupling reactions.
Although embodiments of the present invention have been shown and described, it is intended that the present invention should not be limited thereto, that the particular features, structures, materials or characteristics described may be combined in any suitable manner in any one or more embodiments or examples, and that modifications, substitutions, variations or the like, which are not inventive and may be made by those skilled in the art without departing from the principle and spirit of the present invention and without departing from the scope of the claims.
Claims (5)
1. A process based on metal-free acid dye products characterized by: the method comprises the following steps:
the method comprises the following steps: adding water and hydrochloric acid into a diazo kettle, adding m-aminophenylsulfonylamino G salt under stirring, stirring and dissolving at normal temperature, adding crushed ice, adjusting the temperature to be lower than 10 ℃, adding a quantitative sodium nitrite solution inwards, keeping the acidity to be lower than 1.5, and reacting for 60 minutes to the end point after the addition;
step two: firstly, coupling, namely adding sodium acetate and aniline into a coupling kettle, stirring, then transferring the diazonium salt obtained in the first step into the coupling kettle for coupling, controlling the temperature to be less than 20 ℃ in the material transferring process, adjusting the pH to be 3-4 by using sodium carbonate after the diazonium salt is completely transferred, and reacting for 2 hours;
step three: diazo, adding hydrochloric acid into the reaction liquid until the end point of the reaction, dropwise adding a sodium nitrite solution while stirring, keeping the acidity less than 1.5, and keeping the content of sodium nitrite in micro excess, wherein the end point is reached after the addition of the sodium nitrite solution is finished and the reaction time is 60 minutes;
step four: and step two, adding water, caustic soda liquid and 2-naphthol into a second coupling kettle, stirring, transferring the diazonium salt in the step three into the coupling kettle for coupling, controlling the temperature to be less than 20 ℃ in the material transferring process, adjusting the pH to be =8-9 by using soda after all the diazonium salt is transferred, and reacting for 2 hours.
2. The process according to claim 1 based on metal-free acid dye products, characterized in that: and after the reaction in the second step and the fourth step is finished, detecting that no color reaction is generated by using resorcinol alkaline solution, and thus obtaining the end point.
3. The process according to claim 1 based on metal-free acid dye products, characterized in that: in the feeding process in the first step, the acidity and the excessive sodium sulfite condition are controlled by using Congo red and potassium iodide test paper.
4. The process according to claim 1 based on metal-free acid dye products, characterized in that: in the third step, redundant sodium sulfite is removed by using a small amount of sulfamic acid and is ready for use.
5. The process according to claim 1 based on metal-free acid dye products, characterized in that: and (4) adding the sodium nitrite solution in the step one through trickle flow in a head tank at a constant speed.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211396720.5A CN115678307A (en) | 2022-11-09 | 2022-11-09 | Method based on metal-free acid dye product |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211396720.5A CN115678307A (en) | 2022-11-09 | 2022-11-09 | Method based on metal-free acid dye product |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN115678307A true CN115678307A (en) | 2023-02-03 |
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|---|---|---|---|
| CN202211396720.5A Pending CN115678307A (en) | 2022-11-09 | 2022-11-09 | Method based on metal-free acid dye product |
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| Country | Link |
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| CN (1) | CN115678307A (en) |
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- 2022-11-09 CN CN202211396720.5A patent/CN115678307A/en active Pending
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Application publication date: 20230203 |