CN101585975A - Method for preparing reactive red 3G for wool - Google Patents
Method for preparing reactive red 3G for wool Download PDFInfo
- Publication number
- CN101585975A CN101585975A CN 200810154113 CN200810154113A CN101585975A CN 101585975 A CN101585975 A CN 101585975A CN 200810154113 CN200810154113 CN 200810154113 CN 200810154113 A CN200810154113 A CN 200810154113A CN 101585975 A CN101585975 A CN 101585975A
- Authority
- CN
- China
- Prior art keywords
- reaction
- solution
- add
- hour
- temperature
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 238000000034 method Methods 0.000 title claims abstract description 31
- BFFCQDPRXVYDIA-UHFFFAOYSA-L disodium 6-(2,3-dibromopropanoylamino)-3-[[5-(2,3-dibromopropanoylamino)-2-sulfonatophenyl]diazenyl]-4-hydroxynaphthalene-2-sulfonate Chemical compound [Na+].[Na+].Oc1c(N=Nc2cc(NC(=O)C(Br)CBr)ccc2S([O-])(=O)=O)c(cc2ccc(NC(=O)C(Br)CBr)cc12)S([O-])(=O)=O BFFCQDPRXVYDIA-UHFFFAOYSA-L 0.000 title claims abstract description 12
- 210000002268 wool Anatomy 0.000 title abstract description 4
- 238000006243 chemical reaction Methods 0.000 claims abstract description 21
- 239000007788 liquid Substances 0.000 claims abstract description 7
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 28
- 239000000243 solution Substances 0.000 claims description 28
- LPXPTNMVRIOKMN-UHFFFAOYSA-M sodium nitrite Chemical compound [Na+].[O-]N=O LPXPTNMVRIOKMN-UHFFFAOYSA-M 0.000 claims description 19
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 16
- 239000000047 product Substances 0.000 claims description 16
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 14
- 235000017550 sodium carbonate Nutrition 0.000 claims description 14
- 238000002360 preparation method Methods 0.000 claims description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 11
- 238000006482 condensation reaction Methods 0.000 claims description 10
- 238000003756 stirring Methods 0.000 claims description 10
- 239000012452 mother liquor Substances 0.000 claims description 9
- 239000010813 municipal solid waste Substances 0.000 claims description 9
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 8
- -1 bromo propionyl chloros Chemical compound 0.000 claims description 8
- 238000001035 drying Methods 0.000 claims description 8
- 239000000975 dye Substances 0.000 claims description 8
- 208000006278 hypochromic anemia Diseases 0.000 claims description 8
- 235000010288 sodium nitrite Nutrition 0.000 claims description 8
- 238000009738 saturating Methods 0.000 claims description 7
- 239000012190 activator Substances 0.000 claims description 6
- 239000003795 chemical substances by application Substances 0.000 claims description 6
- 239000012065 filter cake Substances 0.000 claims description 6
- 239000011259 mixed solution Substances 0.000 claims description 6
- 239000012954 diazonium Substances 0.000 claims description 5
- 238000006193 diazotization reaction Methods 0.000 claims description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-O diazynium Chemical compound [NH+]#N IJGRMHOSHXDMSA-UHFFFAOYSA-O 0.000 claims description 5
- 238000012546 transfer Methods 0.000 claims description 5
- 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 4
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 claims description 4
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 claims description 4
- 239000002253 acid Substances 0.000 claims description 4
- 238000005859 coupling reaction Methods 0.000 claims description 4
- 238000001914 filtration Methods 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 4
- 230000035484 reaction time Effects 0.000 claims description 4
- 229910052708 sodium Inorganic materials 0.000 claims description 4
- 239000011734 sodium Substances 0.000 claims description 4
- 229960004418 trolamine Drugs 0.000 claims description 4
- 239000006185 dispersion Substances 0.000 claims description 3
- 239000007791 liquid phase Substances 0.000 claims description 3
- 238000005259 measurement Methods 0.000 claims description 3
- 238000005070 sampling Methods 0.000 claims description 3
- 239000007921 spray Substances 0.000 claims description 3
- 230000001360 synchronised effect Effects 0.000 claims description 3
- 238000012423 maintenance Methods 0.000 claims description 2
- 238000005516 engineering process Methods 0.000 abstract description 11
- 239000012528 membrane Substances 0.000 abstract description 4
- 239000003444 phase transfer catalyst Substances 0.000 abstract description 4
- 230000008569 process Effects 0.000 abstract description 4
- 239000002699 waste material Substances 0.000 abstract description 2
- 239000002351 wastewater Substances 0.000 description 11
- 230000009466 transformation Effects 0.000 description 6
- 230000009286 beneficial effect Effects 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- NLKNQRATVPKPDG-UHFFFAOYSA-M potassium iodide Chemical compound [K+].[I-] NLKNQRATVPKPDG-UHFFFAOYSA-M 0.000 description 3
- 238000010009 beating Methods 0.000 description 2
- 230000001276 controlling effect Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 210000004209 hair Anatomy 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000000985 reactive dye Substances 0.000 description 2
- 229920002472 Starch Polymers 0.000 description 1
- DPDMMXDBJGCCQC-UHFFFAOYSA-N [Na].[Cl] Chemical compound [Na].[Cl] DPDMMXDBJGCCQC-UHFFFAOYSA-N 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000002596 correlated effect Effects 0.000 description 1
- 230000000875 corresponding effect Effects 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 238000010612 desalination reaction Methods 0.000 description 1
- 238000004811 liquid chromatography Methods 0.000 description 1
- 239000002932 luster Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000011265 semifinished product Substances 0.000 description 1
- 235000019698 starch Nutrition 0.000 description 1
- 239000008107 starch Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention provides an improved method for preparing reactive red 3G dye for wool. The method has the advantages of improving process, adopting membrane treatment technology, raising conversion rate by adding phase-transfer catalysts, controlling key links by a central control method, improving product stability, improving product strength through membrane technology and reducing the generation of waste liquid.
Description
Technical field
The present invention relates to the reactive dye for wool field, particularly a kind of mao of preparation method with reactive red 3G.
Background technology
Reactive dye for wool has lovely luster, application performance excellence, characteristics such as easy to use.For example hair is with reactive red 3G dyestuff, and the call number of this dyestuff is Reactive Red 136, and chemical structural formula is:
Hair commonly used at present is as follows with the preparation method and the defective thereof of reactive red 3G dyestuff:
A, two an activators preparation: (1) adds 2 in water, the dissolving of 4-diamino benzene sulfonic acid sodium is standby.(2) in above-mentioned solution, add trash ice and make temperature reach 0-5 ℃, pH=6-6.5, time length 3-4 hour, add 2 then, 3-two bromo propionyl chloros, reaction reach home filter semi-finished product for standby.
The shortcoming of this step is that filter produced a large amount of faint yellow waste water, can't handle after reaction end arrived.
B, condensation reaction: (1) adds γ acid in water, transfer pH=7 with yellow soda ash, and is complete molten standby; (2) add 8-12 ℃ of trash ice cooling in solution, added 2 in 2-3 hour, 3-two bromo propionyl chloros are controlled at 5.5-6.5 with pH, react 1-2 hour, and its transformation efficiency is 96%, and the product that obtains is standby.
C, diazotization reaction: two activators making beating between in water, adding, add trash ice, hydrochloric acid, sodium nitrite solution in 0-5 ℃ of reaction 2-3 hour, keep the potassium iodide starch paper blueness.
D, coupled reaction: add an amount of thionamic acid to above-mentioned from the product of C step, remove excessive nitrite sodium, join then and stir among the B after 10 minutes, it is standby to transfer pH=6-7 to stir after 1-2 hour with yellow soda ash.
E, saltout: in above-mentioned D, add the press filtration after 2 hours of 4%-5% sodium-chlor.
The shortcoming of above-mentioned steps is to produce a large amount of red waste water, and the COD value of waste water is higher a lot.
F, drying: will add the dust-proofing agent making beating among the above-mentioned E, pH=6-7, big tower temperature out is controlled at 100-110 ℃ and carries out drying.
Aforesaid method is original production method, wherein has a large amount of problems, kind, the quality of producing be can not get 100% hold, and the waste water that produces in the whole process is very big, and environment is caused very big harm.
The present invention has carried out process modification to this method, and employing membrane technology, improve transformation efficiency by adding phase-transfer catalyst, control key link by middle control method, improve the stability of product, intensity by membrane technique raising product has reduced the waste liquid generation by above several method.
Summary of the invention
For solving the problems of the technologies described above, the invention provides a kind of mao of improvement preparation method with reactive red 3G dyestuff, this preparation method comprises the steps:
(a) two activators preparations and diazotization between: (1) adds 2 in water, the dissolving of 4-diamino benzene sulfonic acid sodium, add trolamine and EDTA fully stir mixing solutions; (2) adding trash ice in this mixing solutions makes temperature reach 0-5 ℃.In 1.5-3 hour, add 2, the mixed solution of 3-two bromo propionyl chloros and acetone, and control pH=6.0-6.5 with 15% sodium carbonate solution and react; (3) reaction is finished the back and is added hydrochloric acid, and 20-30 ℃ sodium nitrite solution, and controlled temperature is in 8-18 ℃ of reaction 2-4 hour, during the maintenance Sodium Nitrite little excessive, obtain diazonium liquid;
(b) condensation reaction: (1) adds γ acid in water, transfer pH=7 with yellow soda ash, gets solution for standby; (2) in this solution, add trash ice and cool to 8-12 ℃, in 2-3 hour, add 2,3-two bromo propionyl chloros and acetone mixed solution, pH is 4.5-6.5 reaction 1-2 hour with the yellow soda ash regulation and control, obtains condensation reaction solution.
(c) coupled reaction: in the product diazonium liquid of above-mentioned (a) reaction, add an amount of thionamic acid and remove excessive nitrite sodium, then this solution is joined in 18-30 ℃, 1-2 hour in the condensation reaction solution that (b) step obtains, transferring pH with 15% sodium carbonate solution during this time is 5.5-7, stir sampling in per 10 minutes, survey terminal point, OV method and liquid phase method are synchronous in the measurement, and products therefrom is reactive red 3G behind the reaction end.
Preferably, method of the present invention can also comprise following purification step:
(d) press filtration: after terminal point is qualified, with filter filter, mother liquor collects in another retort, filter cake is packed into standby in the bag;
(e) film is saturating: collect mother liquor in the retort, cross film, film and see through in the journey the saturating temperature of controlling diaphragm below 30 ℃, cross behind the film in bag the filter cake dispersion of pulling an oar;
(f) drying: behind the product adding dust-proofing agent with (e) step, control pH=6.5, temperature are carried out the spray tower drying for 105 ℃.
In the aforesaid method, (a) temperature of reaction in (2) is preferably 5 ℃ in the step, and the time is preferably 1.5 hours, and the pH value is preferably 6.0-6.3, and (a) reaction times in (3) is preferably 3 hours in the step.
In the aforesaid method, (b) pH in (2) in the step is preferably 5.0-6.0, and the reaction times is preferably 2 hours.
In the aforesaid method, (c) reaction pH value is preferably 6 in the step, and temperature is preferably 20 ℃ ± 1 ℃.
In the aforesaid method, (f) amount of dust-proofing agent is preferably 1% of product weight in the step.
The beneficial effect of aforesaid method is as follows:
(a) beneficial effect of step is for adding phase-transfer catalyst trolamine, acetone, makes its transformation efficiency bring up to 99.5% by former 98%.And add EDTA and make metal ion in its water obtain covering to keep away, make its finished product coloured light more bright-coloured, and the no waste water generation of two an activators preparation.
(b) condensation reaction of step also is to add by phase-transfer catalyst acetone to bring up to 98.5% transformation efficiency by original 96% transformation efficiency.
(c) step reaction passes through to temperature control and has improved diazotization reaction effect transformation efficiency and also increase.
(c) step is the terminal point controlled step, in order to make terminal point equal theoretical value better, terminal point must reach consistent with liquid chromatography by UV, just can be that terminal point is qualified.
(e) in the step, the mother liquor in the holding tank is improved mother liquor intensity by the saturating technology desalination of film, mother liquor intensity by film by original 80%-85%, intensity is brought up to 100%-110%, reduce the step saltout like this, the cost that economizes in raw materials, and avoided the generation of colorful wastewater.
Embodiment
For specifying technical scheme of the present invention, enumerate embodiment below and describe technical scheme of the present invention in detail, this embodiment does not form any limitation of the invention.
Embodiment
The concrete preparation process of reactive red 3G dyestuff of the present invention is as follows:
(a) two activators and diazotization reaction between: in 20 tons of retort, add and add 2 of 254Kg under 3.5 tons of stirrings of end water, 4-diamino benzene sulfonic acid sodium, make it molten entirely, add the trolamine of 33Kg and the EDTA of 60Kg, abundant stirring and dissolving, complete molten back adds trash ice, controlled temperature 0-5 ℃ added 2 of 280Kg with 1.5 hours, 3-two bromo propionyl chloros and acetone 30Kg mixed solution, and control pH=6.0-6.3 with 15% sodium carbonate solution, after reaction is finished, the hydrochloric acid that adds 112.3Kg, and 25 ℃ sodium nitrite solution, controlled temperature was in 14 ℃ of reactions 3 hours, keep Sodium Nitrite little excessive during this time, obtain diazonium liquid.
(b) condensation reaction: in 20 tons of retort, add 3.5 tons in end water, stir the γ acid that adds 240.3Kg down, transfer pH=7.0 with 15% sodium carbonate solution, complete molten back adds trash ice and cools to 12 ℃, in 3 hours, at the uniform velocity add 2 of 260Kg, the mixed solution of 3-two bromo propionyl chloros and 25Kg acetone, during with 15% sodium carbonate solution control pH=5.0-6.0, finish afterreaction 2 hours, and got condensation reaction solution.
(c) coupled reaction: the Sodium Nitrite in above-mentioned (a) is removed with an amount of thionamic acid, then in 1 hour, simultaneously 20 ℃ ± 1 ℃ of controlled temperature joins it in (b), with 15% yellow soda ash control pH=6, after finishing, stir sampling in per 10 minutes, survey terminal point, OV method and liquid phase method are synchronous in the measurement.
(d) press filtration: after terminal point was qualified, filter, mother liquor were collected in another 20 tons of retort, and filter cake is packed into standby in the bag.
(e) film is saturating: mother liquor is 15 tons in the holding tank, crosses film, film and sees through in the journey the saturating temperature of controlling diaphragm below 30 ℃, crosses behind the film in bag the filter cake dispersion of pulling an oar.
(f) drying: after above-mentioned product being added the dust-proofing agent of product 1% weight, control pH=6.5, temperature are carried out the spray tower drying for 105 ℃.
Present embodiment aspect waste water, output, cost with the correlated beneficial effect of old technology as follows:
| Project | Old technology | Novel process |
| Waste water | 25 tons | 0 ton |
| Output | 1 ton | 1.2 ton |
| Cost | Reduce by 10% |
The method of present embodiment obviously has improvement than the old technology described in the background technology in many-side, at first the waste water generation produces 25 tons of waste water by the finished product of 1 ton of original every generation, then productive rate has improved 20% now, and wastewater flow rate but has been reduced to 0 ton, technology to diverted via effect very obvious.
Dyestuff of the present invention and dyestuff preparation method are 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 (6)
1, a kind of preparation method of reactive red 3G dyestuff is characterized in that this preparation method comprises the steps:
(a) two activators preparations and diazotization between: (1) adds 2 in water, the dissolving of 4-diamino benzene sulfonic acid sodium, add trolamine and EDTA fully stir mixing solutions; (2) adding trash ice in this mixing solutions makes temperature reach 0-5 ℃.In 1.5-3 hour, add 2, the mixed solution of 3-two bromo propionyl chloros and acetone, and control pH=6.0-6.5 with 15% sodium carbonate solution and react; (3) reaction is finished the back and is added hydrochloric acid, and 20-30 ℃ sodium nitrite solution, and controlled temperature is in 8-18 ℃ of reaction 2-4 hour, during the maintenance Sodium Nitrite little excessive, obtain diazonium liquid;
(b) condensation reaction: (1) adds γ acid in water, transfer pH=7 with yellow soda ash, gets solution for standby; (2) in this solution, add trash ice and cool to 8-12 ℃, in 2-3 hour, add 2,3-two bromo propionyl chloros and acetone mixed solution, pH is 4.5-6.5 reaction 1-2 hour with the yellow soda ash regulation and control, obtains condensation reaction solution;
(c) coupled reaction: in the product diazonium liquid of above-mentioned (a) reaction, add an amount of thionamic acid and remove excessive nitrite sodium, then this solution is joined in 18-30 ℃, 1-2 hour in the condensation reaction solution that (b) step obtains, transferring pH with 15% sodium carbonate solution during this time is 5.5-7.0, stir sampling in per 10 minutes, survey terminal point, OV method and liquid phase method are synchronous in the measurement, and products therefrom is reactive red 3G behind the reaction end.
2, method according to claim 1, it comprises that also step (d) is (e) and (f):
(d) press filtration: after terminal point is qualified, with filter filter, mother liquor collects in another retort, filter cake is packed into standby in the bag;
(e) film is saturating: collect mother liquor in the retort, cross film, film and see through in the journey the saturating temperature of controlling diaphragm below 30 ℃, cross behind the film in bag the filter cake dispersion of pulling an oar;
(f) drying: behind the product adding dust-proofing agent with (e) step, control pH=6.5, temperature are carried out the spray tower drying for 105 ℃.
3, method according to claim 1 and 2, wherein the temperature of reaction in (2) is 5 ℃ in (a) step, and the time is 1.5 hours, and the pH value is 6.0-6.3, and (a) reaction times in (3) is 3 hours in the step.
4, method according to claim 1 and 2, (b) pH in (2) in the step is 5.0-6.0, the reaction times is 2 hours.
5, method according to claim 1 and 2, (c) pH value in reaction in the step is 6, temperature is 20 ℃ ± 1 ℃.
6, method according to claim 2, (f) amount of dust-proofing agent is 1% of a product weight in the step.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 200810154113 CN101585975B (en) | 2008-12-12 | 2008-12-12 | Method for preparing reactive red 3G for wool |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 200810154113 CN101585975B (en) | 2008-12-12 | 2008-12-12 | Method for preparing reactive red 3G for wool |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101585975A true CN101585975A (en) | 2009-11-25 |
| CN101585975B CN101585975B (en) | 2013-03-20 |
Family
ID=41370414
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 200810154113 Active CN101585975B (en) | 2008-12-12 | 2008-12-12 | Method for preparing reactive red 3G for wool |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN101585975B (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101481524A (en) * | 2008-12-12 | 2009-07-15 | 天津市德凯化工有限公司 | Preparation of reactive red 3G dye |
| CN105542511A (en) * | 2015-12-22 | 2016-05-04 | 浙江亿得化工有限公司 | A composite active red dye used for wool and a preparing method thereof |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| ES387743A1 (en) * | 1970-01-30 | 1974-07-01 | Ciba Geigy | Monoazo dyestuffs their manufacture and use |
-
2008
- 2008-12-12 CN CN 200810154113 patent/CN101585975B/en active Active
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101481524A (en) * | 2008-12-12 | 2009-07-15 | 天津市德凯化工有限公司 | Preparation of reactive red 3G dye |
| CN105542511A (en) * | 2015-12-22 | 2016-05-04 | 浙江亿得化工有限公司 | A composite active red dye used for wool and a preparing method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN101585975B (en) | 2013-03-20 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN105694524A (en) | Preparation method of acid black 172 | |
| CN107915644A (en) | A kind of method that p-aminophenyl ether is prepared using paranitrochlorobenzene as raw material | |
| CN111217764B (en) | Method for preparing 6-nitro-1, 2, 4-acid oxygen | |
| CN101585975B (en) | Method for preparing reactive red 3G for wool | |
| CN102295536B (en) | Preparation method of high-content trimethylhydroquinone | |
| CN102408743B (en) | Production process of direct blending navy blue D-R dye | |
| CN101481524A (en) | Preparation of reactive red 3G dye | |
| CN101585974B (en) | Method for preparing wool reactive-dye brilliant blue | |
| CN101880465B (en) | Production method for acid dye finished product | |
| CN102633669A (en) | Method for producing 2-amino-4-acetamido benzene alkyl ether by reduction with sodium bisulfide | |
| CN102070552B (en) | Method for preparing 3-amino-5-nitro-2,1-benzisothiazole and diazonium salt thereof | |
| CN101531831B (en) | Production method of direct blended brown D-RS dye | |
| CN101538805B (en) | Novel active black dye and manufacture method thereof for printing and dyeing | |
| CN101580650A (en) | Direct spray drying preparation technology of direct fast black 22 | |
| CN102433025A (en) | Black active dye and preparation method thereof | |
| CN105566949B (en) | A kind of environment-friendly preparation method of sulfur dye solution | |
| CN101481522B (en) | Preparation of red reactive dye for fur | |
| CN104877368A (en) | Chrysophenine G production process | |
| CN100424136C (en) | Method for preparing active red DF-3BS | |
| CN102321387A (en) | Nylon reactive yellow dye and preparation method thereof | |
| CN101580644A (en) | Pollution-free preparation technology of direct fast yellow D-RL | |
| CN203269846U (en) | Device for continuously producing dyes | |
| CN101481531B (en) | Preparation method of reactive dye KN-R | |
| CN106590014A (en) | Direct red-12B dye preparation process | |
| CN101580651A (en) | Pollution-free preparation technology of direct rose FR |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| PE01 | Entry into force of the registration of the contract for pledge of patent right |
Denomination of invention: Method for preparing reactive red 3G for wool Effective date of registration: 20140710 Granted publication date: 20130320 Pledgee: Bank of Dalian Co. Tianjin branch Pledgor: Tianjin Dek Chemical Co.,Ltd. Registration number: 2014990000566 |
|
| PLDC | Enforcement, change and cancellation of contracts on pledge of patent right or utility model | ||
| PC01 | Cancellation of the registration of the contract for pledge of patent right |
Date of cancellation: 20150707 Granted publication date: 20130320 Pledgee: Bank of Dalian Co. Tianjin branch Pledgor: Tianjin Dek Chemical Co.,Ltd. Registration number: 2014990000566 |
|
| PLDC | Enforcement, change and cancellation of contracts on pledge of patent right or utility model | ||
| PE01 | Entry into force of the registration of the contract for pledge of patent right |
Denomination of invention: Method for preparing reactive red 3G for wool Effective date of registration: 20150713 Granted publication date: 20130320 Pledgee: Bank of Dalian Co. Tianjin branch Pledgor: Tianjin Dek Chemical Co.,Ltd. Registration number: 2015990000556 |
|
| PLDC | Enforcement, change and cancellation of contracts on pledge of patent right or utility model | ||
| PC01 | Cancellation of the registration of the contract for pledge of patent right |
Date of cancellation: 20160719 Granted publication date: 20130320 Pledgee: Bank of Dalian Co. Tianjin branch Pledgor: Tianjin Dek Chemical Co.,Ltd. Registration number: 2015990000556 |
|
| PLDC | Enforcement, change and cancellation of contracts on pledge of patent right or utility model | ||
| PE01 | Entry into force of the registration of the contract for pledge of patent right |
Denomination of invention: Method for preparing reactive red 3G for wool Effective date of registration: 20160719 Granted publication date: 20130320 Pledgee: Bank of Dalian Co. Tianjin branch Pledgor: Tianjin Dek Chemical Co.,Ltd. Registration number: 2016990000612 |
|
| PLDC | Enforcement, change and cancellation of contracts on pledge of patent right or utility model | ||
| PC01 | Cancellation of the registration of the contract for pledge of patent right | ||
| PC01 | Cancellation of the registration of the contract for pledge of patent right |
Date of cancellation: 20170721 Granted publication date: 20130320 Pledgee: Bank of Dalian Co. Tianjin branch Pledgor: Tianjin Dek Chemical Co.,Ltd. Registration number: 2016990000612 |
|
| CP02 | Change in the address of a patent holder | ||
| CP02 | Change in the address of a patent holder |
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 Ji'an Road, ZhangGuiZhuang Road, Dongli District, Tianjin Patentee before: Tianjin Dek Chemical Co.,Ltd. |
|
| PP01 | Preservation of patent right | ||
| PP01 | Preservation of patent right |
Effective date of registration: 20230131 Granted publication date: 20130320 |