CN111349348B - Reactive dark blue dye and synthetic method thereof - Google Patents
Reactive dark blue dye and synthetic method thereof Download PDFInfo
- Publication number
- CN111349348B CN111349348B CN201811572704.0A CN201811572704A CN111349348B CN 111349348 B CN111349348 B CN 111349348B CN 201811572704 A CN201811572704 A CN 201811572704A CN 111349348 B CN111349348 B CN 111349348B
- Authority
- CN
- China
- Prior art keywords
- acid
- dye
- chromophore
- temperature
- mother liquor
- 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.)
- Active
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
- C09B62/00—Reactive dyes, i.e. dyes which form covalent bonds with the substrates or which polymerise with themselves
- C09B62/02—Reactive dyes, i.e. dyes which form covalent bonds with the substrates or which polymerise with themselves with the reactive group directly attached to a heterocyclic ring
- C09B62/04—Reactive dyes, i.e. dyes which form covalent bonds with the substrates or which polymerise with themselves with the reactive group directly attached to a heterocyclic ring to a triazine ring
- C09B62/08—Azo dyes
- C09B62/095—Metal complex azo dyes
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
- C09B62/00—Reactive dyes, i.e. dyes which form covalent bonds with the substrates or which polymerise with themselves
- C09B62/44—Reactive dyes, i.e. dyes which form covalent bonds with the substrates or which polymerise with themselves with the reactive group not directly attached to a heterocyclic ring
- C09B62/503—Reactive dyes, i.e. dyes which form covalent bonds with the substrates or which polymerise with themselves with the reactive group not directly attached to a heterocyclic ring the reactive group being an esterified or non-esterified hydroxyalkyl sulfonyl or mercaptoalkyl sulfonyl group, a quaternised or non-quaternised aminoalkyl sulfonyl group, a heterylmercapto alkyl sulfonyl group, a vinyl sulfonyl or a substituted vinyl sulfonyl group, or a thiophene-dioxide group
- C09B62/507—Azo dyes
- C09B62/515—Metal complex azo dyes
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Coloring (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses an active deep blue dye and a synthetic method thereof, wherein the deep blue dye has the following structural general formula:
the synthesis method comprises the following steps: coupling acetyl H acid and diazonium salt of naphthylamine sulfonic acid to obtain coupling reaction liquid, complexing and hydrolyzing the coupling reaction liquid with copper oxide to obtain dye mother liquor chromophore, and introducing active group after condensation reaction of the dye mother liquor chromophore
Description
Technical Field
The invention belongs to the technical field of dyes, and relates to an active dark blue dye and a synthetic method thereof.
Background
The synthesis of active deep blue M-R or active deep blue P-5R generally adopts H acid and cyanuric chloride to carry out primary condensation, then the H acid and cyanuric chloride are coupled with amino C acid diazonium salt, hydrogen peroxide, sodium acetate and copper sulfate aqueous solution are used for carrying out copper oxide complexation, and finally the H acid and para-ester (ammonia water) are carried out secondary condensation, potassium chloride is added for separation, and the drying and standardization are carried out to obtain the commercial dye. The process is simple and easy to synthesize. But simultaneously produces high COD and high chroma dye sewage containing a large amount of inorganic salts, has large difficulty in treating three wastes and is not beneficial to environmental protection.
Disclosure of Invention
The invention aims to provide an active deep blue dye and a clean synthesis process thereof aiming at the requirements of clean production, comprehensive utilization, cost saving and consumption reduction in the current dye industry. The commercial dye is obtained without salting-out separation or direct drying and standardization (wet blending or dry blending) in the dye synthesis process, and the method is favorable for energy conservation, emission reduction and clean production.
In order to achieve the purpose, the invention adopts the following technical scheme:
a clean synthesis method of reactive deep blue dye, wherein the acid structure of the dye has the following general formula:
wherein m is 1-3, X is Cl or F, and Y is NH2、
SO2CH2CH2SO3H、
SO2CH2CH2SO3H、NHCH2CH2SO2CH2CH2Cl or NHCH2CH2OCH2CH2SO2CH2CH2Cl。
A method for synthesizing an active deep blue dye, the method comprising the steps of:
coupling acetyl H acid and diazonium salt of naphthylamine sulfonic acid to obtain coupling reaction liquid, complexing and hydrolyzing the coupling reaction liquid with copper oxide to obtain dye mother liquor chromophore, and introducing active group after condensation reaction of the dye mother liquor chromophore
The finished dye is directly dried to prepare the active deep blue dye.
Preferably, the coupling reaction solution obtained by coupling the acetyl H acid and the diazonium salt of the naphthylamine sulfonic acid specifically comprises the following steps:
1) diazotizing naphthylamine sulfonic acid solution by using ice, hydrochloric acid and sodium nitrite solution at the controlled temperature of 0-5 ℃ to prepare diazonium salt;
2) adding acetyl H acid into the diazonium salt, keeping the pH value of about 6.5 by using a sodium carbonate solution, and keeping the temperature of 5-10 ℃ for reaction to obtain a coupling reaction solution.
Preferably, the step of complexing and hydrolyzing the coupling reaction solution with copper oxide to obtain the dye mother liquor chromophore specifically comprises the following steps:
adding cupric salt into the coupling reaction solution, adding hydrogen peroxide into the coupling reaction solution at the temperature of 30-35 ℃ for reaction to obtain a reaction solution, adding liquid alkali or flake alkali into the reaction solution, carrying out hydrolysis reaction for 1-2 hours at the temperature of 95-100 ℃, wherein the pH value is more than or equal to 12.00, and the temperature is 95-100 ℃, cooling the reaction solution to 20-25 ℃, and adjusting the pH value to 7.0-7.5 by using acid to obtain the dye mother liquor chromophore.
Further preferably, the cupric salt is copper sulfate, copper chloride or copper nitrate.
Further preferably, the acid is hydrochloric acid, sulfuric acid or glacial acetic acid.
Preferably, the naphthylamine sulfonic acid is an amino C acid, a sulfonated C acid, an amino G acid, or 2-naphthylamine-8-sulfonic acid.
Preferably, the active group is introduced after the condensation reaction of the dye mother liquor chromophore
The method specifically comprises the following steps:
carrying out primary condensation on para-ester or meta-ester and cyanuric halide, and then carrying out secondary condensation on the para-ester or meta-ester and a dye mother liquor chromophore;
or, carrying out primary condensation on the dye mother liquor chromophore and cyanuric halide, and then carrying out secondary condensation on the dye mother liquor chromophore and para-ester or meta-ester;
or, carrying out primary condensation on the dye mother liquor chromophore and cyanuric halide, and then carrying out secondary condensation on the dye mother liquor chromophore and 2,2- [ (2-chloroethyl) sulfonyl ] ethylamine hydrochloride or 2-chloroethyl sulfone ethoxy ethylamine hydrochloride;
or, will
And carrying out condensation reaction with a dye mother liquor chromophore.
Preferably, the cyanuric halide is cyanuric chloride or cyanuric fluoride.
Coupling acetyl H acid and naphthylamine sulfonic acid (amino C acid, sulfonated C acid, amino G acid and 2-naphthylamine-8-sulfonic acid) diazonium salt to obtain coupling reaction liquid, complexing copper oxide and hydrolyzing to obtain a dye mother liquor chromophore; and introducing corresponding active groups to the parent chromophore, desalting or directly drying to obtain the active deep blue dye.
Compared with the prior art, the invention has the advantages that:
the method firstly synthesizes the dark blue parent dye and then introduces the active group, so that the dye hydrolysis is less, the damage of hydrogen peroxide to the s-triazine active group is particularly avoided, the finished product does not need salting out, the yield is improved, and the yield is improved and the sewage discharge is reduced.
Detailed Description
Any feature disclosed in this specification may be replaced by alternative features serving equivalent or similar purposes, unless expressly stated otherwise. Unless expressly stated otherwise, each feature is only an example of a generic series of equivalent or similar features. The description is only for the purpose of facilitating understanding of the present invention and should not be construed as specifically limiting the present invention.
Example 1
150ml of water and 0.1 mol of amino-C acid are added into a 500ml beaker, and after pulping for 1 hour, the pH value is adjusted to 7.0-7.5 by liquid alkali to prepare about 20 percent solution. 0.101 mol of sodium nitrite is dissolved by water to prepare about 30 percent solution, and the solution is added into amino C acid and stirred evenly. 50ml of water, 100g of crushed ice and 25ml of 37% hydrochloric acid are added into a 1000ml beaker, the mixed solution of the amino C acid and the sodium nitrite is added dropwise at the temperature of 0-5 ℃ for about 0.5 hour to carry out diazotization reaction, while keeping the congo red test paper to be blue, the starch potassium iodide test paper to be micro blue, the reaction is carried out for 30min under the condition of adding the mixture, and the slightly excessive nitrous acid is balanced by sulfamic acid. V400-.
A500 ml flask was charged with about 0.1 mole of about 20% H acid solution. Controlling the temperature at 30-34 ℃, and dropwise adding 17g of industrial acetic anhydride. The reaction was completed for 2 hours and the endpoint was tested with ehrlichi reagent. And at the end point, adjusting the pH value to 7.5 by using dry powder sodium carbonate, heating to 90-95 ℃, carrying out hydrolysis reaction for 0.5-1 hour, cooling to the normal temperature by using a jacket, and adjusting the pH value to about 7 by using hydrochloric acid for later use. V200-.
After the diazotization reaction is finished, adding the acetyl H acid, then adjusting the pH to 6.5-7 by using 20% of pure alkali solution, keeping the pH, and reacting for 2-3H at the temperature of 5-10 ℃. And V is 600-.
The coupling solution is added into a 2000ml flask, 26.04g (0.1 mol) of 96 percent industrial copper sulfate is added, the temperature is raised to 30 to 35 ℃, 86.55g (0.7 mol) of 27.5 percent industrial hydrogen peroxide is added for copper oxide complexing, and the reaction is carried out for 1 hour. Adding 100g of 30-31% liquid alkali, repeatedly measuring the pH value to be more than or equal to 12.00, heating the mixture to 95-100 ℃ by a jacket, carrying out hydrolysis reaction for 2 hours, cooling the mixture to 20-25 ℃, and adjusting the pH value to 7.0-7.5 by hydrochloric acid to obtain the dye mother liquor chromophore. And V is 800-.
50ml of bottom water and 100g of crushed ice are added into a 1000ml beaker, 1.03 mol of cyanuric chloride is put into the beaker, the temperature T is less than 0 ℃, and the mixture is pulped for 40 minutes. Adding 1.03 mol of para (meta) ester, pulping for 0.5 hour, and adjusting the pH to 3.0-3.5 by using baking soda dry powder. The pH is stable, the temperature T is 10-15 ℃, the temperature V is 300-.
Adding the dye mother liquor chromophore and the first condensation solution into a 2000ml beaker, adjusting the pH value to be 6.5-7 by baking soda, heating to 45-50 ℃ for 1 hour, keeping the pH value, heating well, and reacting for 4-6 hours under the maintained condition.
Filtering, standardizing the filtrate, and spray-drying. The color light is close to domestic active deep blue M-R (deep blue SPE), and the method is suitable for printing and dyeing the cellulose fiber.
Example 2
The amino C acid in the example 1 is changed into the sulfonated C acid, and the other conditions are not changed, so that the active deep blue is suitable for printing and continuous dyeing of the cellulose fiber.
Example 3
The amino C acid in example 1 is changed into amino G acid, and the rest conditions are not changed, so that the reactive deep blue is suitable for printing and continuous dyeing of cellulose fibers.
Example 4
Changing the amino C acid in the example 1 into 2-naphthylamine-8-sulfonic acid, and synthesizing to obtain the active deep blue base under the same conditions, wherein in the example 1, the condensation reaction is adjusted as follows: 50ml of bottom water and 100g of crushed ice are added into a 1000ml beaker, 1.05 mol of industrial cyanuric chloride is put into the beaker, the temperature T is less than 0 ℃, and the mixture is pulped for 40 minutes. Adding the deep blue base, adjusting the pH to 6.5-7 with baking soda dry powder, stabilizing the pH, reacting for 3-4 hours at the temperature of 5-10 ℃, adding 1.1 mol of N-ethyl para (meta) ester, adjusting the pH to 4.0 with baking soda dry powder, maintaining the pH for reaction for 1 hour, heating to 45-50 ℃, maintaining the temperature and the pH for reaction for 10 hours, adjusting the pH to 6.0-6.5, and maintaining the reaction for 1 hour. Filtering, standardizing the filtrate, and spray-drying. The obtained active deep blue is suitable for dip dyeing and continuous dyeing of cellulose fibers.
Example 5
Changing the amino C acid in the example 1 into 2-naphthylamine-8-sulfonic acid, and synthesizing to obtain the active deep blue base under the same conditions, wherein in the example 1, the condensation reaction is adjusted as follows: adding the active deep blue base neutral solution into a 1000ml beaker, adding crushed ice, cooling to-2-0 ℃, dropwise adding 1.05 mol of industrial melamine into the beaker, keeping the pH value at-2-0 ℃ by using liquid alkali at the same time of keeping the pH value at 7-7.5, and finishing the reaction for 30 minutes. Dropwise adding 1.1 mol of 2,2- [ (2-chloroethyl) sulfonyl ] ethylamine hydrochloride, stirring and maintaining for 30 minutes, slowly heating to the temperature of between 20 and 25 ℃, simultaneously adjusting the pH to between 8.0 and 8.5 by using liquid alkali, and reacting for 4 hours at the temperature and the pH. Filtering, performing standard membrane treatment on the filtrate for desalting, and spray-drying after standardization. The obtained active deep blue is suitable for dip dyeing and continuous dyeing of cellulose fibers.
Example 6
The reactive deep blue is suitable for printing and continuous dyeing of cellulose fibers by changing 1 mole of amino C acid in example 1 to 0.5 mole of sulfonated C acid and 0.5 mole of amino C acid mixture and keeping the rest conditions unchanged.
Example 7
In the embodiment 5, the secondary condensation 2,2- [ (2-chloroethyl) sulfonyl ] ethylamine hydrochloride is changed into 2-chloroethyl sulfone ethoxy ethylamine hydrochloride, and the rest conditions are not changed, so that the active deep blue is suitable for dip dyeing and continuous dyeing of the cellulose fiber.
Example 8
In example 1, the secondary condensate of para-ester and cyanuric chloride is changed to be added with 1.05 mol or less of primary product
The other conditions are unchanged, and the obtained active deep blue is suitable for printing the cellulose fiber.
The method can be realized by upper and lower limit values and interval values of intervals of process parameters (such as temperature, time and the like), and embodiments are not listed.
Conventional technical knowledge in the art can be used for the details which are not described in the present invention.
Finally, it should be noted that the above embodiments are only used for illustrating the technical solutions of the present invention and are not limited. Although the present invention has been described in detail with reference to the embodiments, it will be understood by those skilled in the art that various changes may be made and equivalents may be substituted without departing from the spirit and scope of the invention as defined in the appended claims.
Claims (5)
1. A method for synthesizing active dark blue dye is characterized in that the dark blue dye has the following structural general formula:
wherein m is 1-3, X is Cl or F, and Y is NHCH2CH2SO2CH2CH2Cl or NHCH2CH2OCH2CH2SO2CH2CH2Cl；
The synthesis method comprises the following steps:
1) diazotizing naphthylamine sulfonic acid solution by using ice, hydrochloric acid and sodium nitrite solution at the controlled temperature of 0-5 ℃ to prepare diazonium salt;
2) adding acetyl H acid into the diazonium salt, keeping the pH value of the diazonium salt at 6.5 by using a sodium carbonate solution, and keeping the temperature at 5-10 ℃ for reaction to obtain a coupling reaction solution;
3) adding cupric salt into the coupling reaction solution, adding hydrogen peroxide for reaction at the temperature of 30-35 ℃ to obtain reaction solution, adding liquid alkali or flake alkali into the reaction solution, carrying out hydrolysis reaction for 1-2 hours at the temperature of 95-100 ℃ and the pH value of more than or equal to 12.00 and at the temperature of 95-100 ℃, cooling to 20-25 ℃, and adjusting the pH value to 7.0-7.5 by using acid to obtain a dye mother liquor chromophore;
4) carrying out primary condensation on a dye mother liquor chromophore and cyanuric halide, carrying out secondary condensation on the dye mother liquor chromophore and 2,2- [ (2-chloroethyl) sulfonyl ] ethylamine hydrochloride or 2-chloroethyl sulfone ethoxy ethylamine hydrochloride, and directly drying a finished dye to obtain the active deep blue dye.
2. The method of claim 1, wherein the cupric salt is copper sulfate, copper chloride or copper nitrate.
3. The method of synthesis of claim 1, wherein the acid is hydrochloric acid, sulfuric acid or glacial acetic acid.
4. The method of synthesis of claim 1, wherein the naphthylamine sulfonic acid is an amino C acid, a sulfonated C acid, an amino G acid, or 2-naphthylamine-8-sulfonic acid.
5. The method of synthesis according to claim 1, characterized in that the cyanuric halide is cyanuric chloride or cyanuric fluoride.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811572704.0A CN111349348B (en) | 2018-12-21 | 2018-12-21 | Reactive dark blue dye and synthetic method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811572704.0A CN111349348B (en) | 2018-12-21 | 2018-12-21 | Reactive dark blue dye and synthetic method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN111349348A CN111349348A (en) | 2020-06-30 |
| CN111349348B true CN111349348B (en) | 2021-11-23 |
Family
ID=71190148
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201811572704.0A Active CN111349348B (en) | 2018-12-21 | 2018-12-21 | Reactive dark blue dye and synthetic method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN111349348B (en) |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103709784A (en) * | 2013-12-09 | 2014-04-09 | 浙江劲光化工有限公司 | Blue reactive dye for printing, and preparation methods thereof |
| CN104164097A (en) * | 2014-07-29 | 2014-11-26 | 浙江瑞华化工有限公司 | Active deep blue dye composition and high-solubility active deep blue dye, and preparation method and applications of high-solubility active deep blue dye |
| CN106752076A (en) * | 2016-11-28 | 2017-05-31 | 浙江瑞华化工有限公司 | A kind of blue active dye composition and its production and use |
| CN106833017A (en) * | 2016-11-28 | 2017-06-13 | 浙江瑞华化工有限公司 | A kind of blue active dye composition and its production and use |
| CN107828240A (en) * | 2017-11-22 | 2018-03-23 | 浙江劲光实业股份有限公司 | A kind of preparation method and application of dark blue reactive dye mill base |
| CN108467607A (en) * | 2018-04-11 | 2018-08-31 | 江苏安诺其化工有限公司 | A kind of dye composite, preparation method and application |
| CN108640883A (en) * | 2018-04-11 | 2018-10-12 | 江苏安诺其化工有限公司 | A kind of azo compound, preparation method and application |
-
2018
- 2018-12-21 CN CN201811572704.0A patent/CN111349348B/en active Active
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103709784A (en) * | 2013-12-09 | 2014-04-09 | 浙江劲光化工有限公司 | Blue reactive dye for printing, and preparation methods thereof |
| CN104164097A (en) * | 2014-07-29 | 2014-11-26 | 浙江瑞华化工有限公司 | Active deep blue dye composition and high-solubility active deep blue dye, and preparation method and applications of high-solubility active deep blue dye |
| CN106752076A (en) * | 2016-11-28 | 2017-05-31 | 浙江瑞华化工有限公司 | A kind of blue active dye composition and its production and use |
| CN106833017A (en) * | 2016-11-28 | 2017-06-13 | 浙江瑞华化工有限公司 | A kind of blue active dye composition and its production and use |
| CN107828240A (en) * | 2017-11-22 | 2018-03-23 | 浙江劲光实业股份有限公司 | A kind of preparation method and application of dark blue reactive dye mill base |
| CN108467607A (en) * | 2018-04-11 | 2018-08-31 | 江苏安诺其化工有限公司 | A kind of dye composite, preparation method and application |
| CN108640883A (en) * | 2018-04-11 | 2018-10-12 | 江苏安诺其化工有限公司 | A kind of azo compound, preparation method and application |
Non-Patent Citations (1)
| Title |
|---|
| Copper based metal complex reactive azo dyes;NJ Mali, et al;《Journal of the Institution of Chemists (India)》;20011231;第73卷(第4期);152-153 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN111349348A (en) | 2020-06-30 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US4257770A (en) | Disazo dye composition | |
| CN106833012B (en) | A kind of Yellow reactive dyes and its preparation and application | |
| KR100327053B1 (en) | Reactive azo dyes containing a coupling component derived from aminophthalene series | |
| CN116144195B (en) | High-performance alkali-resistant yellow reactive dye and preparation method thereof | |
| CN104277493B (en) | Have high washing fastness and fastness to rubbing reactivity orchil and preparation method concurrently | |
| CN110938039A (en) | Purple reactive dye based on trisazo multichromosome and preparation and application thereof | |
| CN111349348B (en) | Reactive dark blue dye and synthetic method thereof | |
| US3621008A (en) | Direct disazo and tetraazo urea dyes and method of preparation | |
| CN111100478B (en) | Preparation method and application of blue dye with three active groups | |
| CN104672949B (en) | A kind of novel chemically-reactive blue dyes and preparation method thereof | |
| CN109233332B (en) | Reactive orange dye for ink-jet printing and preparation method and application thereof | |
| CN110066527B (en) | Red reactive dye and preparation method thereof | |
| CN105038312B (en) | A kind of red reactive dyes compound and its preparation and application | |
| CN101705019A (en) | Red reactive dye for wool and preparation method thereof | |
| CN112322069A (en) | Monoazo yellow acid dye and preparation method thereof | |
| CN102942803A (en) | Yellow-light red reactive dye and preparation method thereof | |
| CN110041729B (en) | Orange-red reactive dye and preparation method thereof | |
| KR100270402B1 (en) | Reactive orange dyes containing vinyl sulfones | |
| CN110511594B (en) | Reactive yellow dye for ink-jet printing and preparation method and application thereof | |
| US3471469A (en) | Water-soluble monoazo-pyrazolone dyestuffs | |
| JP3567137B2 (en) | Black reactive dye having acetoxyethyl sulfone group | |
| CN101735655B (en) | Red reactive dye for wool and preparation method thereof | |
| JPH06104778B2 (en) | Metal formazan compound and method for dyeing or printing fiber material using the same | |
| CN101735652B (en) | Red reactive dye and preparation method thereof | |
| CN106634038A (en) | Active dark blue dyestuff and preparation method of active dark blue dyestuff |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| CB03 | Change of inventor or designer information |
Inventor after: Liu Zixuan Inventor after: Liu Xing Inventor after: Sha Zhenzhong Inventor after: Liu Zhenguo Inventor after: Zhu Chao Inventor after: Shen Weihua Inventor after: Zeng Lingxin Inventor after: Li Meirong Inventor before: Sha Zhenzhong Inventor before: Liu Zhenguo Inventor before: Zhu Chao Inventor before: Shen Weihua Inventor before: Zeng Lingxin Inventor before: Li Meirong |
|
| CB03 | Change of inventor or designer information | ||
| PE01 | Entry into force of the registration of the contract for pledge of patent right |
Denomination of invention: A reactive deep blue dye and its synthesis method Granted publication date: 20211123 Pledgee: China Postal Savings Bank Co.,Ltd. Songzi Branch Pledgor: HUBEI COLOR ROOT TECHNOLOGY Co.,Ltd. Registration number: Y2024980041847 |
|
| PE01 | Entry into force of the registration of the contract for pledge of patent right |