Reactive dyes and preparation methods thereof

Patent metadata

Field	Value
Publication number	US-12091552-B2
Application number	US-202318366655-A
Country	US
Kind code	B2
Filing date	Aug 7, 2023
Priority date	Aug 11, 2022
Publication date	Sep 17, 2024
Grant date	Sep 17, 2024

Abstract

Disclosed are reactive dyes and preparation methods thereof. The reactive dye may be prepared using heterocyclic primary amine as a diazo component, 4,4′-diamino-2,2′-stilbenedisulfonic acid, s-triazine, or ethylenediamine as a bridging group, and a dimonochlortriazine group as an active group. The color-changing compound is covalently bonded into the fiber chemical structure by nucleophilic substitution reaction between monochlorotriazine and the hydroxyl group in a textile structure, and the size of the conjugated system and the range of electron delocalization of the dye are changed by a reversible isomerization reaction of the hydroxyl group adjacent to the diazo group and the diazo group under different pH regulations. Moreover, the dye has a double color changing structure, which improves the capability of the dye combined with —H/—OH. The pH value range that can cause color changes in the dye is effectively expanded to include weak alkali, weak acid or even neutral conditions.

First claim

What is claimed is:

1. A pH-sensitive color-changing reactive dye having a double-luminescent structure, represented by formula:

2. A preparation method of the pH-sensitive color-changing reactive dye having a double-luminescent structure of claim 1 , comprising:
(i) primary condensation reaction
adding cyanuric chloride and sodium butylnaphthalene sulfonate into ice-water mixture and pulping at 0° C.-5° C. to obtain a cyanuric chloride solution;
adding a parent compound of the reactive dye into water and adjusting pH to 6.0-6.5 to obtain a parent compound solution of the dye compound;
mixing the parent compound solution with the cyanuric chloride solution, adjusting and maintaining pH to 3.0-3.5 with a sodium carbonate solution, continuously reacting at 0° C.-5° C., and detecting a reaction end point by adopting an amino reagent to obtain a primary condensation solution, wherein the parent compound of the reactive dye is 1-amino-8-hydroxy-3,6-naphthalenedisulfonic acid; and
regulating pH of the primary condensation solution to 1.5 with acetic acid, then adding potassium chloride to precipitate solid powder, dispersing the precipitated solid powder in absolute ethanol, filtering, and freeze-drying to obtain a primary condensation product;
(ii) secondary condensation reaction
dissolving the primary condensation product in water to obtain an aqueous solution of the primary condensation product;
mixing the aqueous solution of the primary condensation product with ethylenediamine, wherein the pH of the ethylenediamine is 9, increasing temperature to 30° C.-35° C., regulating and maintaining pH to 4.5-5.0 with the sodium carbonate solution, continuing the reaction at 30° C.-35° C., and detecting a reaction end point by adopting the amino reagent to obtain a secondary condensation solution;
regulating pH of the secondary condensation solution to 2.0 with acetic acid, and then adding potassium chloride to precipitate solid powder; and
dispersing the precipitated solid powder in absolute ethanol, filtering, and freeze-drying to obtain a secondary condensation product;
(iii) diazotization-coupling reaction
dissolving a heterocyclic primary arylamine derivative in acid, adding a diazotization reagent to react at 0° C.-5° C. for 3 h-4 h, and after the reaction is finished, eliminating excess nitrous acid to obtain a heterocyclic primary arylamine diazonium salt;
dissolving the secondary condensation product in water, reducing the temperature of the solution to 10° C.-15ºC, slowly adding the heterocyclic primary arylamine diazo salt to react for 1 h-3 h, adjusting pH to 6, and detecting a reaction end point by adopting 1-amino-8-hydroxy-3,6-naphthalenedisulfonic acid; and
after the reaction is finished, obtaining the reactive dye after salting out, suction filtration, washing with ethanol and drying.

3. The preparation method of claim 2 , wherein the heterocyclic primary arylamine derivative in (iii) is formula 1 or 2:

4. The preparation method of claim 2 , wherein a molar ratio of the secondary condensation solution to the heterocyclic primary arylamine diazo salt in is 1:2.

5. The preparation method of claim 2 , wherein a mass ratio of the cyanuric chloride, the sodium butylnaphthalene sulfonate and the ice-water mixture in (i) is (3.5-4.0):(0.1-0.3):15.

6. A sweat detection sensor employing the pH-sensitive color-changing reactive dye having a double-luminescent structure of claim 1 .

7. The preparation method of claim 2 , wherein a molar ratio of the aqueous solution of the primary condensation product to the ethylenediamine in (ii) is 2:1.

Assignees

• Univ Nantong

Inventors

• Li Min
• Ma Wujun
• Zhou Jialiang
• Qu Wenlin
• Ding Ting
• Mao Lifen
• Li Shiyu

Classifications

• C09B33/048

  the coupling component being a bis-naphthol · CPC title

• D06P1/06

  containing acid groups · CPC title

• G01N33/52

  Use of compounds or compositions for colorimetric, spectrophotometric or fluorometric investigation, e.g. use of reagent paper {and including single- and multilayer analytical elements (immunological elements G01N33/54386; involving labelled immunochemicals G01N33/58; for haemoglobin or occult blood G01N33/72)} · CPC title

• C09B62/453

  Disazo or polyazo dyes · CPC title

• D06P1/382

  reactive group directly attached to heterocyclic group · CPC title