CN115368753B - PH color-changing reactive dye for sweat detection and preparation method thereof - Google Patents
PH color-changing reactive dye for sweat detection and preparation method thereof Download PDFInfo
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- 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
- C09B62/09—Disazo or polyazo dyes
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
- D06P1/00—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed
- D06P1/38—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed using reactive dyes
- D06P1/382—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed using reactive dyes reactive group directly attached to heterocyclic group
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
- D06P3/00—Special processes of dyeing or printing textiles, or dyeing leather, furs, or solid macromolecular substances in any form, classified according to the material treated
- D06P3/58—Material containing hydroxyl groups
- D06P3/60—Natural or regenerated cellulose
- D06P3/66—Natural or regenerated cellulose using reactive dyes
- D06P3/663—Natural or regenerated cellulose using reactive dyes reactive group directly attached to heterocyclic group
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
- D06P3/00—Special processes of dyeing or printing textiles, or dyeing leather, furs, or solid macromolecular substances in any form, classified according to the material treated
- D06P3/58—Material containing hydroxyl groups
- D06P3/60—Natural or regenerated cellulose
- D06P3/68—Preparing azo dyes on the material
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- G01N21/75—Systems in which material is subjected to a chemical reaction, the progress or the result of the reaction being investigated
- G01N21/77—Systems in which material is subjected to a chemical reaction, the progress or the result of the reaction being investigated by observing the effect on a chemical indicator
- G01N21/78—Systems in which material is subjected to a chemical reaction, the progress or the result of the reaction being investigated by observing the effect on a chemical indicator producing a change of colour
- G01N21/80—Indicating pH value
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Abstract
The invention discloses a pH color-changing reactive dye for sweat detection and a preparation method thereof, belonging to the technical field of fine chemical engineering. The invention prepares the pH color-changing reactive dye for sweat detection by taking heterocyclic primary amine as a diazo component, taking a compound containing s-triazinyl as an active group as a coupling component and taking the s-triazinyl as a bridging group. The pH color-changing reactive dye for sweat detection can change the maximum absorption wavelength of a solution by 51nm within 0.70-0.80 pH units; and the pH value at the isoelectric point of the color change (the absorbance value of the solution before and after the color change) is 6.00 to 7.00; solves the problem that the color changing point of the prior pH color changing reactive dye needs to be in a strong acid or strong alkaline condition. The color fixation rate of the printed cotton fabric obtained by using the pH color-changing reactive dye to dye the cotton fabric reaches more than 50%, and the washing, friction and light fastness can reach more than 3-4 levels; can be applied to human sweat detection (pH=4.2-8.3).
Description
Technical Field
The invention relates to a pH color-changing reactive dye for sweat detection and a preparation method thereof, belonging to the technical field of fine chemical engineering.
Background
The color-changing textile can sense environmental changes such as light, temperature, pH and pressure, reflect visual signals and play a role in warning. In addition, the color-changing textile has the characteristics of excellent flexibility, mechanical strength, washability and the like, and has good application prospects in the aspects of wearable devices, flexible sensors and the like. At present, researches on color-changing textiles mainly focus on thermochromic and photochromic, but acid-base color change is not neglected, and the color-changing textile can be applied to monitoring of pH values in a plurality of fields and has the advantages of light weight, large coverage area, air permeability, washability, high strength and the like.
Researchers have shown great interest in textiles dyed with natural dyes, and imparting novel functions to fabrics while dyed with natural dyes has also received increasing attention from researchers. The fabric with the acid-base indication function (the color of the fabric changes obviously and reversibly along with the change of the pH value of the environment) can replace a sensor measuring method and a colorimetry to judge the acidity and the alkalinity of a solution, and can be made into medical gauze and bandages so as to be convenient for observing the wound healing or infection condition. The natural dye is easy to oxidize under the irradiation of external sunlight, and the color-changing textile with pH is poor in light fastness in the taking process by adopting the natural dye for dyeing; in addition, the dye and the fiber are combined only by weak Van der Waals force or hydrogen bond, so that the dye falls off and has poor color-changing circularity under the action of external repeated friction and acid and alkali, and the application range of the dye is greatly limited.
Some researchers have also tuned the structure of the synthetic dye to achieve good pH response. For example: zhang et al (Sensors and Actuators B: chemical,2019,286: 362-369.) prepared pH-staining reactive dyes by condensing anthraquinone dyes with coupling components containing monochlorotriazine and vinyl sulfone sulfate double reactive groups; the dye can generate covalent bonding reaction with cellulose fiber, but due to the structural design of a matrix, the color change point of the dye is in a strong acid or strong alkaline condition, and is extremely limited when being applied to the aspects of pH value approaching neutrality (pH value range of human sweat is 4.2-8.3) such as human health detection and the like, so that the application range of the dye is limited.
Therefore, there is an urgent market demand for preparing a pH-discoloration reactive dye which can be discolored under weak base, weak acid or even neutral conditions.
Disclosure of Invention
[ technical problem ]
At present, dye-uptake of dyes in existing pH color-changing textiles is low, and the color can be changed only under strong acid or strong alkaline conditions, so that the dye-uptake cannot be used for detecting sweat (pH is close to neutral).
Technical scheme
In order to solve the problems, the invention prepares the pH color-changing reactive dye for sweat detection by taking heterocyclic primary amine as a diazo component, taking a compound containing s-triazinyl as an active group as a coupling component and taking the s-triazinyl as a bridging group. The invention uses nucleophilic substitution reaction between the sym-triazine and the hydroxyl in the textile structure, so as to covalently bond the pH color-changing matrix into the fiber chemical structure, and uses reversible isomerization reaction of hydroxyl and diazo at adjacent positions of the diazo under different pH adjustment, thereby changing the conjugated system size and the electronic delocalization range of the dye, and realizing reversible change of the color light of the dye. In addition, the dye has a double-chromophore structure, improves the combination probability of the dye and-H/-OH, effectively adjusts the color-changing pH value of the dye to weak base, weak acid or even neutral conditions, and can be used for detecting sweat.
The first object of the invention is to provide a pH color-changing reactive dye for sweat detection, which has a structural formula as shown in formula I:
wherein X and Y in formula I are each independently of the other formula 1, R 1 、R 2 And R is 3 Is independently-H, -NO 2 、-OCH 3 And halogen;
or, in the formula I, X and Y are respectively and independently formula 2, R 1 And R is 2 Is independently-H, -NO 2 ；
Or, X and Y in formula I are each independently of the other formula 3, R 1 And R is 2 Is independently-H, -NO 2 ；
Or, X and Y in formula I are each independently of the other formula 4, R 1 And R is 2 Is independently-H, -NO 2 ；
Or, X and Y in formula I are each independently of the other formula 5, R 1 And R is 2 Is independently-H, -NO 2 -CN and halogen;
a second object of the present invention is to provide a method for preparing a pH-changing reactive dye for sweat detection, comprising the steps of:
(1) One-time condensation reaction
Adding cyanuric chloride and nekal into the ice-water mixture, and fully pulping at 0-5 ℃ to obtain cyanuric chloride solution; adding 2-amino-5-naphthol-7-sulfonic acid into water, regulating the pH to 6.0-6.5, and fully dissolving to obtain 2-amino-5-naphthol-7-sulfonic acid solution; then mixing 2-amino-5-naphthol-7-sulfonic acid solution and cyanuric chloride solution, regulating the pH value to 3.0-3.5, continuously reacting at 0-5 ℃, and adopting sodium carbonate solution to maintain the pH value of the reaction solution to 3.0-3.5; detecting the reaction end point by adopting an amino reagent to obtain a primary condensation liquid; adjusting the pH value of the primary condensation liquid to 1.5 by adopting acetic acid, and adding potassium chloride to separate out solid powder; dispersing the precipitated solid powder in absolute ethyl alcohol, filtering, freeze-drying to obtain a primary condensation product;
(2) Secondary condensation reaction
Dissolving the primary condensation product in water to obtain a primary condensation solution; adding 1-amino-8-hydroxy-3, 6-naphthalene disulfonic acid into water, and adjusting the pH to 6.0-6.5 to obtain 1-amino-8-hydroxy-3, 6-naphthalene disulfonic acid sodium solution; then adding 1-amino-8-hydroxy-3, 6-naphthalene disulfonic acid solution into the primary condensation solution, raising the temperature to 30-35 ℃, adjusting the pH value to 4.5-5.0, continuously reacting at 30-35 ℃, and adopting sodium carbonate solution to maintain the pH value of the reaction solution to 4.0-4.5; detecting the reaction end point by adopting an amino reagent to obtain a secondary condensation liquid; adjusting the pH value of the secondary condensation liquid to 2.0 by adopting acetic acid, and adding potassium chloride to separate out solid powder; dispersing the precipitated solid powder in absolute ethyl alcohol, filtering, freeze-drying to obtain a secondary condensation product;
(3) Diazotisation-coupling reactions
Dissolving a heterocyclic aromatic primary amine derivative in acid, adding a diazotizing reagent at the temperature of 0-5 ℃ and keeping the temperature for reaction for 3-4 hours, and eliminating excessive nitrous acid after the reaction is finished to obtain heterocyclic aromatic primary amine diazonium salt; dissolving the secondary condensation product in water, reducing the temperature of the solution to 10-15 ℃, slowly adding heterocyclic aromatic primary amine diazonium salt into the solution, continuously reacting for 1-3 hours at the temperature of 10-15 ℃, adjusting the pH value to 6, continuously reacting, and detecting the end point of the reaction by adopting H acid (1-amino-8-hydroxy-3, 6-sodium naphthalene disulfonate); after the reaction is finished, the pH color-changing reactive dye for sweat detection is obtained through salting out, suction filtration, ethanol washing and drying.
In one embodiment of the invention, the mass ratio of the cyanuric chloride, the nekal and the ice water mixture in the step (1) is (3.5-4.0): (0.1-0.3): 15.
in one embodiment of the present invention, the ratio of 2-amino-5-naphthol-7-sulfonic acid to water in step (1) is (0.20 to 0.50): 1.
in one embodiment of the present invention, the 2-amino-5-naphthol-7-sulfonic acid solution in step (1) is pH adjusted with sodium carbonate.
In one embodiment of the present invention, the molar ratio of 2-amino-5-naphthol-7-sulfonic acid to cyanuric chloride in step (1) is 1:1.
in one embodiment of the present invention, the mass ratio of potassium chloride to primary condensate in step (1) is (0.250 to 0.342): 1.
in one embodiment of the invention, the primary condensate in step (1) is adjusted in pH using saturated sodium bicarbonate solution.
In one embodiment of the invention, the mass ratio of the primary condensation product and water in step (2) is 3 to 4:20.
in one embodiment of the present invention, the ratio of 1-amino-8-hydroxy-3, 6-naphthalene disulfonic acid to water in step (2) is from (0.25 to 0.45): 1.
in one embodiment of the invention, the pH of the 1-amino-8-hydroxy-3, 6-naphthalenedisulfonic acid solution in step (2) is adjusted using a saturated sodium carbonate solution.
In one embodiment of the invention, the molar ratio of the primary condensation product and 1-amino-8-hydroxy-3, 6-naphthalenedisulfonic acid in step (2) is 1:1.
in one embodiment of the present invention, the adjustment of the pH in step (2) to 4.5 to 5.0 is performed using a saturated sodium bicarbonate solution.
In one embodiment of the present invention, the mass ratio of potassium chloride to the secondary condensate in step (2) is (0.250 to 0.342): 1.
in one embodiment of the present invention, the heterocyclic aromatic primary amine derivative in step (3) includes one of formula 1, formula 2, formula 3, formula 4 or formula 5.
In one embodiment of the present invention, the acid in step (3) comprises any one or more of hydrochloric acid solution, propionic acid solution, concentrated sulfuric acid solution (98%, w/w) or dilute sulfuric acid (40-70%, w/w), phosphoric acid solution, etc.
In one embodiment of the present invention, the mass ratio of the heterocyclic aromatic primary amine derivative to the acid in step (3) is 0.1 to 10:1.
in one embodiment of the present invention, the diazotizing agent in step (3) is a sodium nitrite solution or a nitrosylsulfuric acid solution, the concentration of the sodium nitrite solution is 30% (w/w), and the concentration of the nitrosylsulfuric acid solution is 40% (w/w).
In one embodiment of the present invention, the molar ratio of the heterocyclic aromatic primary amine to the diazotizing agent in step (3) is 1: (1.1-1.2) to ensure complete diazotization of the diazotisation component.
In one embodiment of the invention, the elimination of excess nitrous acid in step (3) is the addition of sulfamic acid.
In one embodiment of the invention, the mass ratio of the secondary condensation product to water in step (3) is (0.2 to 0.5): 1.
in one embodiment of the invention, the molar ratio of the secondary condensation product to the diazonium salt of a heterocyclic aromatic primary amine in step (3) is 1:2.
a third object of the present invention is the use of the pH-shifting reactive dyes for sweat detection according to the invention for dyeing or printing textiles.
In one embodiment of the invention, the textile comprises cotton, viscose, hemp or a plurality of blends thereof and fabrics thereof.
The fourth object of the invention is to provide a pH color-changing cotton fabric, which is obtained by dyeing cotton fabric with the pH color-changing reactive dye for sweat detection.
A fifth object of the present invention is to provide a sweat detection sensor employing the pH color changing reactive dye or the pH color changing cotton fabric for sweat detection according to the present invention.
[ advantageous effects ]
(1) The pH color-changing reactive dye for sweat detection can change the maximum absorption wavelength of a solution within 0.70-0.80 pH units by 51nm, namely: the color-changing precision is high; and the pH value at the isoelectric point (absorbance value of the solution before and after the color change) is 6.00-7.00, thus solving the problem that the color change point of the existing pH color change reactive dye needs to be under a strong acid or strong alkaline condition.
(2) The pH color-changing reactive dye for sweat detection is used for dyeing cotton fabrics to obtain printed cotton fabrics with the color fixation rate reaching more than 50%, and the water washing, friction and light fastness reaching more than 3-4 levels; can be applied to human sweat detection (pH=4.2-8.3).
Drawings
Fig. 1 is a spectral plot of the dye of example 1 at different pH conditions (ph=2 to 11).
Fig. 2 is a dye-change optical picture of example 1.
Fig. 3 is a spectral plot of the dye of example 1 at different pH conditions (ph=4.01 to 6.51).
FIG. 4 shows the absorbance at the maximum absorption wavelength of the solution before and after the dye of example 1 was changed in accordance with the pH.
FIG. 5 is a graph showing the change of the absorbance ratio with pH of the solution before and after the discoloration of the dye of example 1.
Fig. 6 is a spectral plot of the dye of example 2 at different pH conditions (ph=3 to 12.5).
Fig. 7 is a dye-change optical picture of example 2.
Fig. 8 is a spectral plot of the dye of example 2 at different pH conditions (ph=5.62 to 7.53).
FIG. 9 shows the absorbance at the maximum absorption wavelength of the solution before and after the dye of example 2 was changed with pH.
FIG. 10 is a graph showing the change in absorbance ratio with pH of the solution before and after the dye of example 2 was discolored.
Fig. 11 is a graphical representation of the printed cotton fabric of the dye of example 1 under acidic conditions (ph=5.5).
Fig. 12 is a graphical representation of the printed cotton fabric of the dye of example 1 under alkaline conditions (ph=8.0).
Fig. 13 is a graphical representation of the printed cotton fabric of the dye of example 2 under acidic conditions (ph=5.5).
Fig. 14 is a graphical representation of the printed cotton fabric of the dye of example 2 under alkaline conditions (ph=8.0).
Detailed Description
The following description of the preferred embodiments of the present invention is provided for better illustration of the invention, and should not be construed as limiting the invention.
The testing method comprises the following steps:
1. wash fastness test:
fastness to domestic and commercial laundering according to AATCC61/2003 test procedure 1A and 2A and 3A: accelerated assay.
2. Rubbing color fastness test:
measured according to GB/T3920-1997 "rubbing fastness to textiles colour fastness experiment".
3. Light fastness test:
artificial light fastness to light was tested according to GB/T8427-1998 textile colour fastness test: hernia arc measurement.
4. pH discoloration test:
formulation of pH-discolouring dyes to 1X 10 -4 500mL of a mol/L aqueous solution, then adopting hydrochloric acid, acetic acid/sodium acetate buffer solution, sodium bicarbonate, sodium hydroxide and other pH values of conditional solutions, respectively measuring the sample by adopting an ultraviolet-visible light spectrophotometer (UV-2450, hitachi), and detecting the wavelength range from 380 nm to 780nm.
5. Nuclear magnetic resonance hydrogen spectrum [ ] 1 H-NMR)：
Nuclear magnetic characterization of the samples was performed using a nuclear magnetic resonance spectrometer (AVANCE III) using deuterated water as a solvent.
6. K/S value characterization:
the apparent colour depth of the printed fabric was measured and can be expressed as the K/S value of the printed fabric. According to Kubelka-Munk law, the following formula (1):
wherein: k is the absorption coefficient; s is a scattering coefficient; r is light not transmitted, at lambda max Reflectivity under.
7. Fixation rate:
the fixation rate is the ratio of the K/S value of the printed fabric after soaping to the K/S value of the printed fabric after washing for 10min by 50% DMF at 25 ℃, and the calculation formula is shown in the following formula (2):
example 1
A method of preparing a pH-shifting reactive dye for sweat detection comprising the steps of:
(1) One-time condensation reaction
Adding 3.74g (0.02 mol) of cyanuric chloride and 0.19g of nekal into 15g of ice water mixture, and fully pulping for 1h at the temperature of 0-5 ℃ to obtain cyanuric chloride solution; adding 4.93g (0.02 mol, 97%) of 2-amino-5-naphthol-7-sulfonic acid into 10g of water, regulating the pH to 6.0-6.5 by adopting a saturated sodium carbonate solution, and fully dissolving to obtain a sodium 2-amino-5-naphthol-7-sulfonate solution; mixing 2-amino-5-naphthol-7-sodium sulfonate with cyanuric chloride solution, regulating the pH to 3.0-3.5 by using saturated sodium bicarbonate solution, continuing the reaction at 0-5 ℃, and detecting the reaction end point by using an amino reagent to obtain primary condensation liquid; after the pH value of the primary condensation liquid is regulated to be 1.5 by acetic acid, adding potassium chloride to separate out solid powder (the mass ratio of the potassium chloride to the primary condensation liquid is 0.3:1). The precipitated solid powder is dispersed in absolute ethyl alcohol, filtered, freeze-dried, and the primary condensation product is obtained.
(2) Secondary condensation reaction
A primary condensation solution was prepared by dissolving 3.74g (0.01 mol) of the primary condensation product in 20mL of water. 3.19g (0.01 mol) of 1-amino-8-hydroxy-3, 6-naphthalenedisulfonic acid was added to 10g of water, and the pH was adjusted to 6.0 to 6.5 using a saturated sodium carbonate solution to obtain a 1-amino-8-hydroxy-3, 6-naphthalenedisulfonic acid sodium salt solution. Then adding 1-amino-8-hydroxy-3, 6-naphthalene disulfonic acid solution into the primary condensation solution, raising the temperature to 30-35 ℃, adjusting the pH value to 4.5-5.0, continuously reacting at 30-35 ℃, and adopting sodium carbonate solution to maintain the pH value of the reaction solution to 4.0-4.5. Detecting the reaction end point by adopting an amino reagent to obtain a secondary condensation liquid; after the pH value of the secondary condensation liquid is regulated to 2.0 by acetic acid, a certain amount of potassium chloride is added to separate out solid powder (the mass ratio of the potassium chloride to the secondary condensation liquid is 0.3:1). Dispersing the precipitated solid powder in absolute ethyl alcohol, filtering, freeze drying to obtain the secondary condensation product.
(3) Diazotisation-coupling reactions
15.6g of 98% (w/w) sulfuric acid solution is added into a 250mL three-neck flask, 3.9g (0.02 mol) of 3-amino-5-nitrobenzoisothiazole is slowly added, stirring is carried out for 1h below 50 ℃ to fully dissolve the solution, 6.99g (0.022 mol) of 40% (w/w) nitrosylsulfuric acid solution is slowly added dropwise below 0 ℃, 3.9g of glacial acetic acid is slowly added dropwise at 0-5 ℃ to react for 3-4 h; adding sulfamic acid to eliminate excessive nitrous acid to obtain heterocyclic aromatic primary amine diazonium salt. Dissolving 0.01mol of 7.22g of secondary condensation product in 20mL of water, reducing the temperature to 10-15 ℃, slowly adding the prepared heterocyclic aromatic primary amine diazonium salt into the water, continuously reacting for 2 hours at the temperature of 10-15 ℃, adjusting the pH value to 6, continuously reacting, and detecting the end point of the reaction by adopting H acid (1-amino-8-hydroxy-3, 6-naphthalene disulfonate); after the reaction is finished, the pH color-changing reactive dye for sweat detection is obtained through salting out, suction filtration, ethanol washing and drying.
The structural formula of the obtained pH color-changing reactive dye for sweat detection is as follows:
the synthetic route is as follows:
the structural characterization is as follows:
1 H-NMR (400 MHz, DMSO-d 6): delta 9.43 (s, 2H, -NH-), 9.00 (s, 2H, -OH), 8.36,8.34 (d, 2H, ar-H), 8.26 (s, 2H, ar-H), 8.19,8.17 (d, 2H, ar-H), 8.05 (d, 1H, hydrogen on naphthalene ring), 7.82 (s, 1H, hydrogen on naphthalene ring), 7.79 (d, 1H, hydrogen on naphthalene ring), 7.52 (s, 1H, hydrogen on naphthalene ring), 7.47 (s, 1H, hydrogen on naphthalene ring), 7.41 (s, 1H, hydrogen on naphthalene ring), 7.32 (s, 1H, hydrogen on naphthalene ring).
The performance test is carried out on the obtained pH color-changing reactive dye for sweat detection, and the test result is as follows:
fig. 1 is a spectrum of the dye of example 1 at different pH conditions (ph=2 to 11), and fig. 2 is a color-changing optical picture of the dye. As can be seen from fig. 1 and 2: when the pH value of the solution is more than or equal to 6.0, the solution shows green color (the maximum absorption wavelength is 662 nm), and when the pH value of the solution is less than 6.0, the solution shows blue color (the maximum absorption wavelength is 611 nm).
Fig. 3 is a spectral plot of the dye of example 1 at different pH conditions (ph=4.01 to 6.51). As can be seen from fig. 3: when the solution ph=4.91, the solution showed a blue color, the solution maximum absorption wavelength was 611nm; when the solution ph=5.61, the solution showed green color with a maximum absorption wavelength of 662nm, indicating a 51nm change in the maximum absorption wavelength of the dye in 0.70 pH units. The color-changing precision of the dye is higher.
Fig. 4 and 5 show the absorbance and absorbance ratio at the maximum absorption wavelength of the solution before and after the dye changes color with the pH value. As can be seen from fig. 4 and 5: the pH at the isoelectric point of the solution (absorbance values of the solution before and after the discoloration) was 6.00.
Example 2
A method of preparing a pH-shifting reactive dye for sweat detection comprising the steps of:
(1) The primary condensation reaction is the same as in example 1, step (1);
(2) The secondary condensation reaction is the same as in example 1, step (2);
(3) Diazotisation-coupling reactions
50g of 49% (w/w) sulfuric acid solution is added into a 250mL three-necked flask, 4.38g (0.02 mol) of 2-amino-5, 6-dichlorobenzothiazole is slowly added, and the mixture is stirred for 1h below 50 ℃ to be fully dissolved; slowly dripping 6.99g (0.022 mol) of 40% (w/w) nitrosylsulfuric acid solution below 0-5 ℃ to react for 4 hours; adding sulfamic acid to eliminate excessive nitrous acid to obtain heterocyclic aromatic primary amine diazonium salt; dissolving 0.01mol of 7.22g of secondary condensation product in 20mL of water, reducing the temperature to 10-15 ℃, slowly adding the prepared heterocyclic aromatic primary amine diazonium salt into the water, continuously reacting for 2 hours at the temperature of 10-15 ℃, adjusting the pH value to 6, continuously reacting, and detecting the end point of the reaction by adopting H acid (1-amino-8-hydroxy-3, 6-naphthalene disulfonate); after the reaction is finished, the pH color-changing reactive dye for sweat detection is obtained through salting out, suction filtration, ethanol washing and drying.
The structural formula of the obtained pH color-changing reactive dye for sweat detection is as follows:
the synthetic route is as follows:
the structural characterization is as follows:
1 H-NMR (400 MHz, DMSO-d 6): delta 9.43 (s, 2H, -NH-), 9.00 (s, 2H, -OH), 8.66,8.64 (s, 2H, ar-H), 8.31,8.29 (d, 2H, ar-H), 8.05 (d, 1H, hydrogen on naphthalene ring), 7.82 (s, 1H, hydrogen on naphthalene ring), 7.79 (d, 1H, hydrogen on naphthalene ring), 7.52 (s, 1H, hydrogen on naphthalene ring), 7.47 (s, 1H, hydrogen on naphthalene ring), 7.41 (s, 1H, hydrogen on naphthalene ring), 7.32 (s, 1H, hydrogen on naphthalene ring).
The performance test is carried out on the obtained pH color-changing reactive dye for sweat detection, and the test result is as follows:
fig. 6 is a spectrum of the dye of example 2 under different pH conditions (ph=2 to 11), and fig. 7 is a color-changing optical picture of the dye. As can be seen from fig. 6 and 7: when the pH value of the solution is more than or equal to 7.0, the solution shows blue (the maximum absorption wavelength is 590 nm), and when the pH value of the solution is less than 7.0, the solution shows red (the maximum absorption wavelength is 539 nm).
Fig. 8 is a spectral plot of the dye of example 2 at different pH conditions (ph=4.01 to 6.51). As can be seen from fig. 8: when the solution ph=6.30, the solution showed red color, and the maximum absorption wavelength of the solution was 539nm; when the solution ph=7.06, the solution showed green color with a maximum absorption wavelength of 590nm, indicating that the dye had a 51nm change in the maximum absorption wavelength of the solution within 0.76 pH units. The color-changing precision of the dye is higher.
Fig. 9 and 10 show the absorbance and absorbance ratio at the maximum absorption wavelength of the solution before and after the dye color change, depending on the pH value. As can be seen from fig. 9 and 10: the pH at the isoelectric point of the solution (absorbance values of the solution before and after the discoloration) was 6.84.
Example 3 application of color-changing dye to printing of cotton fabrics
Preparation of pH color-changing cotton fabric (140 g/m) 2 Pure cotton bleached knitted fabric) comprising the steps of:
the formula of the printing paste comprises the following steps: the dye is 40g/L, the raw paste (sodium alginate water solution with the mass concentration of 4%) is 60g/L, the anti-staining salt S is 15g/L, the urea is 60g/L, the sodium carbonate is 25g/L, and the water is added to complement 1000g;
the printing process comprises the following steps: printing, pre-drying (100 ℃,4 min), steaming (105 ℃,6 min), cold water washing, soaping (98 ℃,10 min), reduction washing (85 ℃,15 min), hot water washing (80 ℃), cold water washing and drying.
The cotton fabric obtained in example 3 was immersed in sweat simulation solutions (see table 1) with different pH values, and performance tests were performed, and the test results are shown in table 2, fig. 11 to fig. 14 below:
TABLE 1
| Component names and contents | Acid sweat simulation liquid | Alkali sweat simulation liquid |
| L-histidine hydrochloride monohydrate | 0.5g/L | 0.5g/L |
| Sodium chloride | 5g/L | 5g/L |
| Sodium dihydrogen phosphate dihydrate | 2.2g/L | --- |
| Disodium hydrogen phosphate dihydrate | --- | 2.5g/L |
| 0.1mol/L sodium hydroxide solution | Adjusting pH to 5.5 | Adjusting pH to 8.0 |
TABLE 2
As can be seen from table 2: the dye fixation rates of the printed cotton fabrics prepared by the dyes in the examples 1 and 2 reach more than 50%, and the fastness to washing, rubbing and sunlight reach 3-4 levels and more.
As can be seen from fig. 11 to 12: the printed cotton fabric prepared by the dye of the example 1 is blue under the condition of acid sweat and green under the condition of alkali sweat, and can be applied to human sweat detection.
As can be seen from fig. 13 to 14: the printed cotton fabric prepared by the dye of the example 2 is red under the condition of acid sweat and blue under the condition of alkali sweat, and can be applied to human sweat detection.
Comparative example 1
A method of preparing a pH-shifting dye comprising the steps of:
adding 3.74g (0.02 mol) of cyanuric chloride and 0.19g of nekal into 15g of ice water mixture, and fully pulping for 1h at the temperature of 0-5 ℃ to obtain cyanuric chloride solution; adding 5.5g (0.02 mol) of 2, 5-disulfonic aniline and 25.56g of water into a beaker, stirring uniformly, adjusting the pH to 6.0-6.5 by adopting sodium carbonate, and fully dissolving to obtain a 2, 5-disulfonic aniline solution; then mixing the 2, 5-disulfonic acid aniline solution and the cyanuric chloride solution, adopting saturated sodium bicarbonate solution to adjust the pH value to 3.0-3.5, continuously reacting at the temperature of 0-5 ℃, and adopting sodium carbonate solution to maintain the pH value of the reaction solution to 3.0-3.5. Detecting the reaction end point by adopting an amino reagent to obtain a primary condensation liquid; after the pH value of the primary condensation liquid is regulated to be 1.5 by acetic acid, adding potassium chloride to separate out solid powder (the mass ratio of the potassium chloride to the primary condensation liquid is 0.3:1). The precipitated solid powder is dispersed in absolute ethyl alcohol, filtered, freeze-dried, and the primary condensation product is obtained.
A primary condensation solution was prepared by dissolving 8.18g (0.02 mol) of the primary condensation product in 20mL of water. 10.62g (0.01 mol) of P-3R (C.I. active blue 49) chromophore dry powder is rapidly added into the primary condensation solution, the temperature is increased to 30-35 ℃, the pH value is adjusted to 4.5-5.0 by saturated sodium bicarbonate solution, the reaction is continued at 30-35 ℃, and the pH value of the reaction solution is maintained to 4.5-5.0 by sodium carbonate solution. Detecting the reaction end point by adopting an amino reagent to obtain a secondary condensation liquid; after the pH value of the secondary condensation liquid is regulated to 2.0 by acetic acid, a certain amount of potassium chloride is added to separate out solid powder (the mass ratio of the potassium chloride to the secondary condensation liquid is 0.3:1). Dispersing the precipitated solid powder in absolute ethyl alcohol, filtering, freeze drying to obtain the secondary condensation product.
7.22g (0.02 mol)) of para-ester of meta-sulfonic acid is added into a 250mL beaker, 6mL of 36% (w/w) hydrochloric acid solution is added, the mixture is stirred uniformly, the temperature is reduced to 0-5 ℃, 0.022mol of 30% (w/w) sodium nitrite solution is slowly added, and the reaction is completed for 1 h. Adding sulfamic acid to eliminate excessive nitrous acid to obtain meta-sulfonic acid para-ester diazonium salt. Dissolving 0.02mol of 18.23g of the secondary condensation product in 20mL of water, reducing the temperature to 10-15 ℃, slowly adding the prepared para-diazonium salt of the m-sulfonic acid, continuously reacting for 2 hours at the temperature of 10-15 ℃, adjusting the pH value to 6, continuously reacting, and detecting the end point of the reaction by adopting H acid (1-amino-8-hydroxy-3, 6-sodium naphthalene disulfonate); after the reaction is finished, the pH color-changing dye is obtained through salting out, suction filtration, ethanol washing and drying.
The structural formula of the obtained pH color-changing dye is as follows:
after that, the cotton fabric was printed in the same manner as in example 3, the fixation rate of the dye on the cotton fabric was only 29.36%, and the color change pH value of the dyed fabric was not less than 9.0 (strong alkali condition), which could not be used for sweat detection.
Comparative example 2
A method of preparing a pH-shifting dye comprising the steps of:
adding 3.74g (0.02 mol) of cyanuric chloride and 0.19g of nekal into 15g of ice water mixture, and fully pulping for 1h at the temperature of 0-5 ℃ to obtain cyanuric chloride solution; adding 5.5g (0.02 mol) of 2, 4-diaminobenzenesulfonic acid and 25.56g of water into a beaker, stirring uniformly, adjusting the pH to 6.0-6.5 by adopting sodium carbonate, and fully dissolving to obtain a 2, 4-diaminobenzenesulfonic acid sodium solution; then mixing 2, 4-diaminobenzene sodium sulfonate solution and cyanuric chloride solution, adopting saturated sodium bicarbonate solution to regulate pH value to 3.0-3.5, continuously reacting at 0-5 ℃, and adopting sodium carbonate solution to maintain pH value of reaction solution to 3.0-3.5. Detecting the reaction end point by adopting an amino reagent to obtain a primary condensation liquid; after the pH value of the primary condensation liquid is regulated to be 1.5 by acetic acid, adding potassium chloride to separate out solid powder (the mass ratio of the potassium chloride to the primary condensation liquid is 0.3:1). The precipitated solid powder is dispersed in absolute ethyl alcohol, filtered, freeze-dried, and the primary condensation product is obtained.
A primary condensation solution was prepared by dissolving 7.16g (0.02 mol) of the primary condensation product in 20mL of water. 10.62g (0.01 mol) of P-3R (C.I. active blue 49) chromophore dry powder is rapidly added into the primary condensation solution, the temperature is increased to 30-35 ℃, the pH value is adjusted to 4.5-5.0 by saturated sodium bicarbonate solution, the reaction is continued at 30-35 ℃, and the pH value of the reaction solution is maintained to 4.5-5.0 by sodium carbonate solution. Detecting the reaction end point by adopting an amino reagent to obtain a secondary condensation liquid; after the pH value of the secondary condensation liquid is regulated to 2.0 by acetic acid, a certain amount of potassium chloride is added to separate out solid powder (the mass ratio of the potassium chloride to the secondary condensation liquid is 0.3:1). Dispersing the precipitated solid powder in absolute ethyl alcohol, filtering, freeze drying to obtain the secondary condensation product.
5.83g (0.02 mol)) para-ester was added to a 250mL beaker, 6mL of 36% (w/w) hydrochloric acid solution was added, the mixture was stirred uniformly, the temperature was lowered to 0-5 ℃, 0.022mol of 30% (w/w) sodium nitrite solution was slowly added, and the reaction was completed for 1 hour. Adding sulfamic acid to eliminate excessive nitrous acid to obtain meta-sulfonic acid para-ester diazonium salt. Dissolving 0.02mol of 14.97g of secondary condensation product in 20mL of water, reducing the temperature to 10-15 ℃, slowly adding the prepared para-ester diazonium salt of the m-sulfonic acid into the water, continuously reacting for 2 hours at the temperature of 10-15 ℃, adjusting the pH value to 6, continuously reacting, and detecting the end point of the reaction by adopting H acid (1-amino-8-hydroxy-3, 6-sodium naphthalene disulfonate); after the reaction is finished, the pH color-changing dye is obtained through salting out, suction filtration, ethanol washing and drying.
The structural formula of the obtained pH color-changing dye is as follows:
after that, the cotton fabric was printed in the same manner as in example 3, the fixation rate of the dye on the cotton fabric was only 26.91%, and the color change pH value of the dyed fabric was not more than 1.6 (strong acid condition), which could not be used for sweat detection.
Comparative example 3
A method of preparing a pH-shifting dye comprising the steps of:
(1) The primary condensation reaction is the same as in example 1, step (1);
(2) Secondary condensation reaction
A primary condensation solution was prepared by dissolving 8.80g (0.02 mol) of the primary condensation product in 20mL of water. 7.66g (0.02 mol) of 7-amino-1, 3, 5-naphthalene trisulfonic acid is regulated to pH 9.0 by adopting hydrochloric acid solution, then the mixture is slowly added into primary condensation solution, the temperature is increased to 30-35 ℃, the pH is regulated to 4.5-5.0 by adopting saturated sodium bicarbonate solution, the reaction is continued at 30-35 ℃, and the pH value of the reaction solution is maintained to be 4.5-5.0 by adopting sodium carbonate solution. Detecting the reaction end point by adopting an amino reagent to obtain a secondary condensation liquid; after the pH value of the secondary condensation liquid is regulated to 2.0 by acetic acid, a certain amount of potassium chloride is added to separate out solid powder (the mass ratio of the potassium chloride to the secondary condensation liquid is 0.3:1). Dispersing the precipitated solid powder in absolute ethyl alcohol, filtering, freeze drying to obtain the secondary condensation product.
(3) Diazotisation-coupling reactions
15.6g of 98% (w/w) sulfuric acid solution is added into a 250mL three-necked flask, 3.9g (0.02 mol) of 3-amino-5-nitrobenzoisothiazole is slowly added, stirring is carried out for 1h below 50 ℃ to fully dissolve the solution, 6.99g (0.022 mol) of 40% (w/w) nitrosylsulfuric acid solution is slowly added dropwise below 0 ℃, 3.90g of glacial acetic acid is slowly added dropwise at 0-5 ℃ to finish the reaction for 4 h. Adding sulfamic acid to eliminate excessive nitrous acid to obtain heterocyclic aromatic primary amine diazonium salt. Dissolving 0.01mol of 4.27g of secondary condensation product in 20mL of water, reducing the temperature to 10-15 ℃, slowly adding the prepared heterocyclic aromatic primary amine diazonium salt into the water, continuously reacting for 2 hours at the temperature of 10-15 ℃, adjusting the pH value to 6, continuously reacting, and detecting the end point of the reaction by adopting H acid (1-amino-8-hydroxy-3, 6-naphthalene disulfonate); after the reaction is finished, salting out, suction filtering, ethanol washing and drying are carried out, thus obtaining the pH color-changing dye.
The structural formula of the obtained pH color-changing dye is as follows:
after that, the cotton fabric was printed in the same manner as in example 3, the fixation rate of the dye on the cotton fabric was only 19.06%, the color-changing pH value of the dyed fabric was not more than 5.0, the dyed fabric could not be used for sweat detection, and the washing fastness was 3 grade.
Comparative example 4
A method of preparing a pH-shifting dye comprising the steps of:
(1) The primary condensation reaction is the same as in example 1, step (1);
(2) Secondary condensation reaction
A primary condensation solution was prepared by dissolving 8.80g (0.02 mol) of the primary condensation product in 20mL of water. 7.66g (0.02 mol) of 7-amino-1, 3, 5-naphthalene trisulfonic acid is regulated to pH 9.0 by adopting hydrochloric acid solution, then the mixture is slowly added into primary condensation solution, the temperature is increased to 30-35 ℃, the pH is regulated to 4.5-5.0 by adopting saturated sodium bicarbonate solution, the reaction is continued at 30-35 ℃, and the pH value of the reaction solution is maintained to be 4.5-5.0 by adopting sodium carbonate solution. Detecting the reaction end point by adopting an amino reagent to obtain a secondary condensation liquid; after the pH value of the secondary condensation liquid is regulated to 2.0 by acetic acid, a certain amount of potassium chloride is added to separate out solid powder (the mass ratio of the potassium chloride to the secondary condensation liquid is 0.3:1). Dispersing the precipitated solid powder in absolute ethyl alcohol, filtering, freeze drying to obtain the secondary condensation product.
(3) Diazotisation-coupling reactions
15.6g of 98% (w/w) sulfuric acid solution is added into a 250mL three-necked flask, 3.48g (0.02 mol) of 2, 5-dinitrothiophene is slowly added, stirring is carried out for 1h below 50 ℃ to fully dissolve the 2, 6.99g (0.022 mol) of 40% (w/w) nitrosylsulfuric acid solution is slowly added dropwise below 0 ℃, 3.48g of glacial acetic acid is slowly added dropwise at 0-5 ℃ to finish the reaction for 3-4 h. Adding sulfamic acid to eliminate excessive nitrous acid to obtain heterocyclic aromatic primary amine diazonium salt. Dissolving 0.01mol of 4.27g of secondary condensation product in 20mL of water, reducing the temperature to 10-15 ℃, slowly adding the prepared heterocyclic aromatic primary amine diazonium salt into the water, continuously reacting for 2 hours at the temperature of 10-15 ℃, adjusting the pH value to 6, continuously reacting, and detecting the end point of the reaction by adopting H acid (1-amino-8-hydroxy-3, 6-naphthalene disulfonate); after the reaction is finished, the pH color-changing dye is obtained through salting out, suction filtration, ethanol washing and drying.
The structural formula of the obtained pH color-changing dye is as follows:
after that, the cotton fabric was printed in the same manner as in example 3, the fixation rate of the dye on the cotton fabric was only 19.06%, the color change pH value of the dyed fabric was not more than 3.0 (strong acid condition), the dyed fabric could not be used for sweat detection, and the washing fastness was 3 grade.
Comparative example 5
A method of preparing a pH-shifting dye comprising the steps of:
(1) The primary condensation reaction is the same as in example 1, step (1);
(2) The secondary condensation reaction is the same as in example 1, step (2);
(3) Diazotisation-coupling reactions
18.45g of 98% (w/w) sulfuric acid solution is added into a 250mL three-necked flask, 4.14g (0.02 mol) of 2, 6-dichloro-4-nitroaniline is slowly added, stirring is carried out for 1h below 50 ℃ to fully dissolve, 6.99g (0.022 mol) of 40% (w/w) nitrosylsulfuric acid solution is slowly added dropwise below 0 ℃ to complete the reaction for 4 h; adding sulfamic acid to eliminate excessive nitrous acid to obtain heterocyclic aromatic primary amine diazonium salt. Dissolving 0.01mol of 7.22g of secondary condensation product in 20mL of water, reducing the temperature to 10-15 ℃, slowly adding the prepared heterocyclic aromatic primary amine diazonium salt into the water, continuously reacting for 2 hours at the temperature of 10-15 ℃, adjusting the pH value to 6, continuously reacting, and detecting the end point of the reaction by adopting H acid (1-amino-8-hydroxy-3, 6-naphthalene disulfonate); after the reaction is finished, the pH color-changing dye is obtained through salting out, suction filtration, ethanol washing and drying.
The structural formula of the obtained pH color-changing dye is as follows:
the synthetic route is as follows:
the cotton fabric was then printed as in example 3, the dye fixation on cotton fabric being only 26.37%.
Comparative example 6
A method of preparing a pH-shifting dye comprising the steps of:
adding 3.74g (0.02 mol) of cyanuric chloride and 0.19g of nekal into 15g of ice water mixture, and fully pulping for 1h at the temperature of 0-5 ℃ to obtain cyanuric chloride solution; adding 4.78g (0.02 mol) of 2-amino-5-naphthol-7-sulfonic acid into 15g of water, adjusting the pH to 6.0-6.5 by adopting sodium carbonate, and fully dissolving to obtain 2-amino-5-naphthol-7-sodium sulfonate solution; then mixing 2-amino-5-naphthol-7-sodium sulfonate solution and cyanuric chloride solution, adopting saturated sodium bicarbonate solution to regulate pH value to 3.0-3.5, continuously reacting at 0-5 deg.C, and adopting sodium carbonate solution to maintain pH value of reaction solution to 3.0-3.5. Detecting the reaction end point by adopting an amino reagent to obtain a primary condensation liquid; after the pH value of the primary condensation liquid is regulated to be 1.5 by acetic acid, a certain amount of potassium chloride is added to separate out solid powder (the mass ratio of the potassium chloride to the primary condensation liquid is 0.3:1). The precipitated solid powder is dispersed in absolute ethyl alcohol, filtered, freeze-dried, and the primary condensation product is obtained.
A primary condensation solution was prepared by dissolving 9.44g (0.02 mol) of the primary condensation product in 20mL of water. 4.78g (0.02 mol) of 2-amino-5-naphthol-7-sulfonic acid was added to 15g of water to obtain a 2-amino-5-naphthol-7-sulfonic acid solution; then slowly adding 2-amino-5-naphthol-7-sulfonic acid solution into the primary condensation solution, raising the temperature to 30-35 ℃, adjusting the pH value to 4.5-5.0 by using saturated sodium bicarbonate solution, continuing the reaction at 30-35 ℃, and adopting sodium carbonate solution to maintain the pH value of the reaction solution to 4.5-5.0. Detecting the reaction end point by adopting an amino reagent to obtain a secondary condensation liquid; after the pH value of the secondary condensation liquid is regulated to 2.0 by acetic acid, a certain amount of potassium chloride is added to separate out solid powder (the mass ratio of the potassium chloride to the secondary condensation liquid is 0.3:1). Dispersing the precipitated solid powder in absolute ethyl alcohol, filtering, freeze drying to obtain the secondary condensation product.
50g of 49% (w/w) sulfuric acid solution is added into a 250mL three-necked flask, 4.38g (0.02 mol) of 2-amino-5, 6-dichlorobenzothiazole is slowly added, and the mixture is stirred for 1h below 50 ℃ to be fully dissolved; slowly dripping 6.99g (0.022 mol) of 40% (w/w) nitrosylsulfuric acid solution below 0-5 ℃ to react for 4 hours; adding sulfamic acid to eliminate excessive nitrous acid to obtain heterocyclic aromatic primary amine diazonium salt; dissolving 0.01mol of 5.98g of secondary condensation product in 20mL of water, reducing the temperature to 10-15 ℃, slowly adding the prepared heterocyclic aromatic primary amine diazonium salt into the water, continuously reacting for 2 hours at the temperature of 10-15 ℃, adjusting the pH value to 6, continuously reacting, and detecting the end point of the reaction by adopting H acid (1-amino-8-hydroxy-3, 6-naphthalene disulfonate); after the reaction is finished, the pH color-changing dye is obtained through salting out, suction filtration, ethanol washing and drying.
The structural formula of the obtained pH color-changing dye is as follows:
the synthetic route is as follows:
the cotton fabric was then printed as in example 3, the dye fixation on the cotton fabric being only 41.43%.
While the invention has been described with reference to the preferred embodiments, it is not limited thereto, and various changes and modifications can be made therein by those skilled in the art without departing from the spirit and scope of the invention as defined in the appended claims.
Claims (10)
1. A pH color-changing reactive dye for sweat detection, characterized by the following structural formula:
2. a method of preparing the pH-shifting reactive dye for sweat detection of claim 1, comprising the steps of:
(1) One-time condensation reaction
Adding cyanuric chloride and nekal into the ice-water mixture, and fully pulping at 0-5 ℃ to obtain cyanuric chloride solution; adding 2-amino-5-naphthol-7-sulfonic acid into water, regulating the pH to 6.0-6.5, and fully dissolving to obtain 2-amino-5-naphthol-7-sulfonic acid solution; then mixing 2-amino-5-naphthol-7-sulfonic acid solution and cyanuric chloride solution, regulating the pH value to 3.0-3.5, continuously reacting at 0-5 ℃, and adopting sodium carbonate solution to maintain the pH value of the reaction solution to 3.0-3.5; detecting the reaction end point by adopting an amino reagent to obtain a primary condensation liquid; adjusting the pH value of the primary condensation liquid to 1.5 by adopting acetic acid, and adding potassium chloride to separate out solid powder; dispersing the precipitated solid powder in absolute ethyl alcohol, filtering, freeze-drying to obtain a primary condensation product;
(2) Secondary condensation reaction
Dissolving the primary condensation product in water to obtain a primary condensation solution; adding 1-amino-8-hydroxy-3, 6-naphthalene disulfonic acid into water, and adjusting the pH to 6.0-6.5 to obtain 1-amino-8-hydroxy-3, 6-naphthalene disulfonic acid sodium solution; then adding 1-amino-8-hydroxy-3, 6-naphthalene disulfonic acid solution into the primary condensation solution, raising the temperature to 30-35 ℃, adjusting the pH value to 4.5-5.0, continuously reacting at 30-35 ℃, and adopting sodium carbonate solution to maintain the pH value of the reaction solution to 4.0-4.5; detecting the reaction end point by adopting an amino reagent to obtain a secondary condensation liquid; adjusting the pH value of the secondary condensation liquid to 2.0 by adopting acetic acid, and adding potassium chloride to separate out solid powder; dispersing the precipitated solid powder in absolute ethyl alcohol, filtering, freeze-drying to obtain a secondary condensation product;
(3) Diazotisation-coupling reactions
Dissolving a heterocyclic aromatic primary amine derivative in acid, adding a diazotizing reagent at the temperature of 0-5 ℃ and keeping the temperature for reaction for 3-4 hours, and eliminating excessive nitrous acid after the reaction is finished to obtain heterocyclic aromatic primary amine diazonium salt; dissolving the secondary condensation product in water, reducing the temperature of the solution to 10-15 ℃, slowly adding heterocyclic aromatic primary amine diazonium salt into the solution, continuously reacting for 1-3 hours at the temperature of 10-15 ℃, adjusting the pH value to 6, continuously reacting, and detecting the end point of the reaction by adopting 1-amino-8-hydroxy-3, 6-naphthalene disulfonate; after the reaction is finished, the pH color-changing reactive dye for sweat detection is obtained through salting out, suction filtration, ethanol washing and drying.
3. The process according to claim 2, wherein the molar ratio of 2-amino-5-naphthol-7-sulfonic acid to cyanuric chloride in step (1) is 1:1.
4. the process according to claim 2, wherein the molar ratio of primary condensation product to 1-amino-8-hydroxy-3, 6-naphthalene disulfonic acid in step (2) is 1:1.
5. the method according to claim 2, wherein the heterocyclic aromatic primary amine derivative in step (3) is formula 1 or formula 2:
6. the method according to claim 2, wherein the molar ratio of the secondary condensation product to the diazonium salt of a primary heterocyclic aromatic amine in step (3) is 1:2.
7. the method of claim 2, wherein the diazotizing agent in step (3) is a sodium nitrite solution or a nitrosylsulfuric acid solution.
8. Use of a pH-changing reactive dye for sweat detection according to claim 1 for dyeing or printing textiles.
9. A pH-shifting cotton fabric, characterized in that it is obtained by dyeing cotton fabric with the pH-shifting reactive dye for sweat detection according to claim 1.
10. A sweat detection sensor, characterized in that it employs the pH-changing reactive dye for sweat detection according to claim 1 or the pH-changing cotton fabric according to claim 9.
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| 偶氮类活性染料耐光、汗复合色牢度影响因素的研究;瞿建刚;杨丹;何瑾馨;;印染助剂(01);31-34 * |
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