CN115368753A - 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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- CN115368753A CN115368753A CN202210962830.7A CN202210962830A CN115368753A CN 115368753 A CN115368753 A CN 115368753A CN 202210962830 A CN202210962830 A CN 202210962830A CN 115368753 A CN115368753 A CN 115368753A
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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
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- 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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- 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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- 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. According to the invention, heterocyclic primary amine is used as a diazo component, a compound containing s-triazinyl as an active group is used as a coupling component, and s-triazinyl is used as a bridging group, so that the pH color-changing active dye for sweat detection is prepared. 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 51 nm; and the pH value at the color-changing isoelectric point (the absorbance value of the solution before and after color change) is 6.00-7.00; solves the problem that the color change point of the prior pH color-changing active dye needs to be under strong acid or strong alkaline conditions. The color fixing rate of the printed cotton fabric obtained by using the pH color-changing reactive dye for dyeing the cotton fabric reaches more than 50%, and the color fastness of washing, friction and light fastness can reach more than 3-4 levels; can be applied to human body 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 prospect in the aspects of wearable devices, flexible sensors and the like. At present, researches on color-changing textiles mainly focus on thermal and photochromic properties, but acid-base color change is not negligible at the same time, and the color-changing textile can be applied to monitoring of pH values in many fields and has the advantages of light weight, large coverage area, breathability, washability, high strength and the like.
Researchers have shown great interest in textiles dyed with natural dyes, and there is also increasing interest in imparting novel functions to fabrics while dyeing with natural dyes. The fabric with the acid-base indicating function (the fabric color is obviously reversibly changed along with the change of the environmental pH value) can replace a sensor measuring method and a colorimetric method to judge the pH value of a solution, and can be made into medical gauze and bandage to facilitate the observation of wound healing or infection conditions. Because the natural dye is easy to be oxidized under the irradiation of the external sunlight, the pH color-changing textile dyed by the natural dye has poor light fastness in the process of being taken; in addition, because the dye and the fiber are only combined by weak van der Waals force or hydrogen bonds, the dye falls off and has poor color-changing cyclicity under the repeated external friction and the action of acid and alkali, and the application range of the dye is greatly limited.
There are also some researchers adjusting the structure of the synthetic dye to achieve a good pH response effect. For example: zhang et al (Sensors and actors B: chemical,2019, 286; although the dye can generate covalent bonding reaction with cellulose fibers, due to the design of a parent structure, the color change point of the dye is under a strong acid or strong alkaline condition, so that the dye is greatly limited when being applied to the aspect that the pH value is close to neutral (the pH value range of human sweat is 4.2-8.3) such as human health condition detection and the like, and the application range of the dye is limited.
Therefore, there is an urgent need in the market to produce a reactive dye that changes color at a pH that can change color under weak base, weak acid or even neutral conditions.
Disclosure of Invention
[ problem ] to
At present, dyes in existing pH color-changing textiles have low dye uptake, can change color only under strong acid or strong alkaline conditions, and cannot be used for detecting sweat (pH is close to neutral).
[ solution ]
In order to solve the problems, the invention takes heterocyclic primary amine as a diazo component, a compound containing s-triazinyl as an active group as a coupling component and s-triazinyl as a bridging group, and prepares the pH color-changing active dye for sweat detection. The invention utilizes nucleophilic substitution reaction between s-triazine and hydroxyl in a textile structure to covalently bond a pH color-changing matrix into a fiber chemical structure, and utilizes reversible isomerization reaction between hydroxyl at the adjacent position of a diazo group and the diazo group under different pH adjustments to change the size of a conjugated system and the electronic delocalization range of a dye and realize reversible change of color light of the dye. Moreover, the dye has a double-color body structure, the probability of combination of the dye and-H/-OH is improved, the color change pH value of the dye is effectively adjusted to the conditions of weak base, weak acid and even neutral, and the dye can be used for sweat detection.
The first purpose 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 formula 1 1 、R 2 And R 3 Independently of each other is-H, -NO 2 、-OCH 3 And a halogen;
or, X and Y in formula I are independently formula 2 1 And R 2 Independently is-H, -NO 2 ；
Or, X and Y in formula I are each independently of the other formula 3 1 And R 2 Independently is-H, -NO 2 ；
Or, X and Y in formula I are independently formula 4 1 And R 2 Independently is-H, -NO 2 ；
Or, X and Y in formula I are each independently of the other 5 1 And R 2 Independently is-H, -NO 2 CN and halogen;
a second object of the present invention is to provide a method for preparing a pH color-changing reactive dye for sweat detection, comprising the steps of:
(1) First condensation reaction
Adding cyanuric chloride and nekal in an ice water mixture, and fully pulping at the temperature of 0-5 ℃ to obtain cyanuric chloride solution; adding 2-amino-5-naphthol-7-sulfonic acid into water, adjusting the pH to 6.0-6.5, and fully dissolving to obtain a 2-amino-5-naphthol-7-sulfonic acid solution; then mixing the 2-amino-5-naphthol-7-sulfonic acid solution with a cyanuric chloride solution, adjusting the pH to 3.0-3.5, continuously reacting at the temperature of 0-5 ℃, and maintaining the pH value of the reaction solution to 3.0-3.5 by adopting a sodium carbonate solution; 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, freezing and 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-naphthalenedisulfonic acid into water, and adjusting the pH value to 6.0-6.5 to obtain a 1-amino-8-hydroxy-3, 6-naphthalenedisulfonic acid sodium solution; then adding the 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, continuing the reaction at 30-35 ℃, and adopting a 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, freezing and drying to obtain a secondary condensation product;
(3) Diazotization-coupling reaction
Dissolving heterocyclic aromatic primary amine derivatives in acid, adding a diazotization reagent at the temperature of 0-5 ℃, keeping the temperature for reaction for 3-4 h, 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 the heterocyclic aromatic primary amine diazonium salt into the solution, continuously reacting for 1-3H at the temperature of 10-15 ℃, adjusting the pH value to 6, continuously reacting, and detecting the reaction end point by adopting H acid (1-amino-8-hydroxy-3, 6-sodium naphthalenedisulfonate); after the reaction is finished, salting out, filtering, washing with ethanol, and drying to obtain the pH color-changing reactive dye for sweat detection.
In one embodiment of the invention, the mass ratio of the cyanuric chloride to the nekal to 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 amount 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 pH of the 2-amino-5-naphthol-7-sulfonic acid solution in step (1) is 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 invention, the mass ratio of the potassium chloride to the primary condensation liquid in the step (1) is (0.250-0.342): 1.
in one embodiment of the present invention, the pH of the primary condensation solution in step (1) is adjusted by using a saturated sodium bicarbonate solution.
In one embodiment of the present invention, the mass ratio of the primary condensation product to water in step (2) is 3 to 4:20.
in one embodiment of the present invention, the 1-amino-8-hydroxy-3, 6-naphthalenedisulfonic acid and water are used in a ratio of (0.25 to 0.45) in step (2): 1.
in one embodiment of the present invention, the pH of the 1-amino-8-hydroxy-3, 6-naphthalenedisulfonic acid solution in step (2) is adjusted with a saturated sodium carbonate solution.
In one embodiment of the present 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 pH is adjusted to 4.5 to 5.0 in step (2) by using a saturated sodium bicarbonate solution.
In one embodiment of the invention, the mass ratio of the potassium chloride to the secondary condensation liquid in the step (2) is (0.250-0.342): 1.
in one embodiment of the present invention, the heterocyclic primary arylamine derivative in step (3) comprises 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 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 invention, the molar ratio of heterocyclic primary arylamine to diazotizing agent in step (3) is 1: (1.1-1.2) to ensure the diazotization component to be completely diazotized.
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 present 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 heterocyclic primary arylamine diazonium salt in step (3) is 1:2.
the third object of the invention is the application of the pH color-changing active dye for sweat detection in textile dyeing or printing.
In one embodiment of the invention, the textile comprises cotton, viscose, hemp or a blend thereof and fabrics thereof.
The fourth purpose of the invention is to provide a pH color-changing cotton fabric, which is obtained by dyeing the cotton fabric with the pH color-changing active dye for sweat detection.
A fifth object of the present invention is to provide a sweat detection sensor using 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 higher; and the pH value at the isoelectric point (the absorbance value of the solution before and after color change) of the color change is 6.00-7.00, thereby solving the problem that the color change point of the existing pH color-changing active dye needs to be under the strong acid or strong alkaline condition.
(2) The color fixing rate of the printed cotton fabric obtained by using the pH color-changing reactive dye for sweat detection for dyeing cotton fabric reaches more than 50%, and the fastness to washing, rubbing and sunlight can reach more than 3-4 grades; 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 under different pH conditions (pH = 2-11).
Figure 2 is a color change optical photograph of the dye of example 1.
Fig. 3 is a spectral plot of the dye of example 1 under different pH conditions (pH = 4.01-6.51).
FIG. 4 is a graph showing the change in absorbance with pH at the maximum absorption wavelength of the solution before and after the color change of the dye of example 1.
FIG. 5 shows the absorbance ratio of the solution before and after the color change of the dye in example 1 as a function of pH.
Fig. 6 is a spectral curve of the dye of example 2 under different pH conditions (pH =3 to 12.5).
Fig. 7 is a color changing optical picture of the dye of example 2.
Fig. 8 is a spectral curve of the dye of example 2 under 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 color change of the dye of example 2 as a function of pH.
FIG. 10 is a graph showing the change in the absorbance ratio of the solution before and after the color change of the dye in example 2 according to the change in pH.
Figure 11 is a physical representation of a printed cotton fabric of the dye of example 1 under acidic conditions (pH = 5.5).
Figure 12 is a physical representation of a printed cotton fabric of the dye of example 1 under alkaline conditions (pH = 8.0).
Figure 13 is a physical representation of a printed cotton fabric of the dye of example 2 under acidic conditions (pH = 5.5).
Figure 14 is a physical representation of a printed cotton fabric of the dye of example 2 under alkaline conditions (pH = 8.0).
Detailed Description
The following description is of preferred embodiments of the invention, and it is to be understood that the embodiments are for the purpose of illustrating the invention better and are not to be taken in a limiting sense.
The test method comprises the following steps:
1. and (3) testing fastness to washing:
color fastness to home and commercial laundering according to AATCC61/2003 "test procedures 1A and 2A and 3A: accelerated "measurements.
2. Color fastness to rubbing test:
measured according to GB/T3920-1997 color fastness to rubbing test for textiles.
3. Testing the color fastness to sunlight:
the artificial light color fastness is tested according to GB/T8427-1998 textile color fastness: hernia arc.
4. And (3) pH color change test:
preparing the pH color-changing dye into 1 × 10 -4 500mL of mol/L aqueous solution, then respectively measuring the pH value of the solution by adopting hydrochloric acid, acetic acid/sodium acetate buffer solution, sodium bicarbonate, sodium hydroxide and other conditions and adopting an ultraviolet-visible spectrophotometer (UV-2450, hitachi) to detect the samples, wherein the detection wavelength range is 380-780 nm.
5. Nuclear magnetic resonance hydrogen spectrum ( 1 H-NMR)：
And (3) adopting deuterated water as a solvent, and performing nuclear magnetic characterization on the sample by using a nuclear magnetic resonance spectrometer (AVANCE III).
6. The K/S value is characterized in that:
the apparent color depth of the printed fabric is measured and can be expressed by the K/S value of the printed fabric. According to Kubelka-Munk's law, see formula (1) below:
wherein: k is the extinction coefficient; s is a scattering coefficient; r is at λ when light is not transmitted max Reflectivity of the film.
7. And (3) color fixation rate:
the fixation ratio is a ratio of the K/S value of the printed fabric after soap washing to the K/S value of the printed fabric after washing with 50% DMF for 10min at 25 ℃, and the calculation formula is shown in the following formula (2):
example 1
A method of preparing a pH-color changing reactive dye for sweat detection comprising the steps of:
(1) First 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 (0.02mol, 97%) of 2-amino-5-naphthol-7-sulfonic acid into 10g of water, adjusting the pH to 6.0-6.5 by adopting a saturated sodium carbonate solution, and fully dissolving to obtain a 2-amino-5-naphthol-7-sodium sulfonate solution; then mixing 2-amino-5-naphthol-7-sodium sulfonate with a cyanuric chloride solution, adjusting the pH to 3.0-3.5 by adopting a saturated sodium bicarbonate solution, continuously reacting at the temperature of 0-5 ℃, and 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 adjusted to 1.5 by adopting acetic acid, potassium chloride is added to precipitate solid powder (the mass ratio of the potassium chloride to the primary condensation liquid is 0.3. Dispersing the separated solid powder in absolute ethyl alcohol, filtering, freezing and drying to obtain a primary condensation product.
(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 is added into 10g of water, and the pH is adjusted to 6.0 to 6.5 by using a saturated sodium carbonate solution to obtain a 1-amino-8-hydroxy-3, 6-naphthalenedisulfonic acid sodium solution. Then adding the 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, continuing the reaction at 30-35 ℃, and adopting a 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 a certain amount of potassium chloride to precipitate solid powder (the mass ratio of the potassium chloride to the secondary condensation liquid is 0.3. Dispersing the precipitated solid powder in absolute ethyl alcohol, filtering, freezing and drying to obtain a secondary condensation product.
(3) Diazotization-coupling reaction
Adding 15.6g of 98% (w/w) sulfuric acid solution into a 250mL three-neck flask, slowly adding 3.9g (0.02 mol) of 3-amino-5-nitrobenzoisothiazole, stirring at the temperature of below 50 ℃ for 1h to fully dissolve the same, slowly dropwise adding 6.99g (0.022 mol) of 40% (w/w) nitrosyl sulfuric acid solution at the temperature of below 0 ℃, slowly dropwise adding 3.9g of glacial acetic acid at the temperature of between 0 and 5 ℃, and finishing the reaction for 3 to 4 h; and (3) 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 reaction endpoint by adopting H acid (1-amino-8-hydroxy-3, 6-sodium naphthalenedisulfonate); after the reaction is finished, salting out, filtering, washing with ethanol, and drying to obtain the pH color-changing reactive dye for sweat detection.
The structural formula of the obtained pH color-changing active dye for sweat detection is as follows:
the synthetic route is as follows:
the structure is characterized as follows:
1 H-NMR (400MHz, DMSO-d 6): Δ 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 the naphthalene ring), 7.82 (s, 1H, hydrogen on the naphthalene ring), 7.79 (d, 1H, hydrogen on the naphthalene ring), 7.52 (s, 1H, hydrogen on the naphthalene ring), 7.47 (s, 1H, hydrogen on the naphthalene ring), 7.41 (s, 1H, hydrogen on the naphthalene ring), 7.32 (s, 1H, hydrogen on the naphthalene ring).
The obtained pH color-changing reactive dye for sweat detection is subjected to performance test, and the test result is as follows:
fig. 1 is a spectral curve of the dye of example 1 under different pH conditions (pH =2 to 11), and fig. 2 is a color change 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 (the maximum absorption wavelength is 662 nm), and when the pH value of the solution is less than 6.0, the solution shows blue (the maximum absorption wavelength is 611 nm).
Fig. 3 is a spectral plot of the dye of example 1 under different pH conditions (pH = 4.01-6.51). As can be seen from fig. 3: when the solution pH =4.91, the solution showed blue color, and 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 solution for 0.70 pH units of the dye. Indicating that the color change precision of the dye is higher.
FIGS. 4 and 5 show the ratio of absorbance at the maximum absorption wavelength of the solution before and after the color change of the dye and the absorbance as a function of pH. As can be seen from fig. 4 and 5: the pH value at the isoelectric point for color change (absorbance value of the solution before and after color change) of the solution was 6.00.
Example 2
A method of preparing a pH-color changing reactive dye for sweat detection comprising the steps of:
(1) The primary condensation reaction was the same as in (1) of example 1;
(2) The secondary condensation reaction was the same as in step (2) of example 1;
(3) Diazotization-coupling reaction
50g of 49% (w/w) sulfuric acid solution was put into a 250mL three-necked flask, 4.38g (0.02 mol) of 2-amino-5, 6-dichlorobenzothiazole was slowly added thereto, and the mixture was stirred at 50 ℃ or lower for 1 hour to be sufficiently dissolved; slowly dripping 6.99g (0.022 mol) of 40% (w/w) nitrosyl sulfuric acid solution at the temperature of between 0 and 5 ℃, and reacting for 4 hours; adding sulfamic acid to eliminate excessive nitrous acid and 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 reaction endpoint by adopting H acid (1-amino-8-hydroxy-3, 6-sodium naphthalenedisulfonate); after the reaction is finished, salting out, filtering, washing with ethanol, and drying to obtain the pH color-changing reactive dye for sweat detection.
The structural formula of the obtained pH color-changing reactive dye for sweat detection is as follows:
the synthetic route is as follows:
the structure is characterized as follows:
1 H-NMR (400MHz, DMSO-d 6): Δ 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 the naphthalene ring), 7.82 (s, 1H, hydrogen on the naphthalene ring), 7.79 (d, 1H, hydrogen on the naphthalene ring), 7.52 (s, 1H, hydrogen on the naphthalene ring), 7.47 (s, 1H, hydrogen on the naphthalene ring), 7.41 (s, 1H, hydrogen on the naphthalene ring), 7.32 (s, 1H, hydrogen on the naphthalene ring).
The obtained pH color-changing reactive dye for sweat detection is subjected to performance test, and the test result is as follows:
fig. 6 is a spectral curve of the dye of example 2 under different pH conditions (pH =2 to 11), and fig. 7 is a color change 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 color (the maximum absorption wavelength is 590 nm), and when the pH value of the solution is less than 7.0, the solution shows red color (the maximum absorption wavelength is 539 nm).
Fig. 8 is a spectral plot of the dye of example 2 under different pH conditions (pH = 4.01-6.51). As can be seen from fig. 8: when the solution pH =6.30, the solution showed red color, the solution maximum absorption wavelength was 539nm; when the solution pH =7.06, the solution showed green color with a maximum absorption wavelength of 590nm, indicating a 51nm change in the maximum absorption wavelength of the solution for 0.76 pH units of the dye. The dye has higher color change precision.
FIGS. 9 and 10 show the absorbance at the maximum absorption wavelength of the solution before and after the color change of the dye and the ratio of absorbance to absorbance according to the change of pH. As can be seen from fig. 9 and 10: the pH at the isoelectric point for color change (absorbance of the solution before and after color change) of the solution was 6.84.
Example 3 application of color-changing dyes to printing of Cotton Fabric
Preparation of pH color-changing cotton fabric (140 g/m) 2 Pure cotton bleached knitted fabric) comprising the steps of:
the printing color paste formula is as follows: 40g/L of dye, 60g/L of raw paste (sodium alginate aqueous solution with the mass concentration of 4%), 15g/L of dye-resistant salt S, 60g/L of urea and 25g/L of sodium carbonate, and adding water to supplement 1000g;
the printing process comprises the following steps: printing → pre-baking (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 → drying.
The cotton fabric obtained in example 3 was soaked in sweat simulation solutions (as shown in table 1) with different pH values for performance test, and the test results are shown in table 2 below, fig. 11 to fig. 14:
TABLE 1
| Name and content of the ingredients | Sour 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 color fixing rate of the printed cotton fabric prepared by the dyes in the embodiments 1 and 2 is more than 50%, and the color fastness to washing, rubbing and sunlight is 3-4 grades and more.
As can be seen from fig. 11 to 12: the printed cotton fabric prepared from the dye in the example 1 is blue under the acid sweat condition, is green under the alkali sweat condition, 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 in the example 2 is red under the acid sweat condition, shows blue under the alkali sweat condition, and can be applied to human sweat detection.
Comparative example 1
A method of preparing a pH-chromic 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 acid aniline and 25.56g of water into a beaker, uniformly stirring, adjusting the pH value to 6.0-6.5 by adopting sodium carbonate, and fully dissolving to obtain a 2, 5-disulfonic acid aniline solution; then mixing the 2, 5-disulfonic acid aniline solution and 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 adjusted to 1.5 by adopting acetic acid, potassium chloride is added to precipitate solid powder (the mass ratio of the potassium chloride to the primary condensation liquid is 0.3. Dispersing the precipitated solid powder in absolute ethyl alcohol, filtering, freezing and drying to obtain a primary condensation product.
A primary condensation solution was prepared by dissolving 8.18g (0.02 mol) of the primary condensation product in 20mL of water. Adding 10.62g (0.01 mol) of P-3R (C.I. active blue 49) chromophore dry powder into the primary condensation solution quickly, raising the temperature to 30-35 ℃, adjusting the pH to 4.5-5.0 by using a saturated sodium bicarbonate solution, continuing the reaction at 30-35 ℃, and maintaining the pH value of the reaction solution to 4.5-5.0 by using a sodium carbonate solution. 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 a certain amount of potassium chloride to precipitate solid powder (the mass ratio of the potassium chloride to the secondary condensation liquid is 0.3. Dispersing the precipitated solid powder in absolute ethyl alcohol, filtering, freezing and drying to obtain a secondary condensation product.
Adding 7.22g (0.02 mol)) of m-sulfoacid para-ester into a 250mL beaker, adding 6mL of 36% (w/w) hydrochloric acid solution, uniformly stirring, cooling to 0-5 ℃, slowly adding 0.022mol 30% (w/w) sodium nitrite solution, and reacting for 1 h. Sulfamic acid is added to eliminate excess nitrous acid, and the meta-sulfonic acid para-ester diazonium salt is obtained. Dissolving 0.02mol of 18.23g of secondary condensation product in 20mL of water, reducing the temperature to 10-15 ℃, slowly adding the prepared meta-sulfonic acid para-ester 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 reaction end point by adopting H acid (1-amino-8-hydroxy-3, 6-sodium naphthalenedisulfonate); and after the reaction is finished, salting out, filtering, washing with ethanol, and drying to obtain the pH color-changing dye.
The structural formula of the obtained pH color-changing dye is as follows:
then, the cotton fabric is printed according to the method of the embodiment 3, the fixation rate of the dye on the cotton fabric is only 29.36%, and the color change pH value of the dyed fabric is not less than 9.0 (under a strong alkaline condition), so that the dye cannot be used for sweat detection.
Comparative example 2
A method of preparing a pH-chromic 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-diaminobenzene sulfonic acid and 25.56g of water into a beaker, uniformly stirring, adjusting the pH value to 6.0-6.5 by adopting sodium carbonate, and fully dissolving to obtain a 2, 4-diaminobenzene sulfonic acid sodium solution; then mixing the 2, 4-diaminobenzene sodium sulfonate solution and the cyanuric chloride solution, adjusting the pH value to 3.0-3.5 by adopting a saturated sodium bicarbonate solution, continuing the reaction at the temperature of 0-5 ℃, and maintaining the pH value of the reaction solution to 3.0-3.5 by adopting a sodium carbonate solution. 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 precipitate solid powder (the mass ratio of the potassium chloride to the primary condensation liquid is 0.3. Dispersing the separated solid powder in absolute ethyl alcohol, filtering, freezing and drying to obtain a primary condensation product.
A primary condensation solution was prepared by dissolving 7.16g (0.02 mol) of the primary condensation product in 20mL of water. Adding 10.62g (0.01 mol) of P-3R (C.I. active blue 49) chromophore dry powder into the primary condensation solution quickly, raising the temperature to 30-35 ℃, adjusting the pH to 4.5-5.0 by using a saturated sodium bicarbonate solution, continuing the reaction at 30-35 ℃, and maintaining the pH value of the reaction solution to 4.5-5.0 by using a sodium carbonate solution. 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 a certain amount of potassium chloride to precipitate solid powder (the mass ratio of the potassium chloride to the secondary condensation liquid is 0.3. Dispersing the precipitated solid powder in absolute ethyl alcohol, filtering, freezing and drying to obtain a secondary condensation product.
5.83g (0.02 mol)) of para-ester 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 30% (w/w) of sodium nitrite solution is slowly added, and the reaction is finished for 1 h. Sulfamic acid is added to eliminate excess nitrous acid, and the meta-sulfonic acid para-ester diazonium salt is obtained. Dissolving 0.02mol of 14.97g of secondary condensation product in 20mL of water, reducing the temperature to 10-15 ℃, slowly adding the prepared m-sulfonic acid para-ester 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 reaction end point by adopting H acid (1-amino-8-hydroxy-3, 6-sodium naphthalenedisulfonate); and after the reaction is finished, salting out, filtering, washing with ethanol, and drying to obtain the pH color-changing dye.
The structural formula of the obtained pH color-changing dye is as follows:
then, the cotton fabric is printed according to the method of the embodiment 3, the fixation rate of the dye on the cotton fabric is only 26.91%, and the color change pH value of the dyed fabric is not more than 1.6 (under the strong acid condition), so that the dye cannot be used for sweat detection.
Comparative example 3
A method of preparing a pH-chromic dye comprising the steps of:
(1) The same primary condensation reaction 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 adjusted to pH 9.0 by hydrochloric acid solution, then is slowly added into the primary condensation solution, the temperature is raised to 30 to 35 ℃, saturated sodium bicarbonate solution is used for adjusting the pH to 4.5 to 5.0, the reaction is continued at 30 to 35 ℃, and sodium carbonate solution is used for maintaining the pH value of the reaction solution to 4.5 to 5.0. 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 a certain amount of potassium chloride to precipitate solid powder (the mass ratio of the potassium chloride to the secondary condensation liquid is 0.3. Dispersing the precipitated solid powder in absolute ethyl alcohol, filtering, freezing and drying to obtain a secondary condensation product.
(3) Diazotization-coupling reaction
15.6g of 98% (w/w) sulfuric acid solution was added to a 250mL three-necked flask, 3.9g (0.02 mol) of 3-amino-5-nitrobenzoisothiazole was slowly added thereto, the mixture was stirred at 50 ℃ or lower for 1 hour to dissolve the resulting mixture sufficiently, 6.99g (0.022 mol) of 40% (w/w) nitrosylsulfuric acid solution was slowly added dropwise at 0 ℃ or lower, 3.90g of glacial acetic acid was slowly added dropwise at 0 to 5 ℃, and the reaction was completed for 4 hours. Adding sulfamic acid to eliminate excessive nitrous acid and 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 reaction end point by adopting H acid (1-amino-8-hydroxy-3, 6-sodium naphthalenedisulfonate); after the reaction is finished, salting out, suction filtration, ethanol washing and drying are carried out to obtain the obtained pH color-changing dye.
The structural formula of the obtained pH color-changing dye is as follows:
then, the cotton fabric is printed according to the method of the embodiment 3, the fixation rate of the dye on the cotton fabric is only 19.06 percent, the color change pH value of the dyed fabric is required to be less than or equal to 5.0, the dye cannot be used for sweat detection, and the washing fastness is level 3.
Comparative example 4
A method of preparing a pH-chromic dye comprising the steps of:
(1) The same primary condensation reaction 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 adjusted to pH 9.0 by hydrochloric acid solution, then is slowly added into the primary condensation solution, the temperature is raised to 30 to 35 ℃, saturated sodium bicarbonate solution is used for adjusting the pH to 4.5 to 5.0, the reaction is continued at 30 to 35 ℃, and sodium carbonate solution is used for maintaining the pH value of the reaction solution to 4.5 to 5.0. 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 a certain amount of potassium chloride to precipitate solid powder (the mass ratio of the potassium chloride to the secondary condensation liquid is 0.3. Dispersing the separated solid powder in absolute ethyl alcohol, filtering, freezing and drying to obtain a secondary condensation product.
(3) Diazotization-coupling reaction
15.6g of 98% (w/w) sulfuric acid solution is added into a 250mL three-neck flask, 3.48g (0.02 mol) of 2, 5-dinitrothiophene is slowly added, the mixture is stirred for 1 hour below 50 ℃ to be fully dissolved, 6.99g (0.022 mol) of 40% (w/w) nitrosyl sulfuric acid solution is slowly dripped below 0 ℃, 3.48g of glacial acetic acid is slowly dripped at 0-5 ℃, and the reaction is finished for 3-4 hours. Adding sulfamic acid to eliminate excessive nitrous acid and 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 reaction end point by adopting H acid (1-amino-8-hydroxy-3, 6-sodium naphthalenedisulfonate); after the reaction is finished, salting out, suction filtration, ethanol washing and drying are carried out to obtain the pH color-changing dye.
The structural formula of the obtained pH color-changing dye is as follows:
and then, printing the cotton fabric according to the method in the embodiment 3, wherein the fixation rate of the dye on the cotton fabric is only 19.06 percent, the color change pH value of the dyed fabric is not more than 3.0 (under the condition of strong acid), the dye cannot be used for sweat detection, and the washing fastness is grade 3.
Comparative example 5
A method of preparing a pH-chromic dye comprising the steps of:
(1) The primary condensation reaction was the same as in (1) of example 1;
(2) The secondary condensation was carried out in the same manner as in (2) of example 1;
(3) Diazotization-coupling reaction
Adding 18.45g of 98% (w/w) sulfuric acid solution into a 250mL three-neck flask, slowly adding 4.14g (0.02 mol) of 2, 6-dichloro-4-nitroaniline, stirring for 1h below 50 ℃ to fully dissolve the 2, 6.99g (0.022 mol) of 40% (w/w) nitrosyl sulfuric acid solution, slowly dropwise adding the nitrosyl sulfuric acid solution below 0 ℃, and finishing the reaction for 4 h; adding sulfamic acid to eliminate excessive nitrous acid and 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 reaction end point by adopting H acid (1-amino-8-hydroxy-3, 6-sodium naphthalenedisulfonate); after the reaction is finished, salting out, suction filtration, ethanol washing and drying are carried out to obtain the pH color-changing dye.
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 according to the method of example 3, with the dye only fixing on the cotton fabric at 26.37%.
Comparative example 6
A method of preparing a pH-chromic 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 value to 6.0-6.5 by adopting sodium carbonate, and fully dissolving to obtain a 2-amino-5-naphthol-7-sodium sulfonate solution; then mixing the 2-amino-5-naphthol-7-sodium sulfonate solution with a cyanuric chloride solution, adjusting the pH to 3.0-3.5 by adopting a saturated sodium bicarbonate solution, continuing the reaction at the temperature of 0-5 ℃, and maintaining the pH value of the reaction solution to 3.0-3.5 by adopting a sodium carbonate solution. 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 adjusted to 1.5 by adopting acetic acid, a certain amount of potassium chloride is added to precipitate solid powder (the mass ratio of the potassium chloride to the primary condensation liquid is 0.3. Dispersing the precipitated solid powder in absolute ethyl alcohol, filtering, freezing and drying to obtain a primary condensation product.
A primary condensation solution was prepared by dissolving 9.44g (0.02 mol) of the primary condensation product in 20mL of water. Adding 4.78g (0.02 mol) of 2-amino-5-naphthol-7-sulfonic acid to 15g of water to obtain a 2-amino-5-naphthol-7-sulfonic acid solution; then slowly adding the 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 a saturated sodium bicarbonate solution, continuously reacting at 30-35 ℃, and maintaining the pH value of the reaction solution to 4.5-5.0 by using a sodium carbonate solution. 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 a certain amount of potassium chloride to precipitate solid powder (the mass ratio of the potassium chloride to the secondary condensation liquid is 0.3. Dispersing the separated solid powder in absolute ethyl alcohol, filtering, freezing and drying to obtain a secondary condensation product.
50g of 49% (w/w) sulfuric acid solution was put into a 250mL three-necked flask, 4.38g (0.02 mol) of 2-amino-5, 6-dichlorobenzothiazole was slowly added thereto, and the mixture was stirred at 50 ℃ or lower for 1 hour to be sufficiently dissolved; slowly dripping 6.99g (0.022 mol) of 40% (w/w) nitrosyl sulfuric acid solution at the temperature of between 0 and 5 ℃, and reacting 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 2H at the temperature of 10-15 ℃, adjusting the pH value to 6, continuously reacting, and detecting the reaction end point by adopting H acid (1-amino-8-hydroxy-3, 6-sodium naphthalenedisulfonate); after the reaction is finished, salting out, suction filtration, ethanol washing and drying are carried out to obtain the pH color-changing dye.
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 according to the method of example 3, with the dye only fixing 41.43% on the cotton fabric.
Although the present invention has been described with reference to the preferred embodiments, it should be understood that various changes and modifications can be made therein by one skilled in the art without departing from the spirit and scope of the invention as defined by the appended claims.
Claims (10)
1. A pH color-changing reactive dye for sweat detection is characterized in that the structural formula is as shown in formula I:
wherein X and Y in formula I are independently formula 1 1 、R 2 And R 3 Independently is-H, -NO 2 、-OCH 3 And halogen;
or, X and Y in formula I are independently formula 2 1 And R 2 Independently is-H, -NO 2 ；
Or, X and Y in formula I are each independently of the other formula 3 1 And R 2 Independently is-H, -NO 2 ；
Or, in the formula I, X and Y are respectively and independently formula 4 1 And R 2 Independently is-H, -NO 2 ；
Or, X and Y in formula I are each independently of the other 5 1 And R 2 Independently is-H, -NO 2 CN and halogen;
2. a method of making the pH-color-changing reactive dye for sweat detection of claim 1, comprising the steps of:
(1) First condensation reaction
Adding cyanuric chloride and nekal in an ice water mixture, and fully pulping at the temperature of 0-5 ℃ to obtain cyanuric chloride solution; adding 2-amino-5-naphthol-7-sulfonic acid into water, adjusting the pH to 6.0-6.5, and fully dissolving to obtain a 2-amino-5-naphthol-7-sulfonic acid solution; then mixing the 2-amino-5-naphthol-7-sulfonic acid solution with a cyanuric chloride solution, adjusting the pH to 3.0-3.5, continuously reacting at the temperature of 0-5 ℃, and maintaining the pH value of the reaction solution to 3.0-3.5 by adopting a sodium carbonate solution; 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, freezing and 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-naphthalenedisulfonic acid into water, and adjusting the pH value to 6.0-6.5 to obtain 1-amino-8-hydroxy-3, 6-naphthalenedisulfonic acid sodium solution; then adding the 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, continuing the reaction at 30-35 ℃, and adopting a 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, freezing and drying to obtain a secondary condensation product;
(3) Diazotization-coupling reaction
Dissolving heterocyclic aromatic primary amine derivatives in acid, adding a diazotization reagent at the temperature of 0-5 ℃, keeping the temperature, reacting for 3-4 h, and after the reaction is finished, eliminating excessive nitrous acid 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 the heterocyclic aromatic primary amine diazonium salt into the solution, continuously reacting for 1-3H at the temperature of 10-15 ℃, adjusting the pH value to 6, continuously reacting, and detecting the reaction end point by adopting H acid (1-amino-8-hydroxy-3, 6-sodium naphthalenedisulfonate); after the reaction is finished, salting out, filtering, washing with ethanol, and drying to obtain the pH color-changing reactive dye for sweat detection.
3. The method 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 the primary condensation product to 1-amino-8-hydroxy-3, 6-naphthalenedisulfonic acid in step (2) is 1:1.
5. the method of claim 2, wherein the heterocyclic primary arylamine derivative in step (3) comprises one of formula 1, formula 2, formula 3, formula 4, or formula 5.
6. The process of claim 2, wherein the molar ratio of the secondary condensation product to the heterocyclic primary arylamine diazonium salt in step (3) is 1:2.
7. the process according to claim 2, wherein the diazotizing agent in step (3) is a sodium nitrite solution or a nitrosylsulfuric acid solution.
8. Use of the pH-color changing reactive dye for sweat detection of claim 1 in textile dyeing or printing.
9. A pH-color-changing cotton fabric obtained by dyeing the cotton fabric with the pH-color-changing reactive dye for sweat detection according to claim 1.
10. A sweat detection sensor using the pH-color-changing reactive dye for sweat detection according to claim 1 or the pH-color-changing cotton fabric according to claim 9.
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