CN115386244B - Double-color-body pH color-changing reactive dye and preparation and application thereof - Google Patents
Double-color-body pH color-changing reactive dye and preparation and application 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 double-color-body pH color-changing reactive dye and preparation and application thereof, and belongs to the technical field of fine chemical engineering. The invention prepares the pH color-changing dye with double color bodies 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 ethylenediamine 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 double-chromophore structure improves the combination probability of the dye and-H/-OH, and effectively adjusts the color-changing pH value of the dye to weak base, weak acid or even neutral conditions.
Description
Technical Field
The invention relates to a double-color-body pH color-changing reactive dye and preparation and application thereof, belonging to the technical field of fine chemical engineering.
Background
The pH color-changing textile can generate rapid, obvious and reversible color change when the external pH value changes, and further plays roles of warning, detecting, tracking and the like by transmitting the external change in a nondestructive mode-a visual signal mode. And pH-shifting textiles can be produced in large areas, and localized signals can be represented on the textile as localized color changes. In addition, the pH textile has the advantages of light weight, softness, washability and the like, is widely applied to the aspects of human health condition, wound healing or infection condition, food freshness, water quality, soil pH value, acid-base gas leakage and the like, and is widely paid attention to.
The pH color-changing textile is prepared by applying a compound with a pH indicating function to a fabric through dyeing, coating or printing and the like. For example: CN109763355B impregnating yarn or fabric with a dye containing a concentrate of natural materials (e.g., bayberry, benthic algae, etc.); CN106521987a coats a textile surface with a printing paste containing a pH-changing agent (natural plant pigment); CN103590263a applies a pH indicator dye (congo red dye, alizarin dye, or brilliant yellow dye) to the cotton fabric surface by dyeing; the above methods all use natural dyes as color-changing dyes, but have the problems of poor light fastness and poor durability.
The synthetic dye has the advantages of complete color spectrum, bright color, excellent color fastness and the like, and can also be used as a colorant of the pH color-changing textile. For example: CN114316204a polycondensates congo red, isophorone diisocyanate and polyether diol serving as a pH color-changing dye under the action of a catalyst to prepare a congo red-waterborne polyurethane polymer dye, and applies the congo red-waterborne polyurethane polymer dye to the surface of a textile by adopting a screen printing method; the congo red is connected to the main chain of the polymer through the covalent bond, so that the dissociation of the color bodies is effectively reduced; however, since the polymer dye has film forming property, it affects the pH response speed of the textile on one hand and is unfavorable for the hand feeling and air permeability of the pH color-changing textile on the other hand. Applicant (Sensors and Actuators B: chemical,2014,204: 167-174.) previously prepared a pH-discolored reactive dye by coupling a 3-amino-5-nitrobenzoisothiazole diazonium salt with a coupling component containing an H acid and s-triazine active group, but the dye had very low dye uptake when applied to dyeing of cotton fabrics. 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-based color-changing reactive dye that can undergo covalent bonding reaction with textiles and can change color under weak base, weak acid or even neutral conditions.
Disclosure of Invention
[ technical problem ]
At present, the existing pH color-changing reactive dye has lower dye uptake on fabrics, which results in lower color yield of the dyed fabrics, and the color-changing point needs to be under strong acid or strong alkaline conditions.
Technical scheme
In order to solve the problems, the invention prepares the pH color-changing dye with double color bodies 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 ethylenediamine 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 double-chromophore structure improves the combination probability of the dye and-H/-OH, and effectively adjusts the color-changing pH value of the dye to weak base, weak acid or even neutral conditions.
The first object of the invention is to provide a double-color-body pH color-changing reactive dye, 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 double color body pH color-changing reactive dye, 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 1-amino-8-hydroxy-3, 6-naphthalene disulfonic acid into water, regulating the pH to 6.0-6.5, and fully dissolving to obtain 1-amino-8-hydroxy-3, 6-naphthalene disulfonic acid solution; then mixing 1-amino-8-hydroxy-3, 6-naphthalene disulfonic 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; then adjusting the pH value of the primary condensation liquid to 1.5 by adopting acetic acid, adding potassium chloride to precipitate solid powder, dispersing the precipitated solid powder in absolute ethyl alcohol, filtering, and 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; adjusting the pH of ethylenediamine to 9.0; slowly adding ethylenediamine with pH of 9 into the primary condensation solution, raising the temperature to 30-35 ℃, adjusting the pH to 4.5-5.0, continuing the reaction 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; then acetic acid is adopted to adjust the pH value of the secondary condensation liquid to 2.0, and then potassium chloride is added 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, salting out, suction filtering, ethanol washing and drying are carried out to obtain the double-color-body pH color-changing reactive dye.
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 invention, the ratio of 1-amino-8-hydroxy-3, 6-naphthalenedisulfonic acid to water in step (1) is 0.651:1.
in one embodiment of the invention, the 1-amino-8-hydroxy-3, 6-naphthalene disulfonic acid solution in step (1) is pH adjusted with sodium carbonate.
In one embodiment of the present invention, the molar ratio of 1-amino-8-hydroxy-3, 6-naphthalene disulfonic 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 (0.3 to 0.6): 1.
in one embodiment of the invention, the pH of ethylenediamine in step (2) is adjusted using hydrochloric acid.
In one embodiment of the invention, the molar ratio of primary condensation product to ethylenediamine in step (2) is 2:1.
in one embodiment of the invention, the pH adjustment in step (2) is performed using 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 diazotizing agent in step (3) is a sodium nitrite solution (30% by mass concentration) or a nitrosylsulfuric acid solution (40% by mass concentration).
In one embodiment of the present invention, the molar ratio of the heterocyclic aromatic primary amine derivative 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 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 mass ratio of the heterocyclic aromatic primary amine derivative to the acid in step (3) is 0.01 to 10:1.
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 invention, the elimination of excess nitrous acid in step (3) is the addition of sulfamic acid.
In one embodiment of the invention, the ratio of the amount of secondary condensation product to water used in step (3) is from (0.2 to 0.6): 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.
the third object of the invention is the application of the double-color-body pH color-changing reactive dye in textile dyeing or printing.
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 double-color-body pH color-changing reactive dye.
A fifth object of the present invention is to provide a sweat detection sensor employing the double color body pH color changing reactive dye or pH color changing cotton fabric of the present invention.
[ advantageous effects ]
The double-color-body pH color-changing reactive dye solves the problems that the existing pH color-changing reactive dye has lower dye uptake on fabrics, and color-changing points need to be in strong acid or strong alkaline conditions, and the like, and expands the application under weak base, weak acid and neutral conditions.
Drawings
Fig. 1 is a spectral plot of the dye of example 1 at different pH conditions (ph=1 to 13.8).
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=4.55 to 6.45).
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 (ph=5.02-6.91).
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 physical image of the dye of example 1 printed cotton fabric under acidic conditions.
FIG. 12 is a physical image of the dye of example 1 printed cotton fabric under alkaline conditions.
FIG. 13 is a physical image of the dye of example 2 printed cotton fabric under acidic conditions.
FIG. 14 is a physical view of the dye of example 2 in an alkaline condition of the printed cotton fabric.
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:
the fastness to rubbing is determined according to GB/T3920-1997 "fastness to rubbing for textile colour fastness experiments".
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):
the solvent solutions are not specifically indicated in the examples, and the solvents are all water.
Example 1
A method for preparing a bi-color body pH-changing reactive dye 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 6.51g (0.02 mol, 98%) of 1-amino-8-hydroxy-3, 6-naphthalene disulfonic acid into 10g of water, adjusting the pH to 6.0-6.5 by sodium carbonate, and fully dissolving to obtain a 1-amino-8-hydroxy-3, 6-naphthalene disulfonic acid solution; then mixing 1-amino-8-hydroxy-3, 6-naphthalene disulfonic acid 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.
(2) Secondary condensation reaction
A primary condensation solution was prepared by dissolving 9.58g (0.02 mol) of the primary condensation product in 20mL of water. 0.62g (0.01 mol, 97%) of ethylenediamine is added into the primary condensation solution after the pH is adjusted to 9.0 by using a hydrochloric acid solution, the temperature is raised to 30-35 ℃, the pH is adjusted to 4.5-5.0 by using a 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 using a sodium carbonate solution. Detecting the reaction end point by adopting an amino reagent to obtain a secondary condensation liquid; and (3) 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 (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
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 10.09g of secondary condensation product in 20mL of water, reducing the temperature to 10-15 ℃, slowly adding the prepared 0.02mol of 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-sodium naphthalene disulfonate); after the reaction is finished, salting out, suction filtering, ethanol washing and drying are carried out to obtain the double-color-body pH color-changing reactive dye.
The structural formula of the obtained double-color-body pH color-changing reactive dye 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-), 9.01 (s, 2H, -OH), 8.18 (s, 4H, ar-H and hydrogen on naphthalene ring), 8.07 (s, 2H, ar-H), 7.52 (s, 2H, hydrogen on naphthalene ring), 7.47 (s, 2H, hydrogen on naphthalene ring), 7.01 (s, 2H, -NH), 3.47 (m, 4H, HNCH 2 CH 2 NH)。
And performing performance test on the obtained double-color-body pH color-changing reactive dye, wherein the test result is as follows:
fig. 1 is a spectrum of the dye of example 1 under different pH conditions (ph=1 to 13.8), 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 purple color (the maximum absorption wavelength is 570 nm), and when the pH value of the solution is less than 6.0, the solution shows red color (the maximum absorption wavelength is 520 nm).
Fig. 3 is a spectral plot of the dye of example 1 at different pH conditions (ph=4.55 to 6.45). As can be seen from fig. 3: the maximum absorption wavelength of the solution was 520nm when the pH of the solution was=5.03, and 570nm when the pH of the solution was=6.20, indicating that the dye had a 50nm change in the maximum absorption wavelength of the solution within 1.17 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 5.66.
Example 2
A method for preparing a bi-color body pH-changing reactive 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
15.6g of 98% (w/w) sulfuric acid 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 enable the solution to be fully dissolved, 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 ℃, the reaction is finished for 4h, and sulfamic acid is added to eliminate excessive nitrous acid, so that the heterocyclic aromatic primary amine diazonium salt is obtained. Dissolving 0.01mol of 10.09g of secondary condensation product in 20mL of water, reducing the temperature to 10-15 ℃, slowly adding the prepared 0.02mol of 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-sodium naphthalene disulfonate); after the reaction is finished, salting out, suction filtering, ethanol washing and drying are carried out to obtain the double-color-body pH color-changing reactive dye.
The structural formula of the obtained double-color-body pH color-changing reactive dye 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, 4H, ar-H), 8.26 (s, 2H, ar-H), 8.18 (s, 2H, hydrogen on naphthalene ring), 7.52 (s, 2H, hydrogen on naphthalene ring), 7.47 (s, 2H, hydrogen on naphthalene ring), 7.01 (s, 2H, -NH), 3.47 (m, 4H, HNCH 2 CH 2 NH)。
And performing performance test on the obtained double-color-body pH color-changing reactive dye, wherein the test result is as follows:
fig. 6 is a spectrum of the dye of example 2 at different pH (ph=3 to 12.5), 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 6.5, the solution is green (the maximum absorption wavelength is 675 nm), and when the pH value of the solution is less than 6.5, the solution is purple (the maximum absorption wavelength is 574 nm).
Fig. 8 is a spectral plot of the dye of example 2 at different pH conditions (ph=5.02-6.91). As can be seen from fig. 8: when the solution ph=5.63, the solution showed purple color, and the maximum absorption wavelength of the solution was 574nm; when the solution ph=6.56, the solution showed green color with a maximum absorption wavelength of 675nm, which indicates that the dye had a change in the maximum absorption wavelength of 101nm of the solution within 0.93 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 6.24.
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 make up 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:
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 results of performance testing of printed fabrics
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 above 55%, and the fastness to washing, rubbing and sunlight reach 3-4 levels and above.
As can be seen from fig. 11 to 12: the printed cotton fabric prepared by the dye of the example 1 is red under the condition of acid sweat and purple 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 blue under the condition of acid sweat and green 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, 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 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.
Adding 7.22g (0.02 mol)) of para-ester of m-sulfonic acid into a 250mL beaker, adding 6mL of 36% (w/w) hydrochloric acid solution, stirring uniformly, cooling to 0-5 ℃, slowly adding 0.022mol of 30% (w/w) sodium nitrite solution, and adding sulfamic acid to eliminate excessive nitrous acid after reaction for 1 hour to obtain the diazonium salt of the para-ester of m-sulfonic acid. 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:
the cotton fabric was then printed in the manner of example 3, the fixation of the dye on the cotton fabric being only 29.36% and the dyed fabric having a color change pH value of 9.0 or more (strong alkaline conditions).
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, 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 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.
Adding 5.83g (0.02 mol)) para-ester into a 250mL beaker, adding 6mL 36% (w/w) hydrochloric acid solution, uniformly stirring, cooling to 0-5 ℃, slowly adding 0.022mol 30% (w/w) sodium nitrite solution, and finishing the reaction for 1 h; 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:
the cotton fabric was then printed in the manner of example 3, the fixation of the dye on the cotton fabric being only 26.91% and the dyed fabric having a color change pH of 1.6 or less (strong acid conditions).
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-neck flask, 3.9g (0.02 mol) of 3-amino-5-nitrobenzoisothiazole is slowly added, stirring is carried out for 1h below 50 ℃ to enable the solution to be fully dissolved, 6.99g (0.022 mol) of 40% (w/w) nitrosylsulfuric acid solution is slowly added dropwise below 0 ℃, a certain amount of glacial acetic acid is slowly added dropwise at 0-5 ℃, and the reaction is finished 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 0.02mol of 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 cotton fabric was then printed in the manner of example 3, the fixation of the dye on the cotton fabric being only 19.06%, the color-changing pH of the dyed fabric being at most 5.0 and the washing fastness being of grade 3.
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-neck flask, 3.48g (0.02 mol) of 2, 5-dinitrothiophene is slowly added, stirring is carried out for 1h below 50 ℃ to enable the 2, 5-dinitrothiophene to be fully dissolved, 6.99g (0.022 mol) of 40% (w/w) nitrosylsulfuric acid solution is slowly added dropwise below 0 ℃, a certain amount 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:
the cotton fabric was then printed in the manner of example 3, the fixation of the dye on the cotton fabric being only 19.06%, the dyed fabric having a color change pH value of 3.0 or less (strong acid condition) and a washing fastness of 3.
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 the solution, 6.99g (0.022 mol) of 40% (w/w) nitrosylsulfuric acid solution is slowly added dropwise below 0 ℃ 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 10.09g 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 39.36%.
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. 0.62g (0.01 mol, 97%) of ethylenediamine is added into the primary condensation solution after the pH is adjusted to 9.0 by using a hydrochloric acid solution, the temperature is raised to 30-35 ℃, the pH is adjusted to 4.5-5.0 by using a 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 using a 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.
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 9.07g 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 to obtain the double-color-body pH color-changing reactive dye.
The structural formula of the obtained double-color-body pH color-changing reactive dye is as follows:
the synthetic route is as follows:
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the cotton fabric was then printed as in example 3, the dye fixation on cotton fabric being only 39.36%.
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 (9)
1. The double-color-body pH color-changing reactive dye is characterized by comprising the following structural formula:
2. a process for preparing the bi-color body pH color-changing reactive dye 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 1-amino-8-hydroxy-3, 6-naphthalene disulfonic acid into water, regulating the pH to 6.0-6.5, and fully dissolving to obtain 1-amino-8-hydroxy-3, 6-naphthalene disulfonic acid solution; then mixing 1-amino-8-hydroxy-3, 6-naphthalene disulfonic 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; then adjusting the pH value of the primary condensation liquid to 1.5 by adopting acetic acid, adding potassium chloride to precipitate solid powder, dispersing the precipitated solid powder in absolute ethyl alcohol, filtering, and 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; adjusting the pH of ethylenediamine to 9.0; slowly adding ethylenediamine with pH of 9 into the primary condensation solution, raising the temperature to 30-35 ℃, adjusting the pH to 4.5-5.0, continuing the reaction 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; then acetic acid is adopted to adjust the pH value of the secondary condensation liquid to 2.0, and then potassium chloride is added 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, salting out, suction filtering, ethanol washing and drying are carried out to obtain the double-color-body pH color-changing reactive dye.
3. The method according to claim 2, wherein in the step (1), the mass ratio of the cyanuric chloride, the nekal and the ice water mixture is (3.5-4.0): (0.1-0.3): 15.
4. the process of claim 2, wherein the molar ratio of primary condensation product to ethylenediamine in step (2) is 2:1.
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. use of a bi-color body pH color changing reactive dye according to claim 1 for dyeing or printing textiles.
8. The use according to claim 7, wherein the textile comprises cotton, viscose, hemp or blends thereof and fabrics thereof.
9. A sweat detection sensor employing the dichromatic pH-changing reactive dye of claim 1.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1426382A (en) * | 1972-03-10 | 1976-02-25 | Ciba Geigy Ag | Fibre-reactive metallised idsazo dyestuffs their manufacture and use |
| GB1569246A (en) * | 1977-03-15 | 1980-06-11 | Bayer Ag | Process for the preparation of azo reactive dyestuffs |
| CN108084732A (en) * | 2017-12-12 | 2018-05-29 | 江苏德美科化工有限公司 | A kind of heavy metal free ion high antioxidant activity gray dyes and preparation method thereof |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1426382A (en) * | 1972-03-10 | 1976-02-25 | Ciba Geigy Ag | Fibre-reactive metallised idsazo dyestuffs their manufacture and use |
| GB1569246A (en) * | 1977-03-15 | 1980-06-11 | Bayer Ag | Process for the preparation of azo reactive dyestuffs |
| CN108084732A (en) * | 2017-12-12 | 2018-05-29 | 江苏德美科化工有限公司 | A kind of heavy metal free ion high antioxidant activity gray dyes and preparation method thereof |
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