CN114235767A

CN114235767A - Fluorescent fiber for detecting formaldehyde and preparation method thereof

Info

Publication number: CN114235767A
Application number: CN202111541612.8A
Authority: CN
Inventors: 曾燕艳; 梁志辉; 王玥婷; 罗群; 范洪波; 焦哲; 鲁莉; 黄文俊; 孙煜轲
Original assignee: Dongguan University of Technology
Current assignee: Dongguan University of Technology
Priority date: 2021-12-16
Filing date: 2021-12-16
Publication date: 2022-03-25

Abstract

The invention discloses a fluorescent fiber for detecting formaldehyde and a preparation method thereof. The method comprises the following steps: step 1: uniformly dispersing an AHB fluorescent compound in dimethyl sulfoxide to obtain a solution A; dissolving polycaprolactone in chloroform to obtain a solution B; uniformly mixing the solution A and the solution B to obtain an AHB fiber spinning solution; step 2: putting the AHB fiber spinning solution into an injector, setting the injection voltage, the injection speed and the receiving distance, and spinning; and drying to obtain the fluorescent fiber. Has the advantages that: (1) in the scheme, a novel AHB fluorescent compound is prepared, is 2-amino-6-hydrazino-1H-benzisoquinoline-1, 3- (2H) -diketone, and improves the sensitivity of formaldehyde detection. (2) The fluorescent fiber is used for directly detecting indoor air formaldehyde, and is convenient and fast, strong in operability and high in sensitivity.

Description

Fluorescent fiber for detecting formaldehyde and preparation method thereof

Technical Field

The invention relates to the technical field of formaldehyde detection, in particular to a fluorescent fiber for detecting formaldehyde and a preparation method thereof.

Background

Formaldehyde is an important industrial raw material and is widely applied to the industrial fields of chemical industry, textile industry and the like. For example, the formaldehyde is often applied to interior decoration materials or some daily necessities in a mode of phenolic resin, and the volatilized formaldehyde is toxic gas, can cause symptoms such as cough, nausea and the like caused by stimulation of eyes, nose, throat and the like, and even causes a series of hazards such as pulmonary edema, carcinogenesis, gene mutation and the like after being injected for a long time.

Along with the improvement of quality of life and environmental awareness, people pay more attention to formaldehyde detection, which also promotes the research increase in the aspect. At present, common detection methods comprise spectrophotometry, chromatography and the like, and the two methods are complex to operate and have high requirements on objective factors such as detection environment, operators and the like, so the method has low popularization and high limitation, and is not beneficial to daily routine detection. In the prior art, researchers prepare fluorescent molecular probes for detecting formaldehyde, generate chemical signals by utilizing intermolecular interconversion, and feed the chemical signals back to the outside; but the fluorescent probe is directly used for detection, so that the cost is higher, and the daily storage stability is low; meanwhile, the problems of poor reproducibility, low sensitivity, high detection line and the like exist.

In conclusion, the preparation of the fluorescent fiber for detecting formaldehyde, which has high sensitivity and good stability, is of great significance in solving the problems.

Disclosure of Invention

The invention aims to provide a fluorescent fiber for detecting formaldehyde and a preparation method thereof, so as to solve the problems in the background technology.

In order to solve the technical problems, the invention provides the following technical scheme:

a preparation method of a fluorescent fiber for detecting formaldehyde comprises the following steps:

step 1: uniformly dispersing an AHB fluorescent compound in dimethyl sulfoxide to obtain a solution A; dissolving polycaprolactone in chloroform to obtain a solution B; uniformly mixing the solution A and the solution B to obtain an AHB fiber spinning solution;

step 2: putting the AHB fiber spinning solution into an injector, setting the spraying speed, the spraying voltage and the receiving distance, and carrying out electrostatic spinning; and drying to obtain the fluorescent fiber.

Preferably, the AHB fluorescent compound is 2-amino-6-hydrazino-1H-benzisoquinoline-1, 3- (2H) -diketone with the structural formula

Preferably, in the step 1, the concentration of the solution A is 0.5 g/L-3 g/L; the concentration of the solution B is 20-25%; the volume ratio of the dimethyl sulfoxide to the trichloromethane is 1: 2.

Preferably, in the step 1, the concentration of the solution A is 1.5 g/L; the concentration of the solution B is 25%.

Optimally, in the step 2, the spraying speed is 0.01-0.12 mL/min; the injection voltage is 8-15 kV; the receiving distance is 6-13 cm.

Preferably, in the step 2, the injection speed is 0.05 mL/min; the injection voltage is 10 kV; the receiving distance is 10 cm.

Preferably, the preparation method of the AHB fluorescent compound comprises the following steps: (1) dispersing 3mmol of 4-bromo-1, 8-naphthalic anhydride in 50-60 mL of ethanol solvent under nitrogen atmosphere, dropwise adding 3mmol of hydrazine hydrate, setting the temperature to be 80-85 ℃, refluxing for 5-7 hours, cooling to room temperature, filtering and washing to obtain a crude product; (2) weighing the crude product, hydrazine hydrate and potassium carbonate according to the mass ratio of 2:1: 1.62; dissolving the crude product in ethylene glycol monomethyl ether in a nitrogen atmosphere, adding hydrazine hydrate and potassium carbonate, setting the temperature to be 105-115 ℃, and refluxing for 4-6 hours; and (3) distilling under reduced pressure to remove ethylene glycol monomethyl ether, performing chromatography assistance by using methanol/dichloromethane, and crystallizing by using ethanol to obtain the AHB fluorescent compound.

Preferably, the fluorescent fiber is prepared by the preparation method of the fluorescent fiber for detecting formaldehyde.

Preferably, the fluorescent fiber is applied to detecting formaldehyde, and the detection method comprises the following steps: placing the fluorescent fiber at 0-0.10 mg/m³Standing for 30 minutes in the formaldehyde environment, observing the fluorescence effect under 365nm ultraviolet illumination, taking a picture and recording, testing the gray value of the fluorescence fiber in the picture by adopting ImageJ software, and constructing a linear regression equation y which is ax + b through the linear relation between formaldehyde with different concentrations and the gray value, wherein x is the formaldehyde concentration, y is the gray value, and the linear correlation coefficient is more than 0.95; when the method is used for detecting formaldehyde in the detection environment, the concentration of the formaldehyde in the environment can be directly obtained according to the gray value.

Preferably, when the concentration of the AHB fluorescent compound in solution a is 1.5g/L, the linear regression equation is 701.45x +107.34, and the linear correlation coefficient is 0.9955.

In the technical scheme, a novel AHB fluorescent compound is prepared, and is 2-amino-6-hydrazino-1H-benzisoquinoline-1, 3- (2H) -diketone; and dissolving the fiber in dimethyl sulfoxide as a solvent, injecting the dissolved fiber into a trichloromethane solution containing Polycaprolactone (PCL) to obtain a spinning solution, and spinning to obtain the AHB fluorescent fiber.

Compared with the prior art, the invention has the following beneficial effects:

(1) in the scheme, 2-amino-6-hydrazino-1H-benzisoquinoline-1, 3- (2H) -diketone, of which the 2-position and the 6-position can react with formaldehyde, is prepared through two substitution reactions under different conditions, namely an AHB fluorescent compound; through the cooperation between the two sites, the sensitivity of formaldehyde detection is improved.

Reaction mechanism of AHB fluorescent fiber: mainly because of the electron-donating effect of amino in the structure, the photoinduced electron transfer and fluorescence quenching are realized; therefore, when the AHB fluorescent fiber is not contacted with formaldehyde, no fluorescence phenomenon occurs under 365nm ultraviolet lamp irradiation, and after the AHB fluorescent fiber is contacted with formaldehyde, amino groups react with the formaldehyde to generate-N ═ CH₂Blocking the transfer of photoinduced electrons, resulting in significant fluorescence recovery.

(2) According to the scheme, the fluorescent compound and the polycaprolactone are spun, so that the cost is reduced on the basis of not influencing the formaldehyde detection sensitivity and the fluorescence signal, the daily storage stability of the fluorescent substance is improved, and the fluorescent substance can be stored in a dry environment daily.

In the scheme, the fiber with good appearance is prepared by limiting the concentration of polycaprolactone in the spinning solution and optimizing conditions such as jet voltage, jet speed, receiving distance and the like in the spinning process parameters. When the polycaprolactone is too high, adhesion and beads can be generated in the spraying process, fibers are not easy to form, and irregular winding yarns are more; similarly, the phenomenon of discontinuous curling can be generated when the jet speed is too slow, and the spinning fusion phenomenon can be generated when the jet speed is too fast; the spinning fusion phenomenon can be generated when the jet voltage is too high, and the spinning can not be spun when the receiving distance is too short. The change of the process conditions has influence on the appearance and the tensile property of the fluorescent fiber, so that the stability and the reproducibility of the fluorescent fiber in formaldehyde detection are influenced; the preferred scheme is that the concentration of polycaprolactone is 25 percent; the spraying speed is 0.05 mL/min; the injection voltage is 10 kV; the receiving distance is 8 cm.

(3) In the scheme, the doping amount of the AHB fluorescent compound in the fiber is limited by limiting the volume ratio of dimethyl sulfoxide and chloroform solution as solvents in the solution A and the solution B and the concentration of the solutions, and when the concentration of the solution A is lower than 0.5g/L, the gray value of a fiber photo under ultraviolet irradiation is lower and is not easy to directly distinguish; in general, the higher the amount of doping, the more fluorescentThe higher the reactivity; at present, the concentration of the solution A is 1.5g/L, and the concentration of the fluorescent fiber prepared under the concentration is 0-0.10 mg/m³The linear regression equation y obtained under the formaldehyde concentration is 701.45x +107.34, and the linear correlation coefficient is 0.9955; the formaldehyde concentration in the environment can be directly calculated according to the gray value of the fluorescent fibers in the environment, and the indication error between the test result and the detection result of the standard spectrophotometer is small, so that the fluorescent fibers are used for directly detecting the formaldehyde in the indoor air, and the method is convenient and fast, strong in operability and high in sensitivity.

Drawings

The accompanying drawings, which are included to provide a further understanding of the invention and are incorporated in and constitute a part of this specification, illustrate embodiments of the invention and together with the description serve to explain the principles of the invention and not to limit the invention. In the drawings:

FIG. 1 is a graph of formaldehyde concentration versus gray scale value for the fluorescent fibers of example 1;

FIG. 2 is a scanning electron micrograph of a fluorescent fiber in example 1;

FIG. 3 is a scanning electron micrograph of the fluorescent fiber in comparative example 1;

FIG. 4 is a scanning electron micrograph of the fluorescent fiber in comparative example 2;

FIG. 5 is a scanning electron micrograph of the fluorescent fiber in comparative example 3;

FIG. 6 is a scanning electron micrograph of a fluorescent fiber in comparative example 4;

FIG. 7 is a scanning electron micrograph of a fluorescent fiber in comparative example 5;

FIG. 8 is a scanning electron micrograph of a fluorescent fiber in comparative example 6;

FIG. 9 is a scanning electron micrograph of a fluorescent fiber in comparative example 7;

FIG. 10 is a scanning electron micrograph of a fluorescent fiber in comparative example 8;

FIG. 11 is a scanning electron micrograph of a fluorescent fiber in comparative example 9;

FIG. 12 is a scanning electron micrograph of a fluorescent fiber in comparative example 10;

FIG. 13 is a scanning electron micrograph of a fluorescent fiber in comparative example 11;

FIG. 14 is a scanning electron micrograph of a fluorescent fiber in comparative example 12;

FIG. 15 is a scanning electron micrograph of a fluorescent fiber in comparative example 13;

FIG. 16 is a scanning electron micrograph of a fluorescent fiber in comparative example 14;

FIG. 17 is a scanning electron micrograph of a fluorescent fiber in comparative example 15;

FIG. 18 is a scanning electron micrograph of a fluorescent fiber in comparative example 16;

FIG. 19 is a scanning electron micrograph of a fluorescent fiber in comparative example 17;

FIG. 20 is a scanning electron micrograph of a fluorescent fiber in comparative example 18;

FIG. 21 is a scanning electron micrograph of a fluorescent fiber in comparative example 19;

FIG. 22 is a scanning electron micrograph of a fluorescent fiber in comparative example 20;

FIG. 23 is a scanning electron micrograph of a fluorescent fiber in comparative example 21;

FIG. 24 is a scanning electron micrograph of a fluorescent fiber in comparative example 22;

FIG. 25 is a scanning electron micrograph of a fluorescent fiber in comparative example 23;

FIG. 26 is a scanning electron micrograph of a fluorescent fiber in comparative example 24;

FIG. 27 is a scanning electron micrograph of a fluorescent fiber in comparative example 25;

FIG. 28 is a scanning electron micrograph of a fluorescent fiber in comparative example 26;

FIG. 29 is a scanning electron micrograph of a fluorescent fiber in comparative example 27;

FIG. 30 is a scanning electron micrograph of a fluorescent fiber in comparative example 28;

FIG. 31 is a photograph of the fluorescent fiber of example 1 under ultraviolet light;

FIG. 32 is a photograph of the fluorescent fiber of example 2 under ultraviolet light;

FIG. 33 is a photograph of the fluorescent fiber of example 3 under ultraviolet light;

FIG. 34 is a photograph of the fluorescent fiber of example 4 under ultraviolet light;

FIG. 35 is a photograph of the fluorescent fiber of example 5 under ultraviolet light;

FIG. 36 shows the results of example 1, in which the concentration of formaldehyde in the fluorescent fibers was 0mg/m³A photo under ultraviolet light;

FIG. 37 shows the results of example 1, in which the concentration of formaldehyde in the fluorescent fibers was 0.01mg/m³A photo under ultraviolet light;

FIG. 38 shows the concentration of formaldehyde in the fluorescent fibers of example 1 at 0.02mg/m³A photo under ultraviolet light;

FIG. 39 shows the results of example 1, in which the concentration of formaldehyde in the fluorescent fibers was 0.03mg/m³A photo under ultraviolet light;

FIG. 40 shows the concentration of formaldehyde in the fluorescent fibers of example 1 at 0.04mg/m³A photo under ultraviolet light;

FIG. 41 shows the concentration of formaldehyde in the fluorescent fibers of example 1 at 0.06mg/m³A photo under ultraviolet light;

FIG. 42 shows the concentration of formaldehyde in the fluorescent fibers of example 1 at 0.08mg/m³A photo under ultraviolet light;

FIG. 43 shows the results of example 1, in which the concentration of formaldehyde in the fluorescent fiber was 0.10mg/m³Photo under ultraviolet light.

Detailed Description

The technical solutions in the embodiments of the present invention will be clearly and completely described below, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.

Example 1:

step 1: (1) dispersing 3mmol of 4-bromo-1, 8-naphthalic anhydride in 50mL of ethanol solvent under the atmosphere of nitrogen, dropwise adding 3mmol of hydrazine hydrate, setting the temperature at 82 ℃, refluxing for 6 hours, cooling to room temperature, filtering and washing to obtain a crude product; (2) under the nitrogen atmosphere, 130mg of the crude product is sequentially dissolved in ethylene glycol monomethyl ether, 65mg of hydrazine hydrate and 105mg of potassium carbonate are added, the temperature is set to be 110 ℃, and the reflux is carried out for 6 hours; and (3) distilling under reduced pressure to remove ethylene glycol monomethyl ether, performing chromatography assistance by using methanol/dichloromethane, and crystallizing by using ethanol to obtain the AHB fluorescent compound.

Step 2: uniformly dispersing 3mg of AHB fluorescent compound in 2mL of dimethyl sulfoxide to obtain a solution A with the concentration of 1.5 g/L; dissolving polycaprolactone in 4mL of chloroform to obtain a 25% solution B; uniformly mixing the solution A and the solution B to obtain an AHB fiber spinning solution;

and step 3: placing the AHB fiber spinning solution into an injector, setting the spraying speed to be 0.05mL/min, the spraying voltage to be 10kV, the receiving distance to be 10cm, and carrying out electrostatic spinning; the resulting mixture was dried at 25 ℃ for 1 hour under vacuum to obtain a fluorescent fiber.

Example 2:

step 1: (1) dispersing 3mmol of 4-bromo-1, 8-naphthalic anhydride in 50mL of ethanol solvent under the nitrogen atmosphere, dropwise adding 3mmol of hydrazine hydrate, setting the temperature at 80 ℃, refluxing for 7 hours, cooling to room temperature, filtering and washing to obtain a crude product; (2) under the nitrogen atmosphere, 130mg of the crude product is sequentially dissolved in ethylene glycol monomethyl ether, 65mg of hydrazine hydrate and 105mg of potassium carbonate are added, the temperature is set to be 105 ℃, and the reflux is carried out for 6 hours; and (3) distilling under reduced pressure to remove ethylene glycol monomethyl ether, performing chromatography assistance by using methanol/dichloromethane, and crystallizing by using ethanol to obtain the AHB fluorescent compound.

Step 2: uniformly dispersing 2.5mg of AHB fluorescent compound in 2mL of dimethyl sulfoxide to obtain a solution A with the concentration of 1.25 g/L; dissolving polycaprolactone in 4mL of chloroform to obtain a 25% solution B; uniformly mixing the solution A and the solution B to obtain an AHB fiber spinning solution;

Example 3:

step 1: (1) dispersing 3mmol of 4-bromo-1, 8-naphthalic anhydride in 50-60 mL of ethanol solvent under nitrogen atmosphere, dropwise adding 3mmol of hydrazine hydrate, setting the temperature at 85 ℃, refluxing for 5 hours, cooling to room temperature, filtering and washing to obtain a crude product; (2) under the nitrogen atmosphere, 130mg of the crude product is sequentially dissolved in ethylene glycol monomethyl ether, 65mg of hydrazine hydrate and 105mg of potassium carbonate are added, the temperature is set to be 115 ℃, and reflux is carried out for 4 hours; and (3) distilling under reduced pressure to remove ethylene glycol monomethyl ether, performing chromatography assistance by using methanol/dichloromethane, and crystallizing by using ethanol to obtain the AHB fluorescent compound.

Step 2: uniformly dispersing 2mg of AHB fluorescent compound in 2mL of dimethyl sulfoxide to obtain a solution A with the concentration of 1 g/L; dissolving polycaprolactone in 4mL of chloroform to obtain a 25% solution B; uniformly mixing the solution A and the solution B to obtain an AHB fiber spinning solution;

Example 4:

Step 2: uniformly dispersing 1.5mg of AHB fluorescent compound in 2mL of dimethyl sulfoxide to obtain a solution A with the concentration of 0.75 g/L; dissolving polycaprolactone in 4mL of chloroform to obtain a 25% solution B; uniformly mixing the solution A and the solution B to obtain an AHB fiber spinning solution;

Example 5:

Step 2: uniformly dispersing 1.0mg of AHB fluorescent compound in 2mL of dimethyl sulfoxide to obtain a solution A with the concentration of 0.5 g/L; dissolving polycaprolactone in 4mL of chloroform to obtain a 25% solution B; uniformly mixing the solution A and the solution B to obtain an AHB fiber spinning solution;

Comparative example 1: the solution of solution B was adjusted to 15% and the rest was the same as in example 1.

The concrete modification is as follows:

step 2: uniformly dispersing 3mg of AHB fluorescent compound in 2mL of dimethyl sulfoxide to obtain a solution A with the concentration of 1.5 g/L; dissolving polycaprolactone in 4mL of chloroform to obtain a 15% solution B; uniformly mixing the solution A and the solution B to obtain an AHB fiber spinning solution;

comparative example 2: the solution of solution B was adjusted to 20% and the rest was the same as in example 1.

The concrete modification is as follows:

step 2: uniformly dispersing 3mg of AHB fluorescent compound in 2mL of dimethyl sulfoxide to obtain a solution A with the concentration of 1.5 g/L; dissolving polycaprolactone in 4mL of chloroform to obtain a 20% solution B; uniformly mixing the solution A and the solution B to obtain an AHB fiber spinning solution;

comparative example 3: the solution of solution B was adjusted to 30% and the rest was the same as in example 1.

The concrete modification is as follows:

step 2: uniformly dispersing 3mg of AHB fluorescent compound in 2mL of dimethyl sulfoxide to obtain a solution A with the concentration of 1.5 g/L; dissolving polycaprolactone in 4mL of chloroform to obtain a 30% solution B; uniformly mixing the solution A and the solution B to obtain an AHB fiber spinning solution;

comparative example 4: the ejection speed was set to 0.01mL/min, and the rest was the same as in example 1.

The concrete modification is as follows:

and step 3: placing the AHB fiber spinning solution into an injector, setting the spraying speed to be 0.01mL/min, the spraying voltage to be 10kV, the receiving distance to be 10cm, and carrying out electrostatic spinning; the resulting mixture was dried at 25 ℃ for 1 hour under vacuum to obtain a fluorescent fiber.

Comparative example 5: the ejection speed was set to 0.02mL/min, and the rest was the same as in example 1.

The concrete modification is as follows:

and step 3: placing the AHB fiber spinning solution into an injector, setting the spraying speed to be 0.02mL/min, the spraying voltage to be 10kV, the receiving distance to be 10cm, and carrying out electrostatic spinning; the resulting mixture was dried at 25 ℃ for 1 hour under vacuum to obtain a fluorescent fiber.

Comparative example 6: the ejection speed was set to 0.03mL/min, and the rest was the same as in example 1.

The concrete modification is as follows:

and step 3: placing the AHB fiber spinning solution into an injector, setting the spraying speed to be 0.03mL/min, the spraying voltage to be 10kV, the receiving distance to be 10cm, and carrying out electrostatic spinning; the resulting mixture was dried at 25 ℃ for 1 hour under vacuum to obtain a fluorescent fiber.

Comparative example 7: the injection rate was set to 0.04mL/min, and the rest was the same as in example 1.

The concrete modification is as follows:

and step 3: placing the AHB fiber spinning solution into an injector, setting the spraying speed to be 0.04mL/min, the spraying voltage to be 10kV, the receiving distance to be 10cm, and carrying out electrostatic spinning; the resulting mixture was dried at 25 ℃ for 1 hour under vacuum to obtain a fluorescent fiber.

Comparative example 8: the injection rate was set to 0.06mL/min, and the rest was the same as in example 1.

The concrete modification is as follows:

and step 3: placing the AHB fiber spinning solution into an injector, setting the spraying speed to be 0.06mL/min, the spraying voltage to be 10kV, the receiving distance to be 10cm, and carrying out electrostatic spinning; the resulting mixture was dried at 25 ℃ for 1 hour under vacuum to obtain a fluorescent fiber.

Comparative example 9: the ejection speed was set to 0.07mL/min, and the rest was the same as in example 1.

The concrete modification is as follows:

and step 3: placing the AHB fiber spinning solution into an injector, setting the spraying speed to be 0.07mL/min, the spraying voltage to be 10kV, the receiving distance to be 10cm, and carrying out electrostatic spinning; the resulting mixture was dried at 25 ℃ for 1 hour under vacuum to obtain a fluorescent fiber.

Comparative example 10: the injection rate was set to 0.08mL/min, and the rest was the same as in example 1.

The concrete modification is as follows:

and step 3: placing the AHB fiber spinning solution into an injector, setting the spraying speed to be 0.08mL/min, the spraying voltage to be 10kV, the receiving distance to be 10cm, and carrying out electrostatic spinning; the resulting mixture was dried at 25 ℃ for 1 hour under vacuum to obtain a fluorescent fiber.

Comparative example 11: the injection rate was set to 0.09mL/min, and the rest was the same as in example 1.

The concrete modification is as follows:

and step 3: placing the AHB fiber spinning solution into an injector, setting the spraying speed to be 0.09mL/min, the spraying voltage to be 10kV, the receiving distance to be 10cm, and carrying out electrostatic spinning; the resulting mixture was dried at 25 ℃ for 1 hour under vacuum to obtain a fluorescent fiber.

Comparative example 12: the injection rate was set to 0.10mL/min, and the rest was the same as in example 1.

The concrete modification is as follows:

and step 3: placing the AHB fiber spinning solution into an injector, setting the spraying speed to be 0.10mL/min, the spraying voltage to be 10kV, the receiving distance to be 10cm, and carrying out electrostatic spinning; the resulting mixture was dried at 25 ℃ for 1 hour under vacuum to obtain a fluorescent fiber.

Comparative example 13: the injection rate was set to 0.11mL/min, and the rest was the same as in example 1.

The concrete modification is as follows:

and step 3: placing the AHB fiber spinning solution into an injector, setting the spraying speed to be 0.11mL/min, the spraying voltage to be 10kV, the receiving distance to be 10cm, and carrying out electrostatic spinning; the resulting mixture was dried at 25 ℃ for 1 hour under vacuum to obtain a fluorescent fiber.

Comparative example 14: the injection rate was set to 0.12mL/min, and the rest was the same as in example 1.

The concrete modification is as follows:

and step 3: placing the AHB fiber spinning solution into an injector, setting the spraying speed to be 0.12mL/min, the spraying voltage to be 10kV, the receiving distance to be 10cm, and carrying out electrostatic spinning; the resulting mixture was dried at 25 ℃ for 1 hour under vacuum to obtain a fluorescent fiber.

Comparative example 15: the ejection voltage was set to 8kV, and the rest was the same as in example 1.

The concrete modification is as follows:

and step 3: placing the AHB fiber spinning solution into an injector, setting the spraying speed to be 0.05mL/min, the spraying voltage to be 8kV, the receiving distance to be 10cm, and carrying out electrostatic spinning; the resulting mixture was dried at 25 ℃ for 1 hour under vacuum to obtain a fluorescent fiber.

Comparative example 16: the ejection voltage was set to 9kV, and the rest was the same as in example 1.

The concrete modification is as follows:

Comparative example 17: the ejection voltage was set to 11kV, and the rest was the same as in example 1.

The concrete modification is as follows:

and step 3: placing the AHB fiber spinning solution into an injector, setting the spraying speed to be 0.05mL/min, the spraying voltage to be 11kV, the receiving distance to be 10cm, and carrying out electrostatic spinning; the resulting mixture was dried at 25 ℃ for 1 hour under vacuum to obtain a fluorescent fiber.

Comparative example 18: the ejection voltage was set to 12kV, and the rest was the same as in example 1.

The concrete modification is as follows:

and step 3: placing the AHB fiber spinning solution into an injector, setting the spraying speed to be 0.05mL/min, the spraying voltage to be 12kV, the receiving distance to be 10cm, and carrying out electrostatic spinning; the resulting mixture was dried at 25 ℃ for 1 hour under vacuum to obtain a fluorescent fiber.

Comparative example 19: the ejection voltage was set to 13kV, and the rest was the same as in example 1.

The concrete modification is as follows:

and step 3: placing the AHB fiber spinning solution into an injector, setting the spraying speed to be 0.05mL/min, the spraying voltage to be 13kV, the receiving distance to be 10cm, and carrying out electrostatic spinning; the resulting mixture was dried at 25 ℃ for 1 hour under vacuum to obtain a fluorescent fiber.

Comparative example 20: the ejection voltage was set to 14kV, and the rest was the same as in example 1.

The concrete modification is as follows:

and step 3: placing the AHB fiber spinning solution into an injector, setting the spraying speed to be 0.05mL/min, the spraying voltage to be 14kV, the receiving distance to be 10cm, and carrying out electrostatic spinning; the resulting mixture was dried at 25 ℃ for 1 hour under vacuum to obtain a fluorescent fiber.

Comparative example 21: the ejection voltage was set to 15kV, and the rest was the same as in example 1.

The concrete modification is as follows:

and step 3: placing the AHB fiber spinning solution into an injector, setting the spraying speed to be 0.05mL/min, the spraying voltage to be 15kV, the receiving distance to be 10cm, and carrying out electrostatic spinning; the resulting mixture was dried at 25 ℃ for 1 hour under vacuum to obtain a fluorescent fiber.

Comparative example 22: the receiving distance was set to 6cm, and the rest was the same as in example 1.

The concrete modification is as follows:

and step 3: placing the AHB fiber spinning solution into an injector, setting the spraying speed to be 0.05mL/min, the spraying voltage to be 10kV, the receiving distance to be 6cm, and carrying out electrostatic spinning; the resulting mixture was dried at 25 ℃ for 1 hour under vacuum to obtain a fluorescent fiber.

Comparative example 23: the receiving distance was set to 7cm, and the rest was the same as in example 1.

The concrete modification is as follows:

and step 3: placing the AHB fiber spinning solution into an injector, setting the spraying speed to be 0.05mL/min, the spraying voltage to be 10kV, the receiving distance to be 7cm, and carrying out electrostatic spinning; the resulting mixture was dried at 25 ℃ for 1 hour under vacuum to obtain a fluorescent fiber.

Comparative example 24: the receiving distance was set to 8cm, and the rest was the same as in example 1.

The concrete modification is as follows:

and step 3: placing the AHB fiber spinning solution into an injector, setting the spraying speed to be 0.05mL/min, the spraying voltage to be 10kV, the receiving distance to be 8cm, and carrying out electrostatic spinning; the resulting mixture was dried at 25 ℃ for 1 hour under vacuum to obtain a fluorescent fiber.

Comparative example 25: the receiving distance was set to 9cm, and the rest was the same as in example 1.

The concrete modification is as follows:

and step 3: placing the AHB fiber spinning solution into an injector, setting the spraying speed to be 0.05mL/min, the spraying voltage to be 10kV, the receiving distance to be 9cm, and carrying out electrostatic spinning; the resulting mixture was dried at 25 ℃ for 1 hour under vacuum to obtain a fluorescent fiber.

Comparative example 26: the receiving distance was set to 11cm, and the rest was the same as in example 1.

The concrete modification is as follows:

and step 3: placing the AHB fiber spinning solution into an injector, setting the spraying speed to be 0.05mL/min, the spraying voltage to be 10kV, the receiving distance to be 11cm, and carrying out electrostatic spinning; the resulting mixture was dried at 25 ℃ for 1 hour under vacuum to obtain a fluorescent fiber.

Comparative example 27: the receiving distance was set to 12cm, and the rest was the same as in example 1.

The concrete modification is as follows:

and step 3: placing the AHB fiber spinning solution into an injector, setting the spraying speed to be 0.05mL/min, the spraying voltage to be 10kV, the receiving distance to be 12cm, and carrying out electrostatic spinning; the resulting mixture was dried at 25 ℃ for 1 hour under vacuum to obtain a fluorescent fiber.

Comparative example 28: the receiving distance was set to 13cm, and the rest was the same as in example 1.

The concrete modification is as follows:

and step 3: placing the AHB fiber spinning solution into an injector, setting the spraying speed to be 0.05mL/min, the spraying voltage to be 10kV, the receiving distance to be 13cm, and carrying out electrostatic spinning; the resulting mixture was dried at 25 ℃ for 1 hour under vacuum to obtain a fluorescent fiber.

Experiment 1: the fluorescent fibers prepared in the examples 1 to 5 were placed at 0.057mg/m³Standing for 30min in the formaldehyde environment, observing the fluorescence effect under the ultraviolet illumination with the wavelength of 365nm, taking a picture of the metering ratio, and testing the gray value of the fiber in the picture by using ImageJ software. The fiber gray scale values for different AHB fluorescent compound doping amounts are shown in table 1 below:

TABLE 1

And (4) conclusion: it can be seen from fig. 31 to 35 that the color of the photographs of the fluorescent fibers in examples 1 to 5 becomes darker, and the gray scale value data in the table shows that the gray scale value increases with the increase of the doping amount of the AHB fluorescent compound; the amplification of the embodiments 5-4 is less significant than the slow amplification of the embodiments 4-1 in terms of cost; however, in example 5, the color change becomes less and less noticeable and the response is weaker as the decrease continues, and therefore, the lower doping level affects the observation between after formaldehyde detection.

Experiment 2: scanning electron microscope analysis is carried out on the spun fluorescent fibers in the embodiment 1 and the comparative examples 1-28; the results obtained are shown in FIGS. 3 to 30, and show that: the concentration of polycaprolactone and the influence of electrostatic spinning process parameters have important influence on the fluorescent fibers, when the concentration of PCL is lower than 25%, polymer chains are broken before reaching a collector, the phenomenon of silk flying occurs, and the phenomenon of discontinuous spinning curling also exists in a topography map. When the concentration of PCL is higher than 25%, the polymer is adhered and beaded during the spraying process, so that the fiber forming is affected, irregular and much wire is rolled. When the jet speed is 0.01-0.04 mL/min, the pushing speed is too low, the spinning has the phenomenon of curling or discontinuity, and when the pushing speed is not less than 0.06mL/min, the spinning fusion phenomenon is caused by too high pushing speed. The spinning has the phenomenon of curling or discontinuity caused by too low jet voltage, and the spinning fusion phenomenon can be caused by too high jet voltage; when the jet distance is less than 8cm, the distance from the syringe needle to the collector is too short, resulting in insufficient volatilization of the solvent, resulting in non-spinnability. According to the comparative example and the example, the preferable scheme is as follows: the concentration of PCL is 25%; the spraying speed is 0.05 mL/min; the injection voltage is 10 kV; the receiving distance is 10 cm. Under the scheme, the fluorescent fiber which is continuous and uniform and has a good stretching effect is prepared, so that the fluorescent fiber has good detection stability and reproducibility.

Experiment 3: placing the fluorescent fiber prepared in the embodiment 1 at 0-0.1 mg/m³After reacting for 30min in the formaldehyde environment, observing the fluorescence change under 365nm ultraviolet light, taking a picture for recording, testing the gray value of the picture by adopting ImageJ software, and showing the fluorescence change trend of the fiber caused by formaldehyde with different concentrations by the fiber, wherein the obtained data are shown in a table 2:

TABLE 2

FIGS. 36 to 43 are photographs of the fluorescent fibers of example 1 obtained under ultraviolet irradiation after adsorbing formaldehyde in different formaldehyde concentration environments; a relationship graph of formaldehyde and gray value is obtained by plotting gray value data of the photographs in the table above, and as shown in fig. 1, a linear regression equation is obtained, wherein y is 701.45x +107.34, and the linear correlation coefficient is 0.9955.

The prepared fluorescent fiber is adopted to detect formaldehyde gas in any room, the result obtained according to the linear regression equation is compared with the result obtained by the national standard method GB/T15516-1995 acetylacetone spectrophotometry for measuring air quality formaldehyde, and the indicating value error is calculated, and the result is shown in Table 3.

Wherein, the indicating error is calculated by using a formula as follows:

wherein Ci is a result of formaldehyde detection using a fluorescent fiber, mg/m³(ii) a Cj is the result of formaldehyde detection by acetylacetone spectrophotometry, mg/m³。

TABLE 3

And (4) conclusion: the data show that the detection result of the fluorescent fiber prepared by doping the AHB fluorescent compound on formaldehyde has no obvious difference from the detection result of the national standard method, and the indication error is 1.31-5.97%; the fluorescent fiber can be used for detecting formaldehyde in indoor air, and is convenient and fast, strong in operability and high in sensitivity.

Finally, it should be noted that: although the present invention has been described in detail with reference to the foregoing embodiments, it will be apparent to those skilled in the art that changes may be made in the embodiments and/or equivalents thereof without departing from the spirit and scope of the invention. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.

Claims

1. A preparation method of a fluorescent fiber for detecting formaldehyde is characterized by comprising the following steps: the method comprises the following steps:

2. The method for preparing the fluorescent fiber for detecting formaldehyde as claimed in claim 1, wherein the method comprises the following steps: in the step 1, the AHB fluorescent compound is 2-amino-6-hydrazino-1H-benzisoquinoline-1, 3- (2H) -diketone with the structural formula

3. The method for preparing the fluorescent fiber for detecting formaldehyde as claimed in claim 1, wherein the method comprises the following steps: in the step 1, the concentration of the solution A is 0.5 g/L-3 g/L; the concentration of the solution B is 20-25%; the volume ratio of the dimethyl sulfoxide to the trichloromethane is 1: 2.

4. The method for preparing the fluorescent fiber for detecting formaldehyde as claimed in claim 3, wherein the method comprises the following steps: in the step 1, the concentration of the solution A is 1.5 g/L; the concentration of the solution B is 25%.

5. The method for preparing the fluorescent fiber for detecting formaldehyde as claimed in claim 1, wherein the method comprises the following steps: in the step 2, the spraying speed is 0.01-0.12 mL/min; the injection voltage is 8-15 kV; the receiving distance is 6-13 cm.

6. The method for preparing the fluorescent fiber for detecting formaldehyde as claimed in claim 1, wherein the method comprises the following steps: in the step 2, the injection speed is 0.05 mL/min; the injection voltage is 10 kV; the receiving distance is 10 cm.

7. The method for preparing the fluorescent fiber for detecting formaldehyde as claimed in claim 1, wherein the method comprises the following steps: the preparation method of the AHB fluorescent compound comprises the following steps: (1) dispersing 3mmol of 4-bromo-1, 8-naphthalic anhydride in 50-60 mL of ethanol solvent under nitrogen atmosphere, dropwise adding 3mmol of hydrazine hydrate, setting the temperature to be 80-85 ℃, refluxing for 5-7 hours, cooling to room temperature, filtering and washing to obtain a crude product; (2) weighing the crude product, hydrazine hydrate and potassium carbonate according to the mass ratio of 2:1: 1.62; dissolving the crude product in ethylene glycol monomethyl ether in a nitrogen atmosphere, adding hydrazine hydrate and potassium carbonate, setting the temperature to be 105-115 ℃, and refluxing for 4-6 hours; and (3) distilling under reduced pressure to remove ethylene glycol monomethyl ether, performing chromatography assistance by using methanol/dichloromethane, and crystallizing by using ethanol to obtain the AHB fluorescent compound.

8. The fluorescent fiber prepared by the preparation method of the fluorescent fiber for detecting formaldehyde according to any one of claims 1 to 7.

9. Use of a fluorescent fiber for the detection of formaldehyde according to claim 8, characterized in that: the fluorescent fiber is applied to detecting formaldehyde, and the detection method comprises the following steps: placing the fluorescent fiber at 0-0.10 mg/m³Standing for 30 minutes in the formaldehyde environment, observing the fluorescence effect under 365nm ultraviolet illumination, taking a picture and recording, testing the gray value of the fluorescence fiber in the picture by adopting ImageJ software, and constructing a linear regression equation y which is ax + b through the linear relation between formaldehyde with different concentrations and the gray value, wherein x is the formaldehyde concentration, y is the gray value, and the linear correlation coefficient is more than 0.95; when the method is used for detecting formaldehyde in the detection environment, the concentration of the formaldehyde in the environment can be directly obtained according to the gray value.

10. Use of a fluorescent fiber for the detection of formaldehyde according to claim 9, characterized in that: when the concentration of the AHB fluorescent compound in solution a was 1.5g/L, the linear regression equation was 701.45x +107.34 with a linear correlation coefficient of 0.9955.