CN112876835B - Multicolor fluorescent polymer film with environment humidity response and preparation method and application thereof - Google Patents
Multicolor fluorescent polymer film with environment humidity response and preparation method and application thereof Download PDFInfo
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Abstract
The invention provides a multicolor fluorescent polymer film with environment humidity response and a preparation method and application thereof.A BPPA ligand is obtained by three steps of reactions with triphenylamine as a raw material; ligand BPPA is coordinated with zinc, and the complex is added into a polyethylene glycol (PEG) matrix to construct a luminous Relative Humidity (RH) ratio type sensor. The obtained polymer film can convert the invisible information of RH into obviously different fluorescent colors from blue to yellow (450 nm-547 nm); the multicolor fluorescent polymer film with the environmental humidity response has the excellent performances of high identification degree, high sensitivity, good reversibility, quick response time and the like.
Description
Technical Field
The invention relates to a preparation method and application of a multicolor fluorescent polymer with environment humidity response, belonging to the field of organic photoelectric functional materials.
Background
Humidity detection is of great significance in various fields such as environmental monitoring, chemical engineering processes, agricultural production, cargo storage, biomedical analysis and the like. Semiconductor sensors with fast response and good readability are widely used in everyday applications for measuring relative humidity, and most sensors convert humidity response into electrical signals. High performance semiconductor RH sensors have limited their wider application due to the need for complex operating procedures and external power supply systems. Compared with semiconductor humidity sensors, luminescence sensors have received much attention because of their low cost, simple structure, fast response speed, and high visibility to the naked eye. Humidity sensitive luminescent materials, whose luminescence intensity varies with the RHs, however, this type of RH sensor is sensitive to electromagnetic power and detector sensitivity, making it difficult to accurately measure RH in complex environments. In order to improve the detection performance of the RH sensor, a luminescence ratio type sensor has been developed. However, the emission wavelength variation of these luminescent RH sensors under different RHs is usually narrow, with the maximum range being within 50nm, which is not conducive to direct observation by the naked eye. Therefore, one current challenge is how to fabricate high performance RH sensors with a wide response emission wavelength range under different RHs conditions.
Disclosure of Invention
In order to overcome the defects of the prior art, the invention provides a multicolor fluorescent polymer film with environment humidity response, which can be used as a high-performance RH sensor and solves the problem of narrow response emission wavelength range of the RH sensor under different RHs conditions in the prior art.
The technical scheme adopted by the invention is as follows:
in a first aspect, the invention provides a multicolor fluorescent polymer film with environmental humidity response, which is a film formed by mixing and doping Zn-BPPA and polyethylene glycol (PEG) and coating the mixture on the surface of a transparent weighing body, and is hereinafter referred to as a Zn-BPPA/PEG polymer film, wherein the doping ratio of Zn-BPPA to PEG is 0.1wt%.
In a second aspect, the present invention provides a method for preparing a multicolor fluorescent polymer film with an environmental humidity response, comprising the following steps: and (3) sucking a proper amount of the 0.1wt% Zn-BPPA/PEG polymer doping solution, placing the solution on a transparent glass sheet cleaned by ultrasound and microwave, spin-coating for 30s at the rotating speed of 3000r/min, and airing to obtain the Zn-BPPA/PEG polymer film with humidity response.
In a third aspect, the invention provides an application of a multicolor fluorescent polymer film with an environmental humidity response, wherein the multicolor fluorescent polymer film with the environmental humidity response is irradiated by 365 ultraviolet light, so that multicolor fluorescence under different humidity environments can be realized, further environment humidity visualization is realized, and the multicolor fluorescent polymer film can be applied as a luminous RH ratio type sensor.
The invention principle is as follows: according to the invention, the metal zinc complex is added into the polyethylene glycol (PEG) substrate, so that the prepared luminescent polymer can convert invisible information of environmental RH into visible multicolor fluorescence information, a water bridge is utilized to form a coordination bond between zinc ions and a bipyridine ligand, further the luminescent color change of the film is regulated and controlled, and the visualization of humidity is realized, as shown in figure 5, when 0.1wt% of low mass ratio is doped, the BPPA and Zn are matched 2+ The ionic interaction is very weak, when the relative humidity of the environment is lower than 50%, the thin-touch fluorescence is close to the blue fluorescence of the ligand, and when the environmental humidity is increased by more than 50%When the molecular structure is changed, hydrogen bonds are formed between water molecules in the environment and BPPA ligands, and oxygen atoms in the water molecules and Zn 2+ The ions combine to form Zn-O bonds, so that the color of the film is gradually changed. The more pronounced the color change of the film as the humidity increases.
Has the beneficial effects that: the multicolor fluorescent polymer film with the environmental humidity response provided by the invention has simple synthesis and preparation steps and mild conditions; the obtained 0.1wt% Zn-BPPA/PEG polymer film has the best application effect by changing different mass doping ratios, and can be applied to RH ratio type sensors; the invention provides a multicolor fluorescent polymer film with environmental humidity response.
Under different humidity responses, macroscopic multicolor fluorescence with wide range of fluorescence from blue to yellow (450 nm to 547 nm) can be realized, and the defect that the prior emission wavelength has narrow change (the maximum change range is not more than 50 nm) and is not beneficial to direct observation by naked eyes is overcome;
0.1wt% Zn-BPPA/PEG polymer with humidity response has excellent performances of high sensitivity, good reversibility, fast response time and the like;
the film can show multi-color fluorescence from blue-cyan-yellow green-yellow under the irradiation of white light when placed in different humidity environments (RH is low-high), the discrimination is high, and further the application of environment humidity visualization is realized.
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FIG. 1 illustrates a process for preparing a Zn-BPPA/PEG polymer film according to an embodiment;
FIG. 2 is a BPPA nuclear magnetic structure characterization spectrum according to an embodiment;
FIG. 3a is a fluorescence emission spectrum of humidity response of the 0.1wt% Zn-BPPA/PEG polymer film according to an embodiment;
FIG. 3b is a fluorescence emission spectrum of humidity response of the 0.05wt% Zn-BPPA/PEG polymer film according to an embodiment;
FIG. 3c is a fluorescence emission spectrum of humidity response of the 0.4wt% Zn-BPPA/PEG polymer film according to an embodiment;
FIG. 4 is a graph showing the results of monitoring the ambient humidity during a 365nm LED small bulb test experiment in accordance with an exemplary embodiment;
fig. 5 is a schematic diagram of the visualization of the humidity of the polymer film according to the disclosure.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is described in further detail below with reference to specific embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not to be construed as limiting the invention.
Example 1 preparation of BPPA
The chemical structural formula of the BPPA selected in this example is as follows:
the synthesis of BPPA in this example is divided into three steps:
the first step is as follows: triphenylamine (3 g) was dissolved in chloroform (50 mL) and stirred in an ice-water bath at 0 ℃, N-bromosuccinimide (NBS) (2.2 g) was slowly added to dissolve it completely, and then warmed to room temperature and stirred for 8-12 hours. After the reaction, the reaction solution was dried by distillation under reduced pressure, and then water and CH were added 2 Cl 2 Extracting for three times, collecting organic phase and using anhydrous Na 2 SO 4 Drying, distilling under reduced pressure, removing solvent, and adding CH 2 Cl 2 EtOH recrystallization afforded Compound 1 as a white powder, yield: 96 percent
The second step is that: in N 2 Compound 1 (2 g) was dissolved with ultra dry tetrahydrofuran (30 mL) under protection and placed in a dry ice/acetone bath at-78 ℃; after 10min, n-butyllithium (3.4 mL) was added dropwise and stirred for 1h, followed by addition of trimethyl borate (0.6 mL), warming to room temperature, and stirring for 8-12 h. After the reaction is finished, adding deionized water (10 mL) to quench unreacted n-butyllithium, then adding a small amount of dilute hydrochloric acid to adjust the pH value to acidity, stirring for a little time, and then spin-drying the reaction solution under vacuum; followed by extraction with ethyl acetate and aqueous sodium chloride solution three times to remove inorganic salts formed by the reaction, collecting the organic phase and reacting with anhydrous Na 2 SO 4 Drying, and finally removing the solvent by distillation under reduced pressure to obtain the white powder compound 2, wherein the yield is as follows: and 78 percent.
The third step: in N 2 Compound 2 (1 g) was dissolved with 4,4-dibromo-2,2-bipyridine (434 mg), tetratriphenylphosphine palladium (80.7 mg), and potassium carbonate (2.713 mg) in 50mL of a mixed solvent of toluene, ethanol, and ultrapure water (V) which had been deoxygenated under protection Toluene V B Alcohol(s) :V Water (W) 1) and refluxing at 65 ℃ for 40h. After the reaction is finished, the reaction solution is dried in vacuum, and the product is treated by CH 2 Cl 2 /H 2 Extracting with O for three times, removing excessive inorganic salt, collecting organic phase, and adding anhydrous Na 2 SO 4 Drying, then removal of the solvent by distillation under reduced pressure, and finally purification by column chromatography, gave BBPA as a yellow powder, yield: and 55 percent. 1 H NMR(400MHz) 1 H NMR(400MHz,CD3Cl)δ(ppm):9.16(s,2H),8.80(d,J＝4.0Hz,2H),7.9(d,J＝8.0Hz,4H),7.81(d,J＝4.0Hz,2H),7.7(m,2H),7.58(m,2H),7.49(m,2H),7.35(t,J＝16.0Hz,6H),7.21(m,12H).[m/z]:(calculated,642.79,found,642.29).
Example 2: preparation method of Zn-BPPA/PEG polymer film
Referring to FIG. 1, a certain amount of ligands BPPA and Zn (ClO) are weighed according to 1:1 mol ratio 4 ) 2 ·6H 2 CH with O dissolved in a little methanol 2 Cl 2 1X 10 (10 mL) of the mixed solution was prepared -3 moL/L Zn-BPPA solution. 2.0g of PEG8000 was weighed out to prepare 20mL of 100mg/mL of PEG8000 solution. 0.1wt% Zn-BPPA/PEG doping solution is prepared. Sucking 45 μ L of the doping solution, placing on a transparent glass sheet of 1.5cm × 1.5cm cleaned by ultrasound and microwave, spin-coating at 3000r/min for 30s, and air drying to obtain the Zn-BPPA/PEG polymer film with humidity response. In addition, by changing the doping ratio of Zn-BPPA to PEG, 0.05wt% and 0.4wt% Zn-BPPA/PEG polymer films can be prepared as comparative test examples.
Test example 1: characterization of ligand Zn-BPPA and photophysical property testing of Zn-BPPA/PEG polymer films:
ligand BPPA (5-10 mg) was dissolved in 0.5mL of deuterated reagent and the structure of the compound was characterized using a 400Hz NMR spectrometer, which is shown in FIG. 2.
Measuring the emission spectrum of the polymer film Zn-BPPA/PEG responding to humidity, as shown in FIG. 3a, it can be seen that 0.1wt% of the Zn-BPPA/PEG polymer film has the fluorescence emission from 450nm to 547nm, and the color of the film is from blue to yellow; as shown in FIG. 3b, it can be seen that 0.05wt% Zn-BPPA/PEG polymer film fluorescence emission is from 450nm to 480nm, the film changes from dark blue to light blue, and the change is not obvious; as shown in FIG. 3c, it can be seen that 0.4wt% Zn-BPPA/PEG polymer film fluorescence emission is from 553nm to 558nm, and the film remains almost unchanged in yellow.
Test example 2: bulb test of Zn-BPPA/PEG polymer films
The Zn-BPPA/PEG polymer film is uniformly coated on a 365nm LED small bulb, the bulb is dried in the air, the bulb is placed in different humidity environments, the relative humidity is changed from low to high, after the bulb is electrified, multicolor fluorescence from blue-green-yellow-green appears in the small bulb, and as shown in figure 4, the application of environment humidity visualization is realized.
Claims (7)
1. A multicolor fluorescent polymer film with environment humidity response is characterized in that the polymer film is formed by mixing Zn-BPPA and polyethylene glycol (PEG) according to a doping ratio of 0.1wt% to form 0.1wt% of Zn-BPPA/PEG polymer doping liquid and coating the Zn-BPPA/PEG polymer doping liquid on the surface of a transparent weighing body; the preparation method of the 0.1wt% Zn-BPPA/PEG polymer doping solution comprises the following steps: weighing a certain amount of ligands BPPA and Zn (ClO) according to the molar ratio of 1:1 4 ) 2 ·6H 2 O is dissolved in a little CH 3 CH of OH 2 Cl 2 In the mixed solution, the preparation concentration is 1 × 10 -3 moL/L Zn-BPPA solution; preparing PEG8000 solution with the concentration of 100 mg/mL; zn-BPPA/PEG doping solution is prepared according to the mass ratio of 0.1wt% between Zn-BPPA and PEG 8000.
2. A method for preparing a multicolor fluorescent polymer film with environmental humidity response, which is characterized by comprising the following steps: sucking a proper amount of the 0.1wt% Zn-BPPA/PEG polymer doping solution described in claim 1, spin-coating on a transparent glass sheet, and then air-drying to obtain the polymer film.
3. The method for preparing a multicolor fluorescent polymer film with environmental humidity response according to claim 2, wherein the spin coating comprises the following steps: the Zn-BPPA/PEG polymer doping solution is dripped on a transparent glass sheet at the rotating speed of 3000r/min and is kept for 30s.
4. The method of claim 2, wherein the transparent glass sheet is an ultrasonically and microwave cleaned transparent glass sheet.
5. Use of a multicolored fluorescent polymer film having an ambient humidity response as a material for visualizing ambient humidity, wherein the polymer film of claim 1 is irradiated with 365nm ultraviolet light.
6. The use of the multicolor fluorescent polymer film with ambient humidity response as an ambient humidity visualization material according to claim 5, wherein the polymer film is used as a luminous RH ratio sensor.
7. The application of the multicolor fluorescent polymer film with the environment humidity response as an environment humidity visualization material according to claim 5, wherein 0.1wt% of Zn-BPPA/PEG polymer doping solution is dipped by a brush and evenly smeared on the 365nm LED small bulb, the 365nm LED small bulb is placed in bottles with different humidity after being dried in the air, and after the power is turned on, the small bulb immediately shows multicolor fluorescence from blue-blue green-yellow, so that the application of the environment humidity visualization is realized.
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