Oleylamine zinc complex blue fluorescent material and preparation method thereof

Abstract

The invention discloses an oleylamine zinc complex blue fluorescent material and a preparation method thereof.The preparation method comprises the following steps that S1, anhydrous zinc acetate, oleylamine and octadecene are added according to a certain proportion, heating and stirring treatment is conducted in the nitrogen atmosphere, cooling and centrifugation are conducted after the reaction is finished, and a mixture octadecene solution with unreacted anhydrous zinc acetate removed is obtained; s2, extracting the mixture octadecene solution obtained in S1 by adopting N, N-dimethylformamide (DMF), and taking lower-layer liquid to obtain a mixture DMF solution; and S3, carrying out rotary evaporation treatment on the mixture DMF solution obtained in S2 to obtain the yellow transparent liquid oleylamine zinc complex blue fluorescent material. According to the oleylamine zinc complex blue fluorescent material and the preparation method thereof, the preparation method is easy to operate, the raw materials are easy to obtain, the cost is low, and the oleylamine zinc complex blue fluorescent material is suitable for large-scale production, and the prepared zinc complex has good blue fluorescence emission performance and has wide application prospects in the fields of novel photoluminescent materials and devices.

Description

Technical Field

[0001] The invention relates to the technical field of material chemistry, and in particular to an oleylamine zinc complex blue fluorescent material and a preparation method thereof. Background Art

[0002] Under the excitation of ultraviolet light, electricity or chemical energy, the electrons in the fluorescent material jump from the ground state to the excited state, and then decay back to the ground state through radiation, releasing energy in the form of photons to produce fluorescence. Fluorescent materials are divided into organic fluorescent materials and inorganic fluorescent materials. Organic fluorescent materials usually have groups or structures that can absorb excitation light, usually conjugated bond structures. According to the material structure, they can be divided into three categories: (1) aromatic fused ring compounds with rigid structures; (2) intramolecular charge transfer compounds with conjugated structures; (3) certain metal complexes. There are still many problems and challenges in the current research field of organic fluorescent materials, such as short fluorescence lifetime, weak brightness, and high price.

[0003] With the deepening of research on fluorescent materials, new organic fluorescent materials and metal complex fluorescent materials continue to emerge. In the prior art, the invention patent with announcement number CN112094283B discloses a blue fluorescent material of zinc complex of amrinone and its preparation method, and the complex can form rich and diverse hydrogen bonds, so that the complex produces a specific fluorescence emission spectrum. The invention patent with announcement number CN118027071A discloses a photochromic and fluorescent emitting Zn complex and preparation method, and the complex has a photochromic-photoluminescent dual switch effect. However, its material skeleton structure is complex and the synthesis process is difficult. Since there is a large demand for organic fluorescent materials in application fields such as optoelectronic materials, it is of great significance to design and synthesize organic fluorescent materials with simple molecular skeletons. Summary of the invention

[0004] The invention aims to provide an oleylamine zinc complex blue fluorescent material and a preparation method thereof. The preparation method is simple to operate, the raw materials are readily available, the cost is low, and the method is suitable for large-scale production. The prepared zinc complex has good blue fluorescent emission performance and has broad application prospects in the field of new photoluminescent materials and devices.

[0005] To achieve the above object, the present invention provides a method for preparing an oleylamine zinc complex blue fluorescent material, comprising the following steps: S1. Add anhydrous zinc acetate, oleylamine and octadecene in a certain proportion, heat and stir the mixture under a nitrogen atmosphere, and after the reaction is completed, cool and centrifuge to obtain a mixture octadecene solution from which unreacted anhydrous zinc acetate is removed; S2, extracting the mixed octadecene solution obtained in S1 with N,N-dimethylformamide, taking the lower layer of liquid, and obtaining a mixed DMF solution; S3, subjecting the DMF solution of the mixture obtained in S2 to rotary evaporation to obtain a yellow transparent liquid oleylamine zinc complex blue fluorescent material.

[0006] Preferably, in S1, the anhydrous zinc acetate: the oleylamine: the octadecene=4-8 mmol: 1 mL: 4-5 mL.

[0007] Preferably, in S1, the heating and stirring treatment is specifically: The mixture was heated and stirred under a nitrogen atmosphere, the temperature was raised to 100-120°C and maintained for 10 min, and then the temperature was continued to be raised to 160°C and maintained for 20-60 min in an anhydrous and oxygen-free environment.

[0008] Preferably, in S1, the centrifugal speed is 8000 r / min and the time is 5 min.

[0009] Preferably, S2 is specifically: The mixture of octadecene solution and N,N-dimethylformamide obtained in S1 was transferred to a separatory funnel at a volume ratio of 1-2:5, the solution was shaken evenly and allowed to stand for stratification, and the lower layer of liquid was taken to obtain a mixture DMF solution.

[0010] Preferably, in S3, the rotary evaporation treatment is specifically: The DMF solution of the mixture obtained in S2 was transferred to a rotary evaporator, and the parameters of the rotary evaporator were set as follows: temperature 50° C., air pressure 1 mbar, and time 30 min.

[0011] To achieve the above object, the present invention also provides an oleylamine zinc complex blue fluorescent material, the oleylamine zinc complex blue fluorescent material has two coordination forms, and its chemical formula is ZnC 38 H 77 N2O2 and ZnC 40 H 80 N2O4 is a zinc complex with a certain spatial structure, in which ZnC 38 H 77 The coordination number of N2O2 is 4, ZnC 40 H 80 The coordination number of N2O4 is 2.

[0012] Preferably, the coordination number of the oleylamine zinc complex blue fluorescent material is 4, and under the excitation of 365nm light, there is a fluorescence emission peak in the 425-525nm region, and the maximum emission wavelength is 455nm.

[0013] Preferably, the coordination number of the oleylamine zinc complex blue fluorescent material is 2, and under the excitation of 365nm light, there is a fluorescence emission peak in the 425-525nm region, and the maximum emission wavelength is 485nm.

[0014] Therefore, the present invention adopts the above-mentioned oleylamine zinc complex blue fluorescent material and its preparation method, and the beneficial effects are as follows: (1) The present invention uses anhydrous zinc acetate and oleylamine as raw materials and octadecene as a non-coordinating solvent, and performs thermal synthesis by heating and stirring. During the reaction, the amine group at the end of oleylamine removes protons and chelates with zinc ions to form an oleylamine zinc complex. Different reaction times will change the coordination number of zinc ions, and the oleylamine zinc complex will produce a new excited state, and different fluorescence emission peaks will appear in the photoinduced emission spectrum. Under the excitation of 365nm light, the oleylamine zinc complex with a reaction time of 20min has only one broad fluorescence emission peak in the 425-525nm region, and the maximum emission wavelength is 455nm; the oleylamine zinc complex with a reaction time of 40min has a new emission peak at 485nm; and the emission peak of the oleylamine zinc complex with a reaction time of 60min at 485nm is significantly enhanced.

[0015] (2) The synthesis method of the present invention is simple, the raw materials are easily available, the cost is low, the yield is high and the reproducibility is good, and it has broad application prospects.

[0016] The technical solution of the present invention is further described in detail below through the accompanying drawings and embodiments. BRIEF DESCRIPTION OF THE DRAWINGS

[0017] Figure 1 It is the fluorescence emission spectrum of an oleylamine zinc complex blue fluorescent material and a preparation method thereof according to the present invention; Figure 2 This is a Fourier transform infrared spectrum of an oleylamine zinc complex blue fluorescent material and a preparation method thereof according to Example 3 of the present invention; Figure 3 This is the nuclear magnetic resonance hydrogen spectrum of Example 3 of an oleylamine zinc complex blue fluorescent material and a preparation method thereof of the present invention. DETAILED DESCRIPTION

[0018] The technical solution of the present invention is further described below through the accompanying drawings and embodiments.

[0019] Unless otherwise defined, technical or scientific terms used in the present invention shall have the common meanings understood by one having ordinary skills in the field to which the present invention belongs.

[0020] Embodiment 1 The substances participating in the reaction are all chemically pure. A method for preparing an oleylamine zinc complex blue fluorescent material comprises the following steps: S1. Weigh 0.7339g (4.0mmol) of anhydrous zinc acetate Zn(Ac)2, place it in a 25mL three-necked flask, add 1mL oleylamine and 4mL octadecene, build a reaction device, start stirring under nitrogen atmosphere and heat to 100-120℃, remove the water in the reaction device, and then start heating to 160℃. When the temperature rises to 160℃, start timing and keep it for 20min. After the reaction is completed, cool it naturally to room temperature. Take the cooled sample in a 10mL centrifuge tube and centrifuge it at 8000r / min for 5min to remove the unreacted anhydrous zinc acetate to obtain a mixture octadecene solution.

[0021] S2. Pour the mixed octadecene solution into a 25 mL separatory funnel, add 10 mL of N,N-dimethylformamide (DMF) for extraction, shake the solution evenly, let it stand to separate the layers, take the lower layer of liquid, and obtain a mixed DMF solution.

[0022] S3. Pour the mixed DMF solution into a rotary evaporator and perform rotary evaporation at 50° C. and 1 mbar for 30 min to obtain a yellow transparent liquid, i.e., an oleylamine zinc complex blue fluorescent material (or oleylamine zinc complex).

[0023] Embodiment 2 The substances participating in the reaction are all chemically pure. A method for preparing an oleylamine zinc complex blue fluorescent material comprises the following steps: S1. Weigh 1.1001g (6.0mmol) of Zn(Ac)2, place it in a 25mL three-necked flask, add 1mL of oleylamine and 5mL of octadecene, build a reaction device, start stirring under a nitrogen atmosphere and heat to 100-120℃, remove the water in the reaction device, and then start heating to 160℃. When the temperature rises to 160℃, start timing and keep it for 40min. After the reaction is completed, cool it naturally to room temperature. Take the cooled sample in a 10mL centrifuge tube and centrifuge it at 8000r / min for 5min in a centrifuge to remove the unreacted anhydrous zinc acetate to obtain a mixture octadecene solution.

[0024] S2. Pour the mixed octadecene solution into a 25 mL separatory funnel, add 10 mL of N,N-dimethylformamide (DMF) for extraction, shake the solution evenly, let it stand to separate the layers, take the lower layer of liquid, and obtain a mixed DMF solution.

[0025] S3. Pour the mixed DMF solution into a rotary evaporator and perform rotary evaporation at 50° C. and 1 mbar for 30 min to obtain a yellow transparent liquid, that is, the oleylamine zinc complex blue fluorescent material.

[0026] Embodiment 3 The substances participating in the reaction are all chemically pure. A method for preparing an oleylamine zinc complex blue fluorescent material comprises the following steps: S1. Weigh 1.4678g (8.0mmol) of Zn(Ac)2, place it in a 25mL three-necked flask, add 2mL of oleylamine and 8mL of octadecene, build a reaction device, start stirring under a nitrogen atmosphere and heat to 100-120℃, remove the water in the reaction device, and then start heating to 160℃. When the temperature rises to 160℃, start timing and keep it for 60min. After the reaction is completed, cool it naturally to room temperature. Take the cooled sample in a 10mL centrifuge tube and centrifuge it at 8000r / min for 5min in a centrifuge to remove the unreacted anhydrous zinc acetate to obtain a mixture octadecene solution.

[0027] S2. Pour the mixed octadecene solution into a 25 mL separatory funnel, add 10 mL of N,N-dimethylformamide (DMF) for extraction, shake the solution evenly, let it stand to separate the layers, take the lower layer of liquid, and obtain a mixed DMF solution.

[0028] S3. Pour the mixed DMF solution into a rotary evaporator and perform rotary evaporation at 50° C. and 1 mbar for 30 min to obtain a yellow transparent liquid, that is, the oleylamine zinc complex blue fluorescent material.

[0029] Experimental Testing The luminescence test was carried out using the oleylamine zinc complex blue fluorescent material prepared in Examples 1 to 3.

[0030] like Figure 1 As shown in the emission spectrum of the oleylamine zinc complex reacted at 160°C for 20 minutes under 365nm excitation, the oleylamine zinc complex reacted for 20 minutes in Example 1 has only one broad fluorescence emission peak in the 425-525nm region, and the maximum emission wavelength is 455nm. The oleylamine zinc complexes in Examples 2 and 3 have a new emission peak at 485nm, showing blue-green fluorescence emission, because the coordination number of zinc ions changes when the reaction time is extended, and the oleylamine zinc complex produces a new excited state, and a new fluorescence emission peak appears in the photoinduced emission spectrum.

[0031] like Figure 2 As shown, by comparing the Fourier transform infrared spectra of the monomers (anhydrous zinc acetate, oleylamine and octadecene) before the reaction with the oleylamine zinc complex in Example 3, it was found that the -1 The peak at 1450cm-1 in the infrared spectrum of zinc oleylamine disappeared, indicating that the primary amine group at the end of oleylamine reacted with Zn(Ac)2. -1 and 1560cm -1The two broad absorption bands of -1 and 1586cm -1 , indicating that -COO - Group and Zn 2+ The coordinated structure remains intact in the oleylamine zinc complex, and the characteristic peaks of the symmetric and asymmetric stretching vibrations of C=O in the acetate group appear at 1415 cm -1 and 1568cm -1 , indicating that -COO - Group and Zn 2+ Non-chelating coordination occurs, that is, the existence of a 2-coordinate structure. The absorption peak originating from the C-CH3 and Zn-O stretching mode in the chelating structure changes from 695 cm -1 Blue shift to 672cm -1 At 955cm -1 and 1113cm -1 The Zn-O symmetric and asymmetric stretching vibrations disappeared in the oleylamine zinc complex, indicating that the amine group and -COO - Group and Zn 2+ Coordination chelation forms a tetrahedral coordination structure, namely a 4-coordinate structure.

[0032] Depend on Figure 3 It can be seen that the H NMR spectra of the oleylamine zinc complex in Example 3 and the monomer before the reaction showed the following changes: The chemical shift of -NH2 at the terminal of oleylamine shifted from 1.40ppm to 1.46ppm and 1.52ppm, corresponding to two coordination structures, indicating that -NH2 in the oleylamine zinc complex and Zn 2+ The vinyl characteristic peak at 2.00ppm confirms the presence of vinyl in the oleylamine zinc complex, indicating that it does not participate in the reaction. The methyl characteristic peak of acetate appears at 1.99ppm, resulting in an integral intensity of almost twice that of the monomer before the reaction. A weaker acetate methyl characteristic peak also appears at 1.93ppm, indicating the existence of another different coordination structure. In addition, the amine group and Zn 2+ The coordination of 2-(4-hydroxy-2-nitropropene)-2 resulted in a significant change in the chemical shift of its nearest methylene group, from 2.65 ppm to 2.75 ppm.

[0033] The Fourier transform infrared spectroscopy (FTIR) and nuclear magnetic resonance spectroscopy ( 1 H NMR) analysis showed that the oleylamine zinc complex has two configurations, with the chemical formulas of ZnC 38 H 77 N2O2 and ZnC 40 H 80N2O4 is a zinc complex with a certain spatial structure. The chelated coordination structure of the oleylamine zinc complex, i.e. the 4-coordinate structure, is as follows: The non-chelating coordination structure of the oleylamine zinc complex, i.e., the 2-coordination structure, is as follows: The oleylamine zinc complex blue fluorescent material with a coordination number of 4 has a broad fluorescence emission peak in the 425-525nm region under the excitation of 365nm light, and the maximum emission wavelength is 455nm.

[0034] The oleylamine zinc complex blue-green fluorescent material with a coordination number of 2 has a broad fluorescence emission peak in the 425-525nm region under the excitation of 365nm light, and the maximum emission wavelength is 485nm.

[0035] Therefore, the present invention adopts the above-mentioned oleylamine zinc complex blue fluorescent material and its preparation method. The preparation method is simple to operate, the raw materials are easily available, the cost is low, and it is suitable for large-scale production. The prepared zinc complex has good blue fluorescence emission performance and has broad application prospects in the field of new photoluminescent materials and devices.

[0036] Finally, it should be noted that the above embodiments are only used to illustrate the technical solution of the present invention rather than to limit it. Although the present invention has been described in detail with reference to the preferred embodiments, those skilled in the art should understand that they can still modify or replace the technical solution of the present invention with equivalents, and these modifications or equivalent replacements cannot cause the modified technical solution to deviate from the spirit and scope of the technical solution of the present invention.

Claims

1. A method for preparing a blue fluorescent material of an oleylamine zinc complex, characterized in that: The following steps are involved: S1. Add anhydrous zinc acetate, oleylamine and octadecene in a certain proportion, heat and stir the mixture under a nitrogen atmosphere, and after the reaction is completed, cool and centrifuge to obtain a mixture octadecene solution from which unreacted anhydrous zinc acetate is removed; S2, extracting the mixed octadecene solution obtained in S1 with N,N-dimethylformamide, taking the lower layer of liquid, and obtaining a mixed DMF solution; S3, subjecting the DMF solution of the mixture obtained in S2 to rotary evaporation to obtain a yellow transparent liquid oleylamine zinc complex blue fluorescent material.

2. The method for preparing a blue fluorescent material of oleylamine zinc complex according to claim 1, characterized in that: In S1, the anhydrous zinc acetate: the oleylamine: the octadecene = 4-8 mmol: 1 mL: 4-5 mL.

3. The method for preparing a blue fluorescent material of oleylamine zinc complex according to claim 1, characterized in that: In S1, the heating and stirring treatment is specifically: The mixture was heated and stirred under a nitrogen atmosphere, the temperature was raised to 100-120°C and maintained for 10 min, and then the temperature was continued to be raised to 160°C and maintained for 20-60 min in an anhydrous and oxygen-free environment.

4. The method for preparing a blue fluorescent material of oleylamine zinc complex according to claim 1, characterized in that: In S1, the centrifugal speed is 8000 r / min and the time is 5 min.

5. The method for preparing an oleylamine zinc complex blue fluorescent material according to claim 1, characterized in that: S2 is specifically: The mixture of octadecene solution and N,N-dimethylformamide obtained in S1 was transferred to a separatory funnel at a volume ratio of 1-2:5, the solution was shaken evenly and allowed to stand for stratification, and the lower layer of liquid was taken to obtain a mixture DMF solution.

6. The method for preparing an oleylamine zinc complex blue fluorescent material according to claim 1, characterized in that: In S3, the rotary evaporation treatment is specifically: The DMF solution of the mixture obtained in S2 was transferred to a rotary evaporator, and the parameters of the rotary evaporator were set as follows: temperature 50° C., air pressure 1 mbar, and time 30 min.

7. An oleylamine zinc complex blue fluorescent material prepared by the preparation method of the oleylamine zinc complex blue fluorescent material according to any one of claims 1 to 6.

8. The oleylamine zinc complex blue fluorescent material according to claim 7, characterized in that: The oleylamine zinc complex blue fluorescent material has two coordination forms, and its chemical formula is ZnC 38 H 77 N2O2 and ZnC 40 H 80 N2O4 is a zinc complex with a certain spatial structure, in which ZnC 38 H 77 The coordination number of N2O2 is 4, ZnC 40 H 80 The coordination number of N2O4 is 2.

9. The oleylamine zinc complex blue fluorescent material according to claim 8, characterized in that: The coordination number of the oleylamine zinc complex blue fluorescent material is 4. Under the excitation of 365nm light, it has a fluorescence emission peak in the 425-525nm region, and the maximum emission wavelength is 455nm.

10. The oleylamine zinc complex blue fluorescent material according to claim 8, characterized in that: The coordination number of the oleylamine zinc complex blue fluorescent material is 2. Under the excitation of 365nm light, it has a fluorescence emission peak in the 425-525nm region, and the maximum emission wavelength is 485nm.

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