Preparation method and application of a kind of perylene diimide porous organic polymer material

Abstract

The application discloses a preparation method of a perylene diimide porous organic polymer material and application thereof, and belongs to the technical field of porous organic polymer materials. The preparation method is as follows: 1,6,7,8-tetrachloroperylene-3,4,9,10-tetracarboxylic dianhydride, triamine monomers and diphenyl sulfone are uniformly mixed and transferred into a glass tube, and then, after being cooled by liquid nitrogen, the glass tube is subjected to melt sealing under a vacuum state; then, the sealed glass tube is transferred into a muffle furnace to be heated to perform a polyimide reaction to obtain a product; after the reaction is completed, the product is taken out, and then, the product is subjected to grinding, washing and vacuum drying in sequence to obtain the perylene diimide porous organic polymer. After the perylene diimide porous organic polymer is treated by an organic amine, an excellent light-heat conversion material is obtained. The perylene diimide porous organic polymer has high light-heat conversion efficiency after being treated by the organic amine, and has the advantages of simple synthesis, high yield and good stability, and is suitable for being used as the light-heat conversion material, and has a good application prospect in the field of solar water evaporation.

Description

TECHNICAL FIELD

[0001] The present application belongs to the technical field of porous organic polymer materials, and particularly relates to a kind of preparation and application of perylene diimide porous organic polymer materials. BACKGROUND

[0002] Photo-thermal conversion materials are materials that can effectively absorb light energy and convert it into heat energy. By optimizing these materials, the efficiency of solar energy utilization can be improved, promoting the development of renewable energy, which plays an important role in addressing global energy crisis and reducing dependence on fossil fuels. So far, a variety of high-efficiency photo-thermal materials have been developed. The reported photo-thermal materials mainly include metal nanomaterials, semiconductor materials, carbon-based materials, and organic polymer materials. However, although many photo-thermal materials have been developed, most inorganic reagents have the disadvantages of difficult design, difficult performance control, and environmental and biological toxicity. Similarly, most organic reagents also have the disadvantages of short absorption wavelength, low molar extinction coefficient, and poor light stability. Therefore, developing photo-thermal materials with high photo-thermal conversion efficiency and high stability remains a challenge.

[0003] Compared with organic small molecules, polymer materials often have more levels of structure, thereby realizing the amplification and integration of the functions of structural units. Porous organic polymers (POPs) have high crystallinity, porous open channels, and adjustable chemical composition, and can be modified at the atomic or molecular level by introducing functional monomers or functional groups, thereby exhibiting good light capture and heat conversion capabilities. Recent work has shown that they have good application prospects in photo-thermal conversion. However, most POPs have limited light capture capability, especially in the near-infrared (NIR) region, limiting the utilization of solar energy. In addition, they may also suffer energy loss through radiative relaxation, i.e., most of the charges generated by the excitation of POPs will tend to recombine and release energy through radiative relaxation, and only a small amount of light energy is converted into heat through non-radiative relaxation. Therefore, limited light capture capability and low level of photo-thermal conversion efficiency are the main obstacles hindering the application of POPs in photo-thermal conversion. SUMMARY

[0004] In view of the defects and deficiencies of the prior art, the purpose of the present application is to provide a kind of preparation and application of perylene diimide porous organic polymer materials.

[0005] To achieve the above-mentioned purpose of the application, the present application provides the following technical solutions:

[0006] A kind of perylene diimide porous organic polymer material, the structure of its repeating unit is as follows:

[0007]

[0008] wherein R is a structural unit Or the atom N.

[0009] The preparation reaction equation for the perylene diimide porous organic polymer material described in this invention is as follows:

[0010]

[0011] The preparation method of the above-mentioned perylene diimide porous organic polymer material includes the following steps:

[0012] 1) Mix 1,6,7,8-tetrachloroperylene-3,4,9,10-tetracarboxylic acid dianhydride, triamine monomer and diphenyl sulfone uniformly and transfer to a glass tube. After cooling with liquid nitrogen, melt and seal under vacuum.

[0013] 2) Transfer the sealed glass tube to a muffle furnace for heating and reaction to obtain the product;

[0014] 3) The product was removed, ground, washed, and vacuum dried to obtain perylene diimide porous organic polymer;

[0015] The obtained perylene diimide porous organic polymer was treated with an organic amine to obtain perylene diimide porous organic polymer material.

[0016] The molar ratio of the triamine monomer to 1,6,7,8-tetrachloroperylene-3,4,9,10-tetracarboxylic dianhydride and diphenyl sulfone is 1:1.5:(20-50).

[0017] Preferably, the monomer in step 1) is tris(4-aminophenyl)amine, 2,4,6-tris(4-aminophenyl)-1,3,5-triazine, or 1,3,5-tris(4-aminophenyl)benzene.

[0018] Preferably, the liquid nitrogen cooling time in step 1) is 5 to 15 minutes.

[0019] Preferably, the heating rate in step 2) is 5–10 °C / min.

[0020] Preferably, the heating temperature in step 2) is 300-500°C and the heating time is 1-48 hours.

[0021] Preferably, the grinding method used in step 3) is ball milling, and the grinding time is 5-10 minutes.

[0022] Preferably, the solvents used for washing in step 3) are methanol and tetrahydrofuran, respectively.

[0023] Preferably, the drying temperature of the product in step 3) during vacuum drying is 60-85°C, and the drying time is 12-24 hours.

[0024] Preferably, the organic amine in step 3) is diethylamine, ethylenediamine, trimethylamine, triethylamine, tripropylamine or isopropylamine.

[0025] The application of the perylene diimide porous organic polymer material treated by the organic amine includes being used as a photothermal material for solar water evaporation.

[0026] The perylene diimide porous organic polymer material of the present application has high photothermal conversion efficiency after being treated by the organic amine, is simple to synthesize, has good stability, is suitable for being used as a photothermal conversion material, and has good application prospect in the field of solar water evaporation.

[0027] Specifically:

[0028] 1) The perylene diimide porous organic polymer material is treated by the organic amine, so that a delocalized free radical anion can be generated through a mild photo-induced electron transfer process;

[0029] 2) The perylene diimide porous organic polymer material of the present application is simple to synthesize and has good stability;

[0030] 3) The perylene diimide porous organic polymer material of the present application has a high water evaporation rate after being treated by the organic amine, can be used as a photothermal conversion material, and has wide application prospect. BRIEF DESCRIPTION OF DRAWINGS

[0031] Figure 1 It is an infrared spectrum of t-4Cl-PTPI in the examples.

[0032] Figure 2 It is a powder X-ray diffraction spectrum of t-4Cl-PTPI in the examples.

[0033] Figure 3 It is a carbon solid nuclear magnetic resonance spectrum of t-4Cl-PTPI in the examples.

[0034] Figure 4 It is a thermogravimetric spectrum of t-4Cl-PTPI in the examples.

[0035] Figure 5 It is a nitrogen adsorption-desorption isotherm of t-4Cl-PTPI in the examples.

[0036] Figure 6 It is an ultraviolet-visible absorption spectrum of t-4Cl-PTPI and t-4Cl-PTPI˙ˉ in the examples.

[0037] Figure 7 It is an electron paramagnetic resonance spectrum of t-4Cl-PTPI and t-4Cl-PTPI˙ˉ in the examples.

[0038] Figure 8 The t-4Cl-PTPI˙ˉ temperature curve in the example.

[0039] Figure 9 The t-4Cl-PTPI˙ˉ water evaporation curve in the example. DETAILED DESCRIPTION

[0040] The application will be further described below in conjunction with the examples. It should be understood that the specific examples described herein are intended to explain the application and are not limiting to the application.

[0041] Example 1:

[0042] A kind of perylene diimide porous organic polymer material (for example, taking 2, 4, 6-tris (4-aminophenyl)-1, 3, 5-triazine as a triamine monomer), its preparation method is the following steps:

[0043] Synthesis of t-4Cl-PTPI: 1, 6, 7, 8-tetrachloroperylene-3, 4, 9, 10-tetracarboxylic dianhydride (0.159 mg, 0.3 mm), 2, 4, 6-tris (4-aminophenyl)-1, 3, 5-triazine (0.071 mg, 0.2 mm) and diphenyl sulfone (1.6920 g) are uniformly mixed, the mixture is transferred to a glass tube, cooled in liquid nitrogen for 5 min, and then sealed by melting under vacuum; the sealed glass tube is transferred to a muffle furnace, heated at 10 ℃ / min, heated at 350 ℃ for 1.5 h, and a red product is obtained; the product is taken out, ball milled for 5 min, washed with methanol, and then subjected to Soxhlet extraction with tetrahydrofuran, and dried at 60 ℃ under vacuum for 12 h to obtain the perylene diimide porous organic polymer t-4Cl-PTPI.

[0044] A kind of perylene diimide porous organic polymer material (for example, taking 2, 4, 6-tris (4-aminophenyl)-1, 3, 5-triazine as a triamine monomer) is treated with an organic amine, and the treatment method comprises the following steps:

[0045] 500 mg of t-4Cl-PTPI is placed in a glass bottle, and isopropanolamine vapor is introduced for 10 min, and the treated material is denoted as t-4Cl-PTPI˙ˉ.

[0046] Example 2:

[0047] A kind of perylene diimide porous organic polymer material (for example, taking 2, 4, 6-tris (4-aminophenyl)-1, 3, 5-triazine as a triamine monomer), its preparation method is the following steps:

[0048] 4Cl-PDH-TAPA synthesis: 1,6,7,8-tetrachloroperylene-3,4,9,10-tetracarboxylic dianhydride (0.159 mg, 0.3 mm), tris(4-aminophenyl)amine (0.058 mg, 0.2 mm) and diphenyl sulfone (1.6920 g) were mixed homogeneously, the mixture was transferred into a glass tube, which was sealed by melting under vacuum after being cooled by liquid nitrogen for 5 min; the sealed glass tube was transferred into a muffle furnace, which was heated at 350 °C for 1.5 h with a heating rate of 10 °C / min to obtain a red product; the product was taken out, washed by methanol after ball milling for 5 min, and then Soxhlet extracted by tetrahydrofuran, which was dried at 60 °C under vacuum for 12 h to obtain the perylene diimide porous organic polymer 4Cl-PDH-TAPA.

[0049] A kind of perylene diimide porous organic polymer material (for example, tris (4-aminophenyl) amine is used as triamine monomer) is treated by organic amine, and its treatment method includes the following steps:

[0050] 500 mg of 4Cl-PDH-TAPA was placed in a glass bottle, and isopropylamine vapor was introduced for 10 minutes. The treated material is denoted as 4Cl-PDH-TAPA˙ˉ.

[0051] Example 3:

[0052] A kind of perylene diimide porous organic polymer material (for example, 1,3,5-tris (4-aminophenyl) benzene monomer)

[0053] A kind of perylene diimide porous organic polymer material (for example, 1,3,5-tris (4-aminophenyl) benzene is used as triamine monomer), and its preparation method includes the following steps:

[0054] 4Cl-PDH-TAB synthesis: 1,6,7,8-tetrachloroperylene-3,4,9,10-tetracarboxylic dianhydride (0.159 mg, 0.3 mm), 1,3,5-tris(4-aminophenyl)benzene (0.070 mg, 0.2 mm) and diphenyl sulfone (1.6920 g) were mixed homogeneously, the mixture was transferred into a glass tube, which was sealed by melting under vacuum after being cooled by liquid nitrogen for 5 min; the sealed glass tube was transferred into a muffle furnace, which was heated at 350 °C for 1.5 h with a heating rate of 10 °C / min to obtain a red product; the product was taken out, washed by methanol after ball milling for 5 min, and then Soxhlet extracted by tetrahydrofuran, which was dried at 60 °C under vacuum for 12 h to obtain the perylene diimide porous organic polymer 4Cl-PDH-TAB.

[0055] A kind of perylene diimide porous organic polymer material (for example, 1,3,5-tris (4-aminophenyl) benzene is used as triamine monomer) is treated by organic amine, and its treatment method includes the following steps:

[0056] Take 500 mg 4Cl-PDH-TAB into a glass bottle, and introduce isopropylamine vapor for 10 minutes. The treated material is recorded as 4Cl-PDH-TAB˙ˉ.

[0057] Example 4:

[0058] Different from Examples 1-3, the mixture is transferred into a glass tube, and after being cooled by liquid nitrogen for 15 minutes, it is fusion-sealed under vacuum. The sealed glass tube is transferred into a muffle furnace, and heated at 500 ℃ for 48 h at a heating rate of 5 ℃ / min. The red product is obtained. After the product is taken out, ball-milled for 10 min, washed with methanol, and subjected to Soxhlet extraction with tetrahydrofuran, the polymer material is obtained after vacuum drying at 85 ℃ for 20 h.

[0059] Example 5:

[0060] Different from Examples 1-4, the mixture is transferred into a glass tube, and after being cooled by liquid nitrogen for 10 minutes, it is fusion-sealed under vacuum. The sealed glass tube is transferred into a muffle furnace, and heated at 400 ℃ for 30 h at a heating rate of 7 ℃ / min. The red product is obtained. After the product is taken out, ball-milled for 8 min, washed with methanol, and subjected to Soxhlet extraction with tetrahydrofuran, the polymer material is obtained after vacuum drying at 70 ℃ for 24 h.

[0061] Performance test:

[0062] 1) The infrared spectrum of t-4Cl-PTPI is shown in Figure 1 .

[0063] It can be seen from Figure 1 that the characteristic vibration band at 2232 cm -1 of the terminal cyano group disappears after polymerization, indicating the absence of C≡N group. At the same time, new characteristic vibrations appear at 1578 cm -1 (-C=N- stretching vibration) and 1373 cm -1 (-C-N= stretching vibration), indicating that the nitrile group is successfully converted into triazine structure through trimerization, i.e., the formation of t-4Cl-PTP.

[0064] 2) The powder X-ray diffraction spectrum of t-4Cl-PTPI is shown in Figure 2 .

[0065] It can be seen from Figure 2 that the diffraction peak of t-4Cl-PTPI formed after trimerization of the cyano group is observed at 25.4° in 2θ value, which confirms the formation of the crystalline nature of t-4Cl-PTPI.

[0066] 3) The carbon solid-state nuclear magnetic resonance spectrum of t-4Cl-PTPI is shown in Figure 3 .

[0067] Depend on Figure 3 It can be known that the solid form of t-4Cl-PTPI 13 The C NMR spectrum showed a characteristic peak at 162 ppm, corresponding to the sp2 hybridized carbon atom in the triazine ring, further revealing the formation of t-4Cl-PTPI.

[0068] 4) Thermogravimetric diagram of t-4Cl-PTPI is as follows Figure 4 As shown.

[0069] Depend on Figure 4 It can be seen that t-4Cl-PTPI begins to decompose at 298℃, and the structural unit stabilizes at 400℃ with minimal mass loss, which means that t-4Cl-PTPI has good thermal stability.

[0070] 5) Nitrogen adsorption-desorption isotherms of t-4Cl-PTPI, as shown below Figure 5 As shown.

[0071] Depend on Figure 5 It can be seen that the specific surface area, measured by the volumetric method, is 60.0573 m². 2 / g, total pore volume is 0.083757cm³ 3 / g. t-4Cl-PTPI has a rich porous network.

[0072] 7) The UV-Vis absorption spectra of t-4Cl-PTPI and t-4Cl-PTPI˙ˉ are shown below. Figure 6 As shown.

[0073] Depend on Figure 6 It can be seen that the absorption spectrum of t-4Cl-PTPI˙ˉ shows three new peaks at 778, 926 and 1019 nm, which are characteristic peaks of the free radical anions generated by t-4Cl-PTPI after organic amine treatment.

[0074] 8) The electron spin resonance spectra of t-4Cl-PTPI and t-4Cl-PTPI are as follows: Figure 7 As shown.

[0075] Depend on Figure 7 It can be seen that t-4Cl-PTPI exhibits a typical EPR signal after treatment with organic amines, confirming the presence of free radicals.

[0076] 9) The heating curve of t-4Cl-PTPI˙ˉ is as follows Figure 8 As shown.

[0077] Depend on Figure 8 It can be seen that t-4Cl-PTPI˙ˉ heats up rapidly after being irradiated by a laser with a wavelength of 808nm, and the rate of temperature increase varies with the power of the laser lamp, reaching 0.8W / cm². 2The sample was heated to 185℃ under laser irradiation.

[0078] 10) The water evaporation curve of t-4Cl-PTPI˙ˉ is shown in Figure 9

[0079] It can be seen from Figure 9 that the mass of water in the beaker containing t-4Cl-PTPI˙ˉ decreases after 1h irradiation. The water evaporation rate is 1.77kg m -2 h -1 , and the efficiency is 98.07%.

[0080] The above description is for the technical personnel in the art, and other various corresponding changes and deformations can be made according to the technical solutions and technical concepts of the present application, and all these changes and deformations belong to the protection scope of the claims attached hereto.​

Claims

1. A class of perylene diimide porous organic polymeric materials characterized in that, The structure of the repeating unit is as follows: wherein R is a structural unit or the atom N.

2. The method of producing a perylene diimide porous organic polymer material according to claim 1, characterized by, The method comprises the following steps: 1) uniformly mixing 1,6,7,8-tetrachloroperylene-3,4,9,10-tetracarboxylic dianhydride, triamine monomer and diphenyl sulfone into a glass tube, and then sealing the glass tube after cooling in liquid nitrogen and melting under vacuum; 2) transferring the sealed glass tube into a muffle furnace for heating reaction to obtain a product; 3) taking out the product, grinding, washing, and vacuum drying to obtain a perylene diimide porous organic polymer; 4) treating the obtained perylene diimide porous organic polymer with an organic amine to obtain a perylene diimide porous organic polymer material; The molar ratio of the triamine monomer to 1,6,7,8-tetrachloroperylene-3,4,9,10-tetracarboxylic dianhydride and diphenyl sulfone is 1:1.5:(20-50).

3. The method for preparing perylene diimide porous organic polymer material according to claim 2, characterized in that: The triamine monomer in step 1) is tris(4-aminophenyl)amine, 2,4,6-tris(4-aminophenyl)-1,3,5-triazine or 1,3,5-tris(4-aminophenyl)benzene.

4. The method for preparing perylene diimide porous organic polymer material according to claim 2, characterized in that: The liquid nitrogen cooling time in step 1) is 5-15 min.

5. The method for preparing perylene diimide porous organic polymer material according to claim 2, characterized in that: The heating temperature is 300-500℃, and the heating time is 1-48 h. The grinding method in step 3) is ball milling, and the grinding time is 5-10 min.

6. The method for preparing perylene diimide porous organic polymer material according to claim 2, characterized in that: The washing solvent in step 3) is methanol and tetrahydrofuran in sequence.

7. The method for preparing perylene diimide porous organic polymer material according to claim 2, characterized in that: The drying temperature of the product in the vacuum drying process in step 3) is 60-85℃, and the drying time is usually 12-24 h.

8. The method for preparing perylene diimide porous organic polymer material according to claim 2, characterized in that: The organic amine in step 4) is diethylamine, ethylenediamine, trimethylamine, triethylamine, tripropylamine or isopropylamine.

9. The method for preparing the perylene diimide porous organic polymer material according to claim 2, characterized in that:

10. The perylene diimide porous organic polymer material of claim 1 is used as a photothermal material in solar water evaporation. ​

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