Preparation method and application of perylene diimide porous organic polymer material

Abstract

The invention discloses a preparation method and application of a perylene diimide porous organic polymer material, and belongs to the technical field of porous organic polymer materials.The preparation method comprises the following steps that 1, 6, 7, 8-tetrachloro perylene-3, 4, 9, 10-tetracarboxylic dianhydride, a triamine monomer and diphenyl sulfone are evenly mixed and transferred into a glass tube, after liquid nitrogen cooling, a reaction is carried out, and the perylene diimide porous organic polymer material is obtained; melting and sealing in a vacuum state; then transferring the sealed glass tube into a muffle furnace, heating, and carrying out polyimidization reaction to obtain a product; after the reaction is finished, taking out a product, and sequentially grinding, washing and drying in vacuum to obtain the perylene diimide porous organic polymer. After the perylene diimide porous organic polymer is treated by organic amine, the photothermal conversion material with excellent performance is obtained. The perylene diimide porous organic polymer has high photo-thermal conversion efficiency after being treated by organic amine, is simple to synthesize, high in yield and good in stability, is suitable for being used as a photo-thermal conversion material, and has a very good application prospect in the field of solar water evaporation.

Description

Technical Field

[0001] The invention belongs to the technical field of porous organic polymer materials, and in particular relates to the preparation and application of a type of perylene diimide porous organic polymer material. Background Art

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

[0003] Compared with organic small molecules, polymer materials often have more hierarchical structures, which can achieve the amplification and integration of the functions of structural units. Porous organic polymers (POPs) have high crystallinity, porous open channels, adjustable chemical composition, and can be modified at the atomic or molecular level by introducing functional monomers or functional groups, thus showing good light harvesting and heat conversion capabilities. Recent work has shown that they have good application prospects in photothermal conversion. However, most POPs have limited light harvesting capabilities, especially in the near-infrared (NIR) region, which limits the utilization of solar energy. In addition, they may also suffer energy loss through radiative relaxation, that is, most of the charges generated by POPs excitation will tend to recombine and release energy through radiative relaxation, while a small part of the light energy is converted into heat through non-radiative relaxation. Therefore, limited light harvesting ability and low level of photothermal conversion efficiency are the main obstacles hindering the application of POPs in photothermal conversion. Summary of the invention

[0004] In view of the defects and shortcomings of the prior art, the object of the present invention is to provide a preparation method and application of a perylene diimide porous organic polymer material.

[0005] In order to achieve the above-mentioned invention object, the present invention provides the following technical solutions:

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

[0007]

[0008] Among them, R is the structural unit or atom N.

[0009] The perylene diimide porous organic polymer material of the present invention has the following preparation reaction equation:

[0010]

[0011] The method for preparing the above-mentioned perylene diimide porous organic polymer material comprises the following steps:

[0012] 1) 1,6,7,8-tetrachloroperylene-3,4,9,10-tetracarboxylic dianhydride, triamine monomer and diphenyl sulfone are uniformly mixed and transferred into a glass tube, cooled with liquid nitrogen, and then melted and sealed under vacuum;

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

[0014] 3) taking out the product, grinding, washing and vacuum drying to obtain a perylene diimide porous organic polymer;

[0015] The obtained perylene diimide porous organic polymer is treated with an organic amine to obtain a 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 to 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 in step 3) is ball milling, and the grinding time is 5-10 minutes.

[0022] Preferably, the washing solvents 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 usually 12-24 hours.

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

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

[0026] The beneficial effects of the present invention are as follows: the perylene diimide porous organic polymer material of the present invention has high photothermal conversion efficiency after being treated with organic amines, and has simple synthesis and good stability, and is suitable as a photothermal conversion material, and has good application prospects in the field of solar water evaporation.

[0027] Specifically:

[0028] 1) The present invention treats the perylene diimide porous organic polymer material with an organic amine, so that the perylene diimide porous organic polymer material can generate delocalized radical anions through a mild photoinduced electron transfer process;

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

[0030] 3) The perylene diimide porous organic polymer material of the present invention has a high water evaporation rate after being treated with organic amines, and can be used as a photothermal conversion material, with broad application prospects. BRIEF DESCRIPTION OF THE DRAWINGS

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

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

[0033] Figure 3 This is the carbon solid NMR image of t-4Cl-PTPI in the example.

[0034] Figure 4 This is the thermogravimetric diagram of t-4Cl-PTPI in the example.

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

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

[0037] Figure 7 1 is the electron paramagnetic resonance spectrum of t-4Cl-PTPI and t-4Cl-PTPI in the examples.

[0038] Figure 8 This is the temperature rise curve of t-4Cl-PTPI˙ˉ in the example.

[0039] Fig. 9 This is the water evaporation curve of t-4Cl-PTPI˙ˉ in the example. DETAILED DESCRIPTION

[0040] The present invention is further described in detail below in conjunction with the embodiments. It should be understood that the specific embodiments described herein are only used to explain the present invention and are not limited to the present invention.

[0041] Embodiment 1:

[0042] A type of perylene diimide porous organic polymer material (taking 2,4,6-tris(4-aminophenyl)-1,3,5-triazine as a triamine monomer as an example), the preparation method thereof is as follows:

[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) were uniformly mixed, and the mixture was transferred to a glass tube, cooled with liquid nitrogen for 5 min, and then melted and sealed under vacuum; the sealed glass tube was transferred to a muffle furnace, heated at 10°C / min, and heated at 350°C for 1.5 h to obtain a red product; the product was taken out, ball-milled for 5 min, rinsed with methanol, extracted with tetrahydrofuran Soxhlet, and vacuum dried at 60°C for 12 h to obtain the perylene diimide porous organic polymer t-4Cl-PTPI.

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

[0045] 500 mg of t-4Cl-PTPI was placed in a glass bottle and isopropylamine vapor was passed through for 10 minutes. The treated material was recorded as t-4Cl-PTPI˙ˉ.

[0046] Embodiment 2:

[0047] A type of perylene diimide porous organic polymer material (taking tris(4-aminophenyl)amine as a triamine monomer as an example), the preparation method thereof is as follows:

[0048] Synthesis of 4Cl-PDH-TAPA: 1,6,7,8-tetrachloroperylene-3,4,9,10-tetracarboxylic dianhydride (0.159 mg, 0.3 mm), tri(4-aminophenyl)amine (0.058 mg, 0.2 mm) and diphenyl sulfone (1.6920 g) were uniformly mixed, and the mixture was transferred to a glass tube. After cooling with liquid nitrogen for 5 min, the mixture was melted and sealed under vacuum. The sealed glass tube was transferred to a muffle furnace, heated at 10 °C / min, and heated at 350 °C for 1.5 h to obtain a red product. The product was taken out, ball-milled for 5 min, rinsed with methanol, extracted with tetrahydrofuran, and dried in vacuum at 60 °C for 12 h to obtain the perylene diimide porous organic polymer 4Cl-PDH-TAPA.

[0049] A type of perylene diimide porous organic polymer material (taking tris(4-aminophenyl)amine as a triamine monomer as an example) is treated with an organic amine, and the treatment method includes the following steps:

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

[0051] Embodiment 3:

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

[0053] A type of perylene diimide porous organic polymer material (taking 1,3,5-tris(4-aminophenyl)benzene as a triamine monomer as an example), the preparation method thereof is as follows:

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

[0055] A type of perylene diimide porous organic polymer material (taking 1,3,5-tris(4-aminophenyl)benzene as a triamine monomer as an example) is treated with an organic amine, and the treatment method includes the following steps:

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

[0057] Embodiment 4:

[0058] Different from Examples 1-3, the mixture was transferred to a glass tube, cooled with liquid nitrogen for 15 minutes, and then melted and sealed under vacuum; the sealed glass tube was transferred to a muffle furnace, heated at 5°C / min, and heated at 500°C for 48 hours to obtain a red product; the product was taken out, ball-milled for 10 minutes, rinsed with methanol, extracted with tetrahydrofuran, and vacuum dried at 85°C for 20 hours to obtain a polymer material.

[0059] Embodiment 5:

[0060] Different from Examples 1-4, the mixture was transferred to a glass tube, cooled with liquid nitrogen for 10 minutes, and then melted and sealed under vacuum; the sealed glass tube was transferred to a muffle furnace, heated at 7°C / min, and heated at 400°C for 30 hours to obtain a red product; the product was taken out, ball-milled for 8 minutes, rinsed with methanol, extracted with tetrahydrofuran, and vacuum dried at 70°C for 24 hours to obtain a polymer material.

[0061] Performance Test:

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

[0063] Depend on Figure 1 It can be seen that after polymerization, the terminal cyano group is at 2232 cm -1 The characteristic vibration band at 1578cm -1 (-C=N- stretching vibration) and 1373cm -1 The appearance of a new characteristic vibration at (-CN = stretching vibration) indicates that the nitrile group is successfully converted into a 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 as follows: Figure 2 shown.

[0065] Depend on Figure 2 It can be seen that the diffraction peak of t-4Cl-PTPI formed after cyano trimerization was observed to be 25.4° at a 2θ value, and this peak value confirmed the formation of the crystalline properties of t-4Cl-PTPI.

[0066] 3) The carbon solid NMR image of t-4Cl-PTPI is as follows Figure 3 shown.

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

[0068] 4) Thermogravimetric diagram of t-4Cl-PTPI Figure 4 shown.

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

[0070] 5) Nitrogen adsorption-desorption isotherm of t-4Cl-PTPI Figure 5 shown.

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

[0072] 7) UV-visible absorption spectra of t-4Cl-PTPI and t-4Cl-PTPI˙ˉ are shown in Figure 6 shown.

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

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

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

[0076] 9)T-4Cl-PTPI˙ˉTemperature rise curve Figure 8 shown.

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

[0078] 10) t-4Cl-PTPI˙ˉ water evaporation curve Fig. 9 shown.

[0079] Depend on Fig. 9 It can be seen that the mass of water in the beaker where t-4Cl-PTPI˙ˉ is located decreases after 1 h of illumination. By calculation, the evaporation rate of water is 1.77 kg m -2 h -1 , the efficiency is 98.07%.

[0080] As described above, for those skilled in the art, various other corresponding changes and modifications can be made based on the technical solutions and technical concepts of the present invention, and all these changes and modifications belong to the protection scope of the appended claims of the present invention.

Claims

1. A type of perylene diimide porous organic polymer material, characterized in that: The structure of its repeating unit is as follows: Among them, R is the structural unit or atom N.

2. The method for preparing the perylene diimide porous organic polymer material according to claim 1, characterized in that: The following steps are involved: 1) 1,6,7,8-tetrachloroperylene-3,4,9,10-tetracarboxylic dianhydride, triamine monomer and diphenyl sulfone are uniformly mixed and transferred into a glass tube, cooled with liquid nitrogen, and then melted and sealed under vacuum; 2) transferring the sealed glass tube to 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 the perylene diimide porous organic polymer material according to claim 2, characterized in that: In step 1), the triamine monomer 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 the perylene diimide porous organic polymer material according to claim 2, characterized in that: The liquid nitrogen cooling time in step 1) is 5 to 15 minutes.

5. The method for preparing the perylene diimide porous organic polymer material according to claim 2, characterized in that: Step 2) the heating temperature rise rate is 5-10°C / min; The heating temperature is 300-500° C., and the heating time is 1-48 hours.

6. The method for preparing the perylene diimide porous organic polymer material according to claim 2, characterized in that: Step 3) The grinding method is ball milling, and the grinding time is 5-10 minutes.

7. The method for preparing the perylene diimide porous organic polymer material according to claim 2, characterized in that: Step 3) The washing solvents are methanol and tetrahydrofuran, respectively.

8. The method for preparing the perylene diimide porous organic polymer material according to claim 2, characterized in that: Step 3) The drying temperature of the product during vacuum drying is 60-85° C., and the drying time is usually 12-24 hours.

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

10. Use of the perylene diimide porous organic polymer material according to claim 1 as a photothermal material in solar water evaporation.

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