Preparation method and application of pyrrole-boron-based porous conjugated polymer material
By using aldol condensation reactions of pyrroloboryl methyl or methylene functionalized monomers with aldehyde monomers, the synthesis challenges of pyrroloboryl porous conjugated polymers were solved, and highly efficient photocatalytic materials were prepared, achieving improvements in high specific surface area and photocatalytic performance.
Patent Information
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2024-11-20
- Publication Date
- 2026-05-22
AI Technical Summary
The synthesis of pyrroloborone-based porous conjugated polymers is difficult to achieve in the existing technology, especially due to the lack of pyrroloborone monomers with aldol condensation reactivity, resulting in low degree of polymerization and non-porous structure, and the solvothermal reaction limits its large-scale preparation.
A pyrroloboryl methyl or methylene functionalized monomer is used to carry out an aldol condensation reaction with a centrosymmetric aldehyde monomer in the presence of a catalyst to form a pyrroloboryl porous conjugated polymer through carbon-carbon double bond linkage. The reaction conditions are optimized to achieve efficient preparation.
A BPCP material with high specific surface area and uniform pore size distribution was successfully prepared, achieving high efficiency in the photocatalytic preparation of hydrogen peroxide without the need for metal co-catalysts and sacrificial agents, thus enhancing the material's potential for functional applications.
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Figure CN122071585A_ABST
Abstract
Description
Technical Field
[0001] This invention belongs to the field of porous conjugated polymer technology, and relates to a method for preparing and applying a pyrrole-boron-based porous conjugated polymer material. Background Technology
[0002] Pyrroleboryl conjugated porous polymers (BPCPs) are a class of organic porous materials composed of monomers with pyrroleboryl (pyrroleboryl) units linked by carbon-carbon double bonds. They have the characteristics of narrow band gap, suitable band structure, high degree of conjugation, excellent carrier transport and separation properties, high chemical and thermal stability, strong designability and easy functionalization. They have wide applications in next-generation organic semiconductor devices, photocatalytic energy conversion and storage, photothermal therapy, gas adsorption and separation.
[0003] However, despite the numerous advantages of BPCP materials, their synthesis still faces several challenges, primarily due to the lack of pyrroloborone monomers with aldol condensation reactivity. This makes the use of pyrroloborone units in the preparation of porous conjugated polymers extremely difficult. Traditional solvothermal synthesis under alkaline conditions often results in low polymerization degrees and the formation of non-porous structures. Furthermore, solvothermal reaction methods significantly limit the large-scale preparation of pyrroloborone-based porous polymers.
[0004] Therefore, future research will focus on developing new synthetic methods to overcome the above challenges and achieve the efficient preparation of pyrroloboron-based porous conjugated polymers and their widespread application in practical applications. Summary of the Invention
[0005] To address the aforementioned problems in the prior art, the present invention aims to provide a method for preparing and applying pyrroloborone-based porous conjugated polymer materials, thereby overcoming the shortcomings of the prior art.
[0006] One objective of this invention is achieved through the following technical solution:
[0007] A method for preparing a pyrroloboron-based porous conjugated polymer material includes the following steps:
[0008] Pyrroloboryl methyl or methylene functionalized monomers and centrosymmetric aldehyde monomers undergo aldol condensation in a catalyst-containing reaction system to polymerize and form pyrroloboryl-based porous conjugated polymer materials.
[0009] In the presence of a catalyst, pyrroloborylmethyl or methylene functionalized monomers and centrosymmetric aldehyde monomers undergo aldol condensation. The pyrroloborylmethyl or methylene functionalized monomers and centrosymmetric aldehyde monomers are linked by carbon-carbon double bonds and polymerize to form BPCP materials.
[0010] Preferably, the pyrroloborylmethyl or methylene functionalized monomer is one or more of the structures shown in formulas (A)-(E):
[0011]
[0012] Wherein, R1 is -H, -X, -COOH, -CN, -NO2, -(CH2)nCH3, -CO2(CH2)nCH3, -O(CH2)nCH3, One or more of the following, where X is one or more of F, Cl, Br, and I, and n is a natural number from 0 to 10; R2 is -H, -CN, One or more of the following, where R is one or more of -H and -(CH2)nCH3;
[0013]
[0014] Wherein, R3 is -H, -X, -COOH, -CN, -NO2, -(CH2)nCH3, -CO2(CH2)nCH3, -O(CH2)nCH3, One or more of the following, X is one or more of F, Cl, Br, I, and n is a natural number from 0 to 10;
[0015]
[0016] Among them, R4 and R5 are each selected independently from one or more of -H and -(CH2)nCH3, and one of R4 and R5 must be -(CH2)nCH3, where n is a natural number from 0 to 10;
[0017]
[0018] R6 is selected from one or more of -(CH2)nCH3 and -(CH2)nCN, where n is a natural number from 0 to 10;
[0019]
[0020] Preferably, the pyrroloborylmethyl or methylene functionalized monomer is one or more of the structures shown in Formulas 1-42:
[0021]
[0022]
[0023] Preferably, the centrosymmetric aldehyde monomer is one or more of the following: C2 symmetric aldehyde monomer, C3 symmetric aldehyde monomer, and C4 symmetric aldehyde monomer.
[0024] Preferably, the centrosymmetric aldehyde monomer is one or more of the structures shown in Formula 1-1 to Formula 1-15:
[0025]
[0026] Preferably, the amounts of the pyrroloborylmethyl or methylene functionalized monomer and the centrosymmetric aldehyde monomer are such that the molar ratio of the methyl or methylene group of the pyrroloborylmethyl or methylene functionalized monomer to the aldehyde group of the centrosymmetric aldehyde monomer is 0.8–1.2:0.8–1.2.
[0027] Preferably, the catalyst is an acidic or basic catalyst, including but not limited to one or more of benzoic acid, benzoic anhydride, p-toluenesulfonic acid, difluoroacetic acid, trifluoroacetic acid, acetic acid, p-fluorobenzoic acid, phthalic acid, terephthalic acid, trimesic acid, cesium carbonate, potassium carbonate, sodium hydroxide, potassium hydroxide, and 1,8-diazabicycloundec-7-ene.
[0028] The mass ratio of the catalyst to the pyrroloborylmethyl or methylene functionalized monomer can be listed as 1 to 30:1, and more specifically 1.5 to 20:1.
[0029] Preferably, the reaction system further includes an organic solvent, wherein the organic solvent is one or more selected from dimethylacetamide, dimethylformamide, o-dichlorobenzene, n-butanol, toluene, mesitylene, n-butanol, and dioxane.
[0030] Preferably, the aldol condensation reaction is carried out in an anaerobic environment.
[0031] Preferably, the temperature of the aldol condensation reaction is 100–250°C, more preferably 120–200°C, for example, 120, 130, 140, 150, 160, 170, 180, 190, or 200°C; the time of the aldol condensation reaction is 1–20 days, more preferably 3–15 days, for example, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, or 15 days.
[0032] The aldol condensation reaction of pyrroloborylmethyl or methylene functionalized monomers and centrosymmetric aldehyde monomers can be carried out in the absence of organic solvents or in the presence of organic solvents.
[0033] When the aldol condensation reaction of a pyrroloborylmethyl or methylene functionalized monomer and a centrosymmetric aldehyde monomer is carried out under organic solvent-free conditions, the preparation method preferably includes the following steps:
[0034] A homogeneous reaction system is formed by mixing pyrroloborylmethyl or methylene functionalized monomers, a centrosymmetric aldehyde monomer, and a catalyst; the homogeneous reaction system is then heated to carry out an aldol condensation reaction.
[0035] Preferably, the preparation method further includes: first evacuating the homogeneous mixed reaction system under vacuum for 1-30 minutes and then sealing it, followed by heating the homogeneous mixed reaction system. When the reaction system contains no organic solvent, an oxygen-free environment is created by directly evacuating and sealing it.
[0036] When the aldol condensation reaction of a pyrroloborylmethyl or methylene functionalized monomer and a centrosymmetric aldehyde monomer is carried out in the presence of an organic solvent, preferably, the preparation method includes the following steps:
[0037] Pyrroloborylmethyl or methylene functionalized monomers and centrosymmetric aldehyde monomers are dissolved in an organic solvent, and a catalyst is added and mixed evenly to form a homogeneous reaction system; the homogeneous reaction system is heated to carry out aldol condensation reaction.
[0038] Preferably, the preparation method further includes: first freezing the homogeneous reaction system with liquid nitrogen, then evacuating it for 1-30 minutes and sealing it, and then heating the homogeneous reaction system. When the reaction system contains organic solvent, it is first frozen with liquid nitrogen and then evacuated and sealed to create an oxygen-free environment.
[0039] Preferably, after the aldol condensation reaction is completed, the reaction product is washed with a solvent and dried to obtain the BPCP material. Examples of solvents include methanol, ethanol, acetone, and tetrahydrofuran.
[0040] The mechanism by which this invention successfully prepares BPCP materials is as follows: a carbon-carbon double bond-bridged framework material is formed through a pyrroloboronic-induced aldol condensation reaction. Then, through the optimization of the reaction system (such as reaction solvent and catalyst) and reaction parameters (such as reaction time and temperature), the thermodynamically controlled crystal self-repair and kinetically driven polymerization process are brought into equilibrium, thereby obtaining a porous BPCP material.
[0041] The second objective of this invention is achieved through the following technical solution:
[0042] A pyrroloboron-based porous conjugated polymer material is prepared by the following steps: pyrroloboron-based methyl or methylene functionalized monomers and centrosymmetric aldehyde monomers are subjected to an aldol condensation reaction in a catalyst-containing reaction system to polymerize and form a pyrroloboron-based porous conjugated polymer material.
[0043] Preferably, the pyrrole-boron-based porous conjugated polymer material has a fully conjugated structure.
[0044] Preferably, the specific surface area of the pyrrole-boron-based porous conjugated polymer material is ≥1000 m². 2 / g, further preferably 1000-2000m 2 / g; pore size distribution is 0.1–2.0 nm, more preferably 0.5–1.2 nm.
[0045] The third objective of this invention is achieved through the following technical solution:
[0046] Application of a pyrrole-boron-based porous conjugated polymer material in the field of photocatalysis.
[0047] Preferably, the pyrrole-boron-based porous conjugated polymer material, as an organic semiconductor catalyst, can directly convert air and water into hydrogen peroxide without the need for the addition of metal co-catalysts and / or sacrificial agents.
[0048] Preferably, the photocatalytic hydrogen peroxide production efficiency of the pyrrole-boron-based porous conjugated polymer material is ≥30 mmol / g. -1 h -1 More preferably 30–60 mmol g -1 h -1 .
[0049] Compared with the prior art, the present invention has the following beneficial effects:
[0050] 1. This invention provides a universal method for synthesizing BPCP materials: a centrosymmetric pyrroloboryl monomer containing methyl or methylene groups and a centrosymmetric aldehyde monomer are combined under optimized reaction conditions through an aldol condensation reaction, connecting the two building units through carbon-carbon double bonds to obtain a porous conjugated pyrroloboryl porous conjugated polymer material.
[0051] 2. The present invention provides a universal BPCP material preparation method that can achieve the synthesis and functionalization of porous conjugated polymer materials in one step without the need for additional reversible chemical reaction design.
[0052] 3. This invention optimizes the polymerization strategy of aldol condensation, employing an aldol condensation strategy induced by pyrroloborylmethyl functionalized monomers with excellent in-plane conjugation and high luminescence efficiency to synthesize on a large scale a series of products with ultra-high specific surface areas (≥1000 m²). 2 BPCP materials with characteristics of uniform pore size distribution (0.1–2.0 nm) and g / g.
[0053] 4. The BPCP material prepared by this invention has significant performance in the photocatalytic preparation of hydrogen peroxide, and can achieve the highest photocatalytic hydrogen peroxide production efficiency (54.8 mmol g-1h-1) currently available; moreover, this material does not require the addition of metal co-catalysts and sacrificial agents in the photocatalytic process, and can directly convert air and water into hydrogen peroxide.
[0054] 5. This invention solves the problem of the single structure of traditional porous conjugated polymer materials and the difficulty in functionalizing them for photocatalytic conversion of high-value-added products by using aldol condensation reactions of various centrosymmetric pyrroloboryl monomers containing methyl or methylene groups and aldehyde monomers with centrosymmetry.
[0055] In summary, this invention not only provides an efficient method for synthesizing BPCP materials, but also enables these materials to exhibit excellent performance in the photocatalytic preparation of hydrogen peroxide, opening up new avenues for the design and application of future organic semiconductor catalysts. Attached Figure Description
[0056] Figure 1 This is a synthesis route diagram of BPCP materials in some embodiments of the present invention;
[0057] Figure 2 The B-sp prepared in Example 1 of this invention 2 Infrared spectrum of c-COF-1;
[0058] Figure 3 The B-sp prepared in Example 1 of this invention 2 solid-state NMR spectrum of c-COF-1;
[0059] Figure 4 The B-sp prepared in Example 1 of this invention 2 X-ray diffraction pattern of c-COF-1 and calculation simulation data;
[0060] Figure 5 The B-sp prepared in Example 1 of this invention 2 Nitrogen adsorption-desorption data of c-COF-1;
[0061] Figure 6 The B-sp prepared in Example 1 of this invention 2 Pore size distribution data of c-COF-1;
[0062] Figure 7 The B-sp prepared in Example 2 of this invention 2 X-ray diffraction pattern and computational simulation data of c-COF-2;
[0063] Figure 8 The B-sp prepared in Example 3 of this invention2 X-ray diffraction pattern and computational simulation data of c-COF-3;
[0064] Figure 9 The B-sp prepared in Example 1 of this invention 2 Data graph of photocatalytic preparation of photo-oxidized hydrogen using c-COF-1. Detailed Implementation
[0065] The technical solution of the present invention will be further described and illustrated below with reference to specific embodiments and accompanying drawings. It should be understood that the specific embodiments described herein are only for the purpose of helping to understand the present invention and are not intended to limit the specific scope of the present invention. Furthermore, the accompanying drawings used herein are merely for better illustrating the content disclosed in the present invention and do not limit the scope of protection. Unless otherwise specified, the raw materials used in the embodiments of the present invention are all commonly used in the art. Experimental methods in the following embodiments that do not specify specific conditions are generally performed under conventional conditions or according to the conditions recommended by the manufacturer.
[0066] like Figure 1 As shown, some embodiments of the present invention provide a method for preparing a BPCP material, comprising: thoroughly mixing a pyrroloboryl methyl or methylene functionalized monomer, an aldehyde monomer, and a catalyst to form a homogeneous mixed reaction system; heating the homogeneous mixed reaction system to promote aldol condensation under high temperature, wherein the pyrroloboryl methyl or methylene functionalized monomer and the aldehyde monomer are connected by carbon-carbon double bonds to polymerize and form a pyrroloboryl porous conjugated polymer material.
[0067] Example 1
[0068] In this embodiment, B-sp 2 The preparation of c-COF-1 includes the following steps:
[0069] (1) Sealing reaction: Pyrroloborylmethyl functionalized monomer (Formula 1) (30mg), 1,4-bis(4-aldehydephenyl)benzene (Formula 1-5) (69.25mg) and benzoic anhydride (109.43mg) were added to a quartz glass tube and mixed evenly. After vacuuming for 15 minutes, the quartz glass tube was melt-sealed. Then the quartz glass tube was heated at 180℃ for 3 days.
[0070] (2) Post-reaction treatment: After the reaction, the product was washed with acetone and tetrahydrofuran solvent, and then dried under vacuum to obtain the pyrrole-boron-based porous conjugated polymer material B-sp. 2 c-COF-1.
[0071] The pyrrole-boron-based porous conjugated polymer material B-sp obtained in this embodiment 2 The infrared spectral characterization results of c-COF-1 are as follows: Figure 2As shown, 1637cm -1 The infrared vibration peaks indicate the formation of carbon-carbon double bonds. Figure 3 The solid-state carbon NMR spectrum, with a signal at ~130 ppm, further confirms B-sp. 2 The formation of carbon-carbon double bonds in c-COF-1. B-sp 2 The powder X-ray diffraction pattern of c-COF-1 is as follows: Figure 4 As shown, this material exhibits good crystallinity. Simultaneously, nitrogen adsorption-desorption experiments demonstrate that the prepared B-sp... 2 c-COF-1 has a high concentration of 1840m 2 g -1 Specific surface area ( Figure 5 It also has two main pore size distributions, 0.6 nm and 1.2 nm, respectively. Figure 6 ).
[0072] Photocatalytic preparation of hydrogen peroxide: 5 mg B-sp 2 c-COF-1 was dispersed in 50 mL of water, sonicated for 3 min, and then placed under simulated sunlight. The concentration of H2O2 produced in the heterogeneous aqueous solution was determined by the potassium titanium oxalate method: after a fixed light exposure time interval, 1.5 mL of the reaction solution was extracted using a syringe with a 0.25 μm syringe filter at the top, and then mixed with 2.5 mL of the prepared potassium titanium oxalate solution (0.02 mol / L). -1 The mixture was then analyzed, and the concentration of H2O2 was calculated using a UV-Vis spectrophotometer based on the absorbance at 400 nm. The B-sp prepared in Example 1... 2 Data on the photocatalytic preparation of photo-oxidized hydrogen using c-COF-1 are available in [link to data]. Figure 9 .
[0073] Example 2
[0074] In this embodiment, B-sp 2 The preparation of c-COF-2 includes the following steps:
[0075] (1) Sealing reaction: Pyrroloborylmethyl functionalized monomer (Formula 1) (30mg), 2,5-dihydroxyterephthalaldehyde (Formula 1-2) (32.44mg), and benzoic anhydride (109.43mg) were added to a quartz glass tube and mixed evenly. After vacuuming for 15 minutes, the quartz glass tube was melt-sealed. Then, the quartz glass tube was heated at 200℃ for 5 days.
[0076] (2) Post-reaction treatment: After the reaction, the product was washed with acetone and tetrahydrofuran solvent, and then dried under vacuum to obtain the pyrrole-boron-based porous conjugated polymer material B-sp. 2 c-COF-2.
[0077] Figure 7 B-sp prepared in Example 2 2 The X-ray diffraction pattern of c-COF-2 shows that the material has good crystallinity.
[0078] Example 3
[0079] In this embodiment, B-sp 2 The preparation of c-COF-3 includes the following steps:
[0080] (1) Sealing reaction: Pyrroloborylmethyl functionalized monomer (Formula 1) (30mg), 4,4'-biphenyldicarboxaldehyde (Formula 1-3) (50.85mg), and benzoic anhydride (109.43mg) were added to a quartz glass tube and mixed evenly. After vacuuming for 15 minutes, the quartz glass tube was melt-sealed. Then, the quartz glass tube was heated at 180°C for 7 days.
[0081] (2) Post-reaction treatment: After the reaction, the product was washed with acetone and tetrahydrofuran solvent, and then dried under vacuum to obtain the pyrrole-boron-based porous conjugated polymer material B-sp. 2 c-COF-3.
[0082] Figure 8 B-sp prepared in Example 3 2 The X-ray diffraction pattern of c-COF-2 shows that the material has good crystallinity.
[0083] Example 4
[0084] In this embodiment, B-sp 2 The preparation of c-COF-4 includes the following steps:
[0085] (1) Sealing reaction: Add pyrroloborylmethyl functionalized monomer (Formula 2) (30mg), 4,4'-biphenyldicarboxaldehyde (Formula 1-3) (44.41mg), and benzoic anhydride (109.43mg) to a quartz glass tube and mix them evenly. After vacuuming for 15 minutes, the quartz glass tube is sealed. Then, the quartz glass tube is heated at 150℃ for 3 days.
[0086] (2) Post-reaction treatment: After the reaction, the product was washed with acetone and tetrahydrofuran solvent, and then dried under vacuum to obtain the pyrrole-boron-based porous conjugated polymer material B-sp. 2 c-COF-4.
[0087] Example 5
[0088] In this embodiment, B-sp 2 The preparation of c-COF-5 includes the following steps:
[0089] (1) Sealing reaction: Add pyrroloborylmethyl functionalized monomer (Formula 3) (30mg), 2,5-dihydroxyterephthalaldehyde (Formula 1-2) (32.44mg), and benzoic anhydride (109.43mg) to a quartz glass tube and mix them evenly. After vacuuming for 15 minutes, the quartz glass tube is sealed. Then, the quartz glass tube is heated at 150℃ for 3 days.
[0090] (2) Post-reaction treatment: After the reaction, the product was washed with acetone and tetrahydrofuran solvent, and then dried under vacuum to obtain the pyrrole-boron-based porous conjugated polymer material B-sp. 2 c-COF-5.
[0091] Example 6
[0092] In this embodiment, B-sp 2 The preparation of c-COF-6 includes the following steps:
[0093] (1) Sealing reaction: Pyrroloborylmethyl functionalized monomer (Formula 4) (35 mg), 1,3,6,8-tetra(4-formylphenyl)pyrene (Formula 1-11) (120.18 mg), 1,4-dioxane (1 mL), mesitylene (1 mL), and trifluoroacetic acid (300 μL) were added to a quartz glass tube and mixed evenly. The mixture was frozen with liquid nitrogen and vacuumed for 15 minutes to seal the quartz glass tube. Then the quartz glass tube was heated at 200 °C for 3 days.
[0094] (2) Post-reaction treatment: After the reaction, the product was washed with acetone and tetrahydrofuran solvent, and then dried under vacuum to obtain the pyrrole-boron-based porous conjugated polymer material B-sp. 2 c-COF-6.
[0095] Example 7
[0096] In this embodiment, B-sp 2 The preparation of c-COF-7 includes the following steps:
[0097] (1) Sealing reaction: Add pyrroloborylmethyl functionalized monomer (Formula 38) (55mg), 1,3,6,8-tetra(4-formylphenyl)pyrene (Formula 1-11) (55mg), 1,4-dioxane (1mL), mesitylene (1mL), and trifluoroacetic acid (300μL) to a quartz glass tube and mix well. Freeze with liquid nitrogen, evacuate for 15 minutes, and then seal the quartz glass tube. Then place the quartz glass tube at 200℃ for 3 days.
[0098] (2) Post-reaction treatment: After the reaction, the product was washed with acetone and tetrahydrofuran solvent, and then dried under vacuum to obtain the pyrrole-boron-based porous conjugated polymer material B-sp. 2c-COF-7.
[0099] Example 8
[0100] In this embodiment, B-sp 2 The preparation of c-COF-8 includes the following steps:
[0101] (1) Sealing reaction: Add pyrroloborylmethyl functionalized monomer (Formula 39) (55mg), 1,3,6,8-tetra(4-formylphenyl)perylene (Formula 1-12) (55mg), 1,4-dioxane (1mL), mesitylene (1mL), and trifluoroacetic acid (300μL) to a quartz glass tube and mix well. Freeze with liquid nitrogen, evacuate for 15 minutes, and then seal the quartz glass tube. Then place the quartz glass tube at 180℃ for 3 days.
[0102] (2) Post-reaction treatment: After the reaction, the product was washed with acetone and tetrahydrofuran solvent, and then dried under vacuum to obtain the pyrrole-boron-based porous conjugated polymer material B-sp. 2 c-COF-8.
[0103] Example 9
[0104] In this embodiment, B-sp 2 The preparation of c-COF-9 includes the following steps:
[0105] (1) Sealing reaction: Add pyrroloborylmethyl functionalized monomer (Formula 40) (40mg), tetraaldehyde phenylporphyrin (Formula 1-13) (44mg), 1,4-dioxane (1mL), mesitylene (1mL), and trifluoroacetic acid (300μL) to a quartz glass tube and mix well. Freeze with liquid nitrogen and evacuate for 15 minutes to seal the quartz glass tube. Then place the quartz glass tube at 120℃ and heat for 3 days.
[0106] (2) Post-reaction treatment: After the reaction, the product was washed with acetone and tetrahydrofuran solvent, and then dried under vacuum to obtain the pyrrole-boron-based porous conjugated polymer material B-sp. 2 c-COF-9.
[0107] Example 10
[0108] In this embodiment, B-sp 2 The preparation of c-COF-10 includes the following steps:
[0109] (1) Sealing reaction: Add pyrroloborylmethyl functionalized monomer (Formula 41) (40mg), tetraaldehyde tetraphenylethylene (Formula 1-15) (52mg), 1,4-dioxane (1mL), mesitylene (1mL), and potassium carbonate (40mg) to a quartz glass tube and mix well. Freeze with liquid nitrogen and evacuate for 15 minutes to seal the quartz glass tube. Then place the quartz glass tube at 120℃ and heat for 3 days.
[0110] (2) Post-reaction treatment: After the reaction, the product was washed with water, acetone, and tetrahydrofuran solvent, and then dried under vacuum to obtain the single-crystal carbon-carbon double bond covalent organic framework material B-sp. 2 c-COF-10.
[0111] All aspects, embodiments, and features of this invention should be considered illustrative in all respects and not limiting of the invention; the scope of the invention is defined only by the claims. Other embodiments, modifications, and uses will become apparent to those skilled in the art without departing from the spirit and scope of the invention as claimed.
[0112] In the preparation method of this invention, the order of the steps is not limited to the listed order. For those skilled in the art, variations in the order of the steps without creative effort are also within the scope of protection of this invention. Furthermore, two or more steps or actions can be performed simultaneously.
[0113] Finally, it should be noted that the specific embodiments described herein are merely illustrative examples of the invention and are not intended to limit the implementation of the invention. Those skilled in the art can make various modifications or additions to the described specific embodiments or use similar methods to replace them; it is neither necessary nor possible to exemplify all embodiments here. However, these obvious variations or modifications derived from the essential spirit of the invention still fall within the scope of protection of the invention, and interpreting them as any additional limitation would contradict the spirit of the invention.
Claims
1. A method for preparing a pyrroloboron-based porous conjugated polymer material, characterized in that, The preparation method includes the following steps: Pyrroloboryl methyl or methylene functionalized monomers and centrosymmetric aldehyde monomers undergo aldol condensation in a catalyst-containing reaction system to polymerize and form pyrroloboryl-based porous conjugated polymer materials.
2. The preparation method according to claim 1, characterized in that, The pyrroloborylmethyl or methylene functionalized monomer is one or more of the structures shown in formulas (A)-(E): Wherein, R1 is -H, -X, -COOH, -CN, -NO2, -(CH2)nCH3, -CO2(CH2)nCH3, -O(CH2)nCH3, One or more of the following, where X is one or more of F, Cl, Br, and I, and n is a natural number from 0 to 10; R2 is -H, -CN, One or more of the following, where R is one or more of -H and -(CH2)nCH3; Wherein, R3 is -H, -X, -COOH, -CN, -NO2, -(CH2)nCH3, -CO2(CH2)nCH3, -O(CH2)nCH3, One or more of the following, X is one or more of F, Cl, Br, I, and n is a natural number from 0 to 10; Among them, R4 and R5 are each selected independently from one or more of -H and -(CH2)nCH3, and one of R4 and R5 must be -(CH2)nCH3, where n is a natural number from 0 to 10; R6 is selected from one or more of -(CH2)nCH3 and -(CH2)nCN, where n is a natural number from 0 to 10; 3. The preparation method according to claim 1 or 2, characterized in that, The pyrroloborylmethyl or methylene functionalized monomer is one or more of the structures shown in Formulas 1-42:
4. The preparation method according to claim 1, characterized in that, The centrosymmetric aldehyde monomer is one or more of the structures shown in Formula 1-1 to Formula 1-15:
5. The preparation method according to claim 1, characterized in that, The amounts of pyrroloboryl methyl or methylene functionalized monomers and centrosymmetric aldehyde monomers are such that the molar ratio of the methyl or methylene group of the pyrroloboryl methyl or methylene functionalized monomer to the aldehyde group of the centrosymmetric aldehyde monomer is 0.8–1.2:0.8–1.
2. And / or, the catalyst is one or more of benzoic acid, benzoic anhydride, p-toluenesulfonic acid, difluoroacetic acid, trifluoroacetic acid, acetic acid, p-fluorobenzoic acid, phthalic acid, terephthalic acid, trimesic acid, cesium carbonate, potassium carbonate, sodium hydroxide, potassium hydroxide, and 1,8-diazabicycloundec-7-ene; And / or, the reaction system further includes an organic solvent, said organic solvent being one or more of dimethylacetamide, dimethylformamide, o-dichlorobenzene, n-butanol, toluene, mesitylene, n-butanol, and dioxane; And / or, the aldol condensation reaction is carried out in an anaerobic environment; And / or, the aldol condensation reaction is carried out at a temperature of 100–250°C for a time of 1–20 days.
6. The preparation method according to claim 1, characterized in that, The preparation method includes the following steps: A pyrroloborylmethyl or methylene functionalized monomer, a centrosymmetric aldehyde monomer, and a catalyst are mixed to form a homogeneous mixed reaction system. The homogeneous mixed reaction system is first evacuated for 1 to 30 minutes and then sealed. The homogeneous mixed reaction system is then heated to carry out an aldol condensation reaction.
7. The preparation method according to claim 1, characterized in that, The preparation method includes the following steps: Pyrroloborylmethyl or methylene functionalized monomers and centrosymmetric aldehyde monomers are dissolved in an organic solvent, and a catalyst is added and mixed evenly to form a homogeneous reaction system. The homogeneous reaction system is first frozen with liquid nitrogen, then evacuated for 1 to 30 minutes and sealed. The homogeneous reaction system is then heated to carry out an aldol condensation reaction.
8. A pyrroloboron-based porous conjugated polymer material, characterized in that, It is prepared by the preparation method described in claim 1.
9. The pyrrole-boron-based porous conjugated polymer material according to claim 8, characterized in that, The pyrrole-boron-based porous conjugated polymer material has a fully conjugated structure; And / or, the specific surface area of the pyrrole-boron-based porous conjugated polymer material is ≥1000 m². 2 / g, with a pore size distribution of 0.1–2.0 nm.
10. The application of the pyrrole-boron-based porous conjugated polymer material as described in claim 8 in the field of photocatalysis.