Anthracene-based triazine polymer, preparation method and application
By introducing diphenylamine groups on the anthracene unit and crosslinking with cyanochloride, the triazine skeleton polymer was constructed, which solved the problem of insufficient adsorption of polymers with low specific surface area, and achieved the effect of efficiently trapping radioactive iodine.
Patent Information
- Application Number
- CN202510655917.3
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2025-05-21
- Publication Date
- 2025-08-19
AI Technical Summary
Existing low specific surface area polymers have low adsorption properties and are difficult to meet the demand for efficient capture of radioactive iodine.
Using 9,10-dibromoanthracene as the initial monomer, dianiline groups were introduced through Buchwald-Hartwig amination reaction, and then cross-linked with cyanochloride to construct a triazine skeleton polymer with a three-dimensional conjugated network structure to form a porous material with high density electron donor sites.
The synthesis route is simple, the thermal chemical stability is good, and the unique conjugated frame structure is used to significantly improve the adsorption performance, especially the ability to capture iodine under low specific surface area conditions.
Smart Images
Figure CN120504831A_ABST
Abstract
Description
Technical Field
[0001] The present invention relates to the technical field of porous materials, and in particular to an anthracene-based triazine polymer, a preparation method and applications thereof. Background Art
[0002] Porous organic polymers (POPs) are topological network materials constructed from lightweight elements such as C, H, O, and N through strong covalent bonds (C-C, CO, and CN, etc.). Their unique structural diversity, pore tunability, and flexible functional group modification capabilities give them significant advantages in the field of radioactive iodine capture. Polymers with hierarchical pore structures can be obtained using different monomers and polymerization methods, thereby achieving control over pore size and specific surface area, thereby realizing multifunctional adsorption. Secondly, by embedding specific functional groups into the POPs backbone for modification, specific adsorption can be achieved, further enhancing their applicability in complex environments. Currently, researchers generally believe that the capture performance of porous adsorbents for I2 is significantly positively correlated with the strength of their electron donor-acceptor interactions. Based on this, the following strategies should be followed in the design of POPs backbones: ① Constructing high-density electron donor sites by introducing heteroatomic groups containing lone pairs of electrons (such as triazine rings and pyridinic nitrogen); ② Constructing electron-rich conjugated π systems to enhance the backbone electron delocalization effect and promote the formation of charge-transfer complexes. ③ Through the π-π stacking effect, the porous skeleton structure is effectively supported, providing a good interactive microenvironment for iodine molecules and effectively improving the utilization rate of active sites.
[0003] Based on the above discussion, we used electron-rich anthracene units as the conjugated base and hypothesized that a non-planar propeller structure similar to triphenylamine could be synthesized by introducing diphenylamine to construct a derivative monomer (YW) with strong electron-donating ability. This facilitated the subsequent cross-linking of the nitrogen-rich triazine framework via Friedel–Crafts alkylation reaction, thereby constructing a polymer (POP-W) with a high density of electron-donating sites. Furthermore, the rigid triazine and anthracene units effectively maintain the stability of the pore structure, increasing the number of active sites accessible to iodine molecules. This unique "rigid-flexible" backbone design provides a new approach to breaking through the performance bottlenecks of existing adsorption materials. Summary of the Invention
[0004] The purpose of the present invention is to provide an anthracene-based triazine polymer, a preparation method and an application thereof, in order to solve the problem of low adsorption of existing low specific surface area polymers.
[0005] To achieve the above objectives, in a first aspect, the present invention provides a method for preparing an anthracene-based triazine polymer, comprising the following steps:
[0006] Weigh 9,10-dibromoanthracene, diphenylamine, and sodium tert-butoxide into a first two-necked flask, add a predetermined amount of toluene solution, add tris(dibenzylideneacetone)dipalladium(0) and tri-tert-butylphosphine to the first two-necked flask under argon protection, and heat to react to obtain a reaction solution;
[0007] The reaction solution was spin-dried, dissolved in dichloromethane solution, and then poured into water for extraction until clear. The organic phase was collected, spin-dried, and weighed to a constant weight to obtain an intermediate product.
[0008] Pre-treating the intermediate product to obtain a semi-finished product;
[0009] The semi-finished product is sequentially subjected to Soxhlet extraction and purification with dichloromethane, methanol and acetone, and then placed in an oven for drying to obtain a triazine porous organic polymer.
[0010] Wherein, in “weighing 9,10-dibromoanthracene, diphenylamine and sodium tert-butoxide into a first two-necked flask, adding a preset amount of toluene solution, adding tris(dibenzylideneacetone)dipalladium(0) and tri-tert-butylphosphine into the first two-necked flask under argon protection, and heating to react to obtain a reaction solution”, the weighing amount of the 9,10-dibromoanthracene is 1 mol part; the weighing amount of the diphenylamine is 3 mol parts; the weighing amount of the sodium tert-butoxide is 5 mol parts; the weighing amount of the tris(dibenzylideneacetone)dipalladium(0) is 0.03 mol parts; the weighing amount of the tri-tert-butylphosphine is 0.09 mol parts; the heating reaction includes primary heating and secondary heating, the primary heating temperature is 50° C., the reaction time is 0.5 h, the secondary heating temperature is 110° C., and the reaction time is 48 h.
[0011] The process of “pre-treating the intermediate product to obtain a semi-finished product” includes the following steps:
[0012] Weigh the intermediate product and cyanuric chloride into a second two-necked round-bottom flask, dissolve them in a preset amount of o-dichlorobenzene to obtain a solution, and add a preset amount of methanesulfonic acid solution to the second two-necked round-bottom flask under argon protection;
[0013] The solution is heated to a preset temperature under argon protection to react, and the mixture is cooled to room temperature;
[0014] The precipitate obtained by filtering the mixture is washed with water, dichloromethane and methanol in sequence to obtain a semi-finished product.
[0015] Among them, in “heating the dissolved liquid to a preset temperature under argon protection for reaction, obtaining a mixture and cooling it to room temperature”, the preset temperature is 140° C. and the reaction time is 72 hours.
[0016] Among them, in “the semi-finished product is subjected to Soxhlet extraction and purification with dichloromethane, methanol and acetone in sequence, and then placed in an oven for drying to obtain a triazine porous organic polymer”, the purification time is 96 hours and the drying time is 24 hours.
[0017] In the second aspect, an anthracene-based triazine polymer is prepared using the preparation method of the anthracene-based triazine polymer described in the first aspect, including 9,10-dibromoanthracene, diphenylamine, sodium tert-butoxide, toluene, tris(dibenzylideneacetone)dipalladium(0), tri-tert-butylphosphine, cyanuric chloride, methanesulfonic acid and o-dichlorobenzene.
[0018] In a third aspect, an application of an anthracene-based triazine polymer is provided, which uses the anthracene-based triazine polymer described in the second aspect in the field of fixation and recovery of radioactive iodine from nuclear waste.
[0019] The present invention discloses an anthracene-based triazine polymer, a preparation method and an application thereof, comprising the following steps: weighing 9,10-dibromoanthracene, diphenylamine and sodium tert-butoxide into a first two-necked flask, adding a preset amount of toluene solution, adding tris(dibenzylideneacetone)dipalladium(0) and tri-tert-butylphosphine into the first two-necked flask under argon protection, heating for reaction to obtain a reaction liquid; spin-drying the reaction liquid, adding a dichloromethane solution to dissolve the reaction liquid, and then pouring the reaction liquid into water for extraction until it is clarified, collecting an organic phase, spin-drying the organic phase, and weighing the organic phase to a constant weight to obtain an intermediate product; pre-treating the intermediate product to obtain a semi-finished product; and sequentially performing Soxhlet extraction and purification on the semi-finished product using dichloromethane, methanol and acetone, and then drying the semi-finished product in an oven to obtain a triazine porous organic polymer. This invention uses 9,10-dibromoanthracene as the starting monomer, introducing diphenylamine groups at the 9,10 positions via a Buchwald-Hartwig amination reaction to produce the intermediate product YW. This product is then cross-linked and polymerized with cyanuric chloride via a Friedel-Crafts alkylation reaction to construct a three-dimensional conjugated network structure, resulting in the synthesis of a novel triazine-based polymer. This polymer exhibits a simple synthetic route, excellent thermochemical stability, and a unique conjugated framework structure. This overcomes the problem of low adsorption of existing low-surface-area polymers. BRIEF DESCRIPTION OF THE DRAWINGS
[0020] In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the following briefly introduces the drawings required for use in the embodiments or the description of the prior art. Obviously, the drawings described below are only some embodiments of the present invention. For ordinary technicians in this field, other drawings can be obtained based on these drawings without paying any creative work.
[0021] Figure 1 The present invention provides a flow chart of a method for preparing anthracene-based triazine polymer.
[0022] Figure 2 This is the synthesis route of the anthracene-based triazine polymer POP-W of the present invention (i: sodium tert-butoxide, tris(dibenzylideneacetone)dipalladium(0), tri-tert-butylphosphine and toluene; ii: methanesulfonic acid and o-dichlorobenzene).
[0023] Figure 3 This is the molecular structure of the anthracene-based triazine polymer POP-W according to an embodiment of the present invention.
[0024] Figure 4 This is an infrared test image of the anthracene-based triazine polymer POP-W according to an embodiment of the present invention (abscissa: wave number).
[0025] Figure 5 This is a graph showing the adsorption of iodine vapor by the anthracene-based triazine polymer POP-W according to an embodiment of the present invention (abscissa: time, ordinate: iodine adsorption amount).
[0026] Figure 6 The pseudo-first-order kinetic fitting curve and pseudo-second-order kinetic fitting curve of the anthracene-based triazine polymer POP-W adsorbing iodine vapor in the embodiment of the present invention are shown in Table 1. (Abscissa: time, ordinate: iodine adsorption amount R 2 : correlation coefficient).
[0027] Figure 7 This is a graph showing the adsorption of iodine in n-hexane solution by an anthracene-based triazine polymer POP-W according to an embodiment of the present invention (abscissa: concentration, ordinate: iodine adsorption amount).
[0028] Figure 8 The H NMR spectrum of intermediate YW in the examples of the present invention is shown in Figure 2 (abscissa: chemical shift).
[0029] Figure 9 This is a flow chart for pre-processing intermediate products to obtain semi-finished products. DETAILED DESCRIPTION
[0030] The following describes embodiments of the present invention in detail, examples of which are shown in the accompanying drawings, wherein the same or similar reference numerals throughout represent the same or similar elements or elements having the same or similar functions. The embodiments described below with reference to the accompanying drawings are exemplary and are intended to be used to explain the present invention, and are not to be construed as limiting the present invention.
[0031] See also Figures 1 to 9 In a first aspect, the present invention provides a method for preparing anthracene-based triazine polymer, comprising the following steps:
[0032] S1: Weigh 9,10-dibromoanthracene, diphenylamine, and sodium tert-butoxide into a first two-necked flask, add a predetermined amount of toluene solution, and under argon protection, add tris(dibenzylideneacetone)dipalladium(0) and tri-tert-butylphosphine to the first two-necked flask, and heat to react to obtain a reaction solution;
[0033] The weighed amount of the 9,10-dibromoanthracene is 1 mol part; the weighed amount of the diphenylamine is 3 mol parts; the weighed amount of the sodium tert-butoxide is 5 mol parts; the weighed amount of tris(dibenzylideneacetone)dipalladium(0) is 0.03 mol parts; the weighed amount of the tri-tert-butylphosphine is 0.09 mol parts; the heating reaction includes primary heating and secondary heating, the primary heating temperature is 50°C, the reaction time is 0.5h, the secondary heating temperature is 110°C, and the reaction time is 48h.
[0034] Specifically, 1 mol of 9,10-dibromoanthracene, 3 mol of diphenylamine, and 5 mol of sodium tert-butoxide were weighed and added to a first two-necked round-bottom flask, a preset amount of toluene solution was added, and under argon protection, 0.03 mol of tris(dibenzylideneacetone)dipalladium(0) and 0.09 mol of tri-tert-butylphosphine were added to the first two-necked round-bottom flask, the temperature was raised to 50° C., and after 0.5 h, the temperature was raised to 110° C., and the reaction was refluxed for 48 h to obtain a reaction solution;
[0035] S2: The reaction solution was spin-dried, dissolved in dichloromethane solution, and then poured into water for extraction until clarified. The organic phase was collected, spin-dried, and weighed to a constant weight to obtain an intermediate product;
[0036] Specifically, the reaction solution was spin-dried, dissolved in dichloromethane, and then poured into water, extracted multiple times until clarified, the organic phase was collected, spin-dried, and separated by silica gel column chromatography (dichloromethane / petroleum ether, gradient elution), the product was collected, spin-dried, and dried in a vacuum drying oven to constant weight to obtain the intermediate product YW.
[0037] S3 pre-treats the intermediate product to obtain a semi-finished product;
[0038] S31: weigh the intermediate product and cyanuric chloride, add them to a second two-necked round-bottom flask, dissolve them in a preset amount of o-dichlorobenzene to obtain a solution, and add a preset amount of methanesulfonic acid solution to the second two-necked round-bottom flask under argon protection;
[0039] Specifically, 1.5 mol parts of compound YW and 2 mol parts of cyanuric chloride were added to a dry second two-necked round-bottom flask, respectively, and dissolved with an appropriate amount of o-dichlorobenzene to obtain a solution. 14 mol parts of methanesulfonic acid was added under argon protection.
[0040] S32: heating the solution to a preset temperature under argon protection to react, obtaining a mixture and cooling the mixture to room temperature;
[0041] The preset temperature is 140° C. and the reaction time is 72 hours.
[0042] Specifically, the mixture was heated to 140° C. under argon protection, reacted for 72 hours, and then cooled to room temperature.
[0043] S33: The precipitate obtained by filtering the mixture is washed with water, dichloromethane, and methanol in sequence to obtain a semi-finished product.
[0044] Specifically, the precipitate obtained by filtration is washed with water, dichloromethane and methanol in sequence to obtain a semi-finished product.
[0045] S4: The semi-finished product is subjected to Soxhlet extraction and purification with dichloromethane, methanol and acetone in sequence, and then placed in an oven for drying to obtain a triazine porous organic polymer.
[0046] The purification time was 96 hours, and the drying time was 24 hours.
[0047] Specifically, the semi-finished product was further purified by Soxhlet extraction with dichloromethane, methanol, and acetone for 96 hours, and finally placed in a 130° C. oven for vacuum drying for 24 hours to obtain black powder POP-W, which is a porous organic polymer.
[0048] Example:
[0049] Synthesis of intermediate YW: Weigh 9,10-dibromoanthracene (1.31 g, 3.9 mmol), diphenylamine (1.68 g, 9.77 mmol), and sodium tert-butoxide (2.72 g, 19.5 mmol), and add them to a 250 mL two-necked round-bottom flask. Pour 60 mL of toluene solution into the two-necked round-bottom flask, evacuate and fill with argon for 3 cycles to completely replace the air in the round-bottom flask with argon to achieve oxygen-free conditions. Then add tris(dibenzylideneacetone)dipalladium(0) (0.11 g, 0.12 mmol) and tri-tert-butoxide. phosphine (0.15 mL, 0.35 mmol); repeat the vacuum and argon filling cycle 3 times, heat to 50 ° C, and then heat to 110 ° C after 0.5 h, reflux for 48 h, judge the completion of the reaction by thin layer chromatography on silica gel plate, cool to room temperature, and post-process: the reaction solution is spin-dried, extracted with dichloromethane and water several times until clear, the organic phase is collected, spin-dried, and separated by silica gel column chromatography (dichloromethane / petroleum ether, gradient elution), the product is collected, spin-dried, and dried in a vacuum drying oven to constant weight to obtain a light yellow powder, i.e., intermediate YW, with a yield of 70%. 1H NMR(500MHz,Chloroform-d)δ8.18(dd,J=6.8,3.2Hz,4H),7.35(dd,J=6.8,3.2Hz,4H),7.23–7.16(m,8H),7.11(d,J=7.6Hz,8H),6.94–6.87(m,4H).
[0050] Synthesis of the target molecule POP-W: To a 250 mL dry, two-necked round-bottom flask, intermediate YW (0.96 g, 1.875 mmol), cyanuric chloride (0.46 g, 2.5 mmol), and 12.5 mL of o-dichlorobenzene solution were added. The mixture was evacuated and, under argon, methanesulfonic acid (1.2 mL, 17.5 mmol) was added. After three cycles of evacuation and argon filling, the temperature was raised to 140°C and refluxed for 72 hours. Post-treatment: After the mixture cooled to room temperature, the filtered precipitate was washed sequentially with water, dichloromethane, and methanol. The product was further purified by Soxhlet extraction with dichloromethane, methanol, and acetone for 96 hours. Finally, the product was dried in a vacuum oven at 130°C for 24 hours to obtain POP-W, a black powder.
[0051] From the infrared test chart ( Figure 4 ) It can be seen that the reaction monomer 9,10-dibromoanthracene is at 580 cm -1 The disappearance of the C-Br stretching vibration peak and the peak at 1588 cm -1 The stretching vibration peak of CN appeared, proving the successful synthesis of intermediate YW. In addition, compared with intermediate YW, the stretching vibration peak of CN of polymer POP-W was weakened, but still existed obviously, as well as the peak at 1721cm -1 The C=N stretching vibration peak of the tricyano ring appeared, indicating the successful synthesis of the polymer POP-W.
[0052] In the second aspect, an anthracene-based triazine polymer is prepared using the preparation method of the anthracene-based triazine polymer described in the first aspect, including 9,10-dibromoanthracene, diphenylamine, sodium tert-butoxide, toluene, tris(dibenzylideneacetone)dipalladium(0), tri-tert-butylphosphine, cyanuric chloride, methanesulfonic acid and o-dichlorobenzene.
[0053] In a third aspect, an application of an anthracene-based triazine polymer is provided, which uses the anthracene-based triazine polymer described in the second aspect in the field of fixation and recovery of radioactive iodine from nuclear waste.
[0054] The above disclosure is merely a preferred embodiment of an anthracene-based triazine polymer, preparation method, and application of the present invention. It is certainly not intended to limit the scope of the present invention. A person skilled in the art will understand that implementing all or part of the processes of the above embodiment and making equivalent changes in accordance with the claims of the present invention still fall within the scope of the invention.
Claims
1. A method for preparing anthracene-based triazine polymer, characterized in that: The following steps are involved: Weigh 9,10-dibromoanthracene, diphenylamine, and sodium tert-butoxide into a first two-necked flask, add a predetermined amount of toluene solution, add tris(dibenzylideneacetone)dipalladium(0) and tri-tert-butylphosphine to the first two-necked flask under argon protection, and heat to react to obtain a reaction solution; The reaction solution was spin-dried, dissolved in dichloromethane solution, and then poured into water for extraction until clear. The organic phase was collected, spin-dried, and weighed to a constant weight to obtain an intermediate product. Pre-treating the intermediate product to obtain a semi-finished product; The semi-finished product is sequentially subjected to Soxhlet extraction and purification with dichloromethane, methanol and acetone, and then placed in an oven for drying to obtain a triazine porous organic polymer.
2. The method for preparing anthracene-based triazine polymer according to claim 1, wherein: In the step of "weighing 9,10-dibromoanthracene, diphenylamine and sodium tert-butoxide into a first two-necked flask, adding a preset amount of toluene solution, adding tris(dibenzylideneacetone)dipalladium(0) and tri-tert-butylphosphine into the first two-necked flask under argon protection, and heating to react to obtain a reaction solution", the weighing amount of 9,10-dibromoanthracene is 1 mol part; the weighing amount of diphenylamine is 3 mol parts; the weighing amount of sodium tert-butoxide is 5 mol parts; the weighing amount of tris(dibenzylideneacetone)dipalladium(0) is 0.03 mol parts; and the weighing amount of tri-tert-butylphosphine is 0.09 mol parts; the heating reaction includes primary heating and secondary heating, the primary heating temperature is 50°C, the reaction time is 0.5 h, and the secondary heating temperature is 110°C, and the reaction time is 48 h.
3. The method for preparing anthracene-based triazine polymer according to claim 1, wherein: In "pre-treating the intermediate product to obtain a semi-finished product", the following steps are included: Weigh the intermediate product and cyanuric chloride and add them to a second two-necked round-bottom flask, dissolve them in a preset amount of o-dichlorobenzene to obtain a solution, and add a preset amount of methanesulfonic acid solution to the second two-necked round-bottom flask under argon protection; The solution is heated to a preset temperature under argon protection to react, and the mixture is cooled to room temperature; The precipitate obtained by filtering the mixture is washed with water, dichloromethane and methanol in sequence to obtain a semi-finished product.
4. The method for preparing anthracene-based triazine polymer according to claim 3, wherein: In the step of “heating the solution to a preset temperature under argon protection to react, obtaining a mixture and cooling the mixture to room temperature”, the preset temperature is 140° C., and the reaction time is 72 h.
5. The method for preparing anthracene-based triazine polymer according to claim 1, wherein: In the step “the semi-finished product is subjected to Soxhlet extraction and purification with dichloromethane, methanol and acetone in sequence, and then placed in an oven for drying to obtain a triazine porous organic polymer”, the purification time is 96 hours, and the drying time is 24 hours.
6. An anthracene-based triazine polymer prepared by the method for preparing an anthracene-based triazine polymer according to any one of claims 1 to 5, characterized in that: The reagents include 9,10-dibromoanthracene, diphenylamine, sodium tert-butoxide, toluene, tris(dibenzylideneacetone)dipalladium(0), tri-tert-butylphosphine, cyanuric chloride, methanesulfonic acid and o-dichlorobenzene.
7. An application of an anthracene-based triazine polymer, using the anthracene-based triazine polymer according to claim 6, characterized in that: Used in the field of fixation and recovery of radioactive iodine in nuclear waste.