A triazine polymer based on bithiophene and preparation method thereof
Synthesis of triazine polymers by reaction between bithiophene and melamine solves the problem of lacking triazine skeleton polymers with bithiophene as monomers in the prior art, and achieves efficient preparation of Fe3+ fluorescent sensing materials.
Patent Information
- Application Number
- CN202410356635.9
- Authority / Receiving Office
- CN · China
- Patent Type
- Patents(China)
- Current Assignee / Owner
- Filing Date
- 2024-03-27
- Publication Date
- 2025-06-06
- Estimated Expiration
- 2044-03-27
AI Technical Summary
There has been no reports of polymers containing triazine frameworks using bithiophene as a monomer starting material in the prior art.
The intermediate was synthesized under argon protection using 5,5'-dibromO-2,2'-bithiophene and 4-methoxycarbonylbenzene boric acid phenyl boronic acid phenyl ester as raw materials, and the reaction of tetrahydrofuran solution and anhydrous sodium bicarbonate, and tetrakis(triphenylphosphorus)palladium as catalyst. Then, the amine aldehyde condensation reaction was carried out with melamine, and finally the target molecule was obtained by Soxhlet extraction and vacuum drying.
The polymer with a triazine skeleton was successfully synthesized, showing good fluorescence quenching performance, suitable for the fluorescence sensing of Fe3+, with high adsorption ability and good permeability.
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Figure CN118165205B_ABST
Abstract
Description
Technical Field
[0001] The invention relates to the technical field of polymer fluorescence performance, and in particular to a bithiophene-based triazine polymer and a preparation method thereof. Background Art
[0002] Porous organic polymers (POPs) are a new type of porous carbon materials with the characteristics of high surface area, rich adjustable cavity structure, high chemical stability and easy post-modification. Among them, covalent triazine frameworks (CTFs) are an organic polymer material composed of 1,3,5-triazine aromatic rings, which have the characteristics of planar π conjugation and good physical, chemical and thermal stability. In addition, since the triazine structure is rich in nitrogen, it will produce a strong heteroatom effect, so that the triazine polymer has rich functional centers and active sites, which can be used to adsorb metal ions, resulting in the quenching of triazine polymer fluorescence. Therefore, POPs can be used as a good ion adsorption material.
[0003] Studies have shown that the introduction of sulfur and nitrogen atoms into porous organic frameworks can create POPs materials rich in sulfur and nitrogen atoms that are more functional. Bithiophene molecules not only contain sulfur atoms, but also have good hole transport properties, rigid structures, and large π conjugated systems. Melamine provides a large amount of nitrogen, which has a variety of connection methods and good electron-donating ability. It can form hydrogen bonds with a series of nitroaromatic compounds, leading to fluorescence quenching. Therefore, these functionalized POPs are more effective for Fe 3+ It exhibits a high adsorption capacity, thus quenching the fluorescence of POPs. In addition, the polymer is a conjugated rigid pore structure, which can effectively prevent the aggregation of conjugated polymer chains caused by fluorescence quenching, has good permeability, and is an ideal new material for fluorescence sensing. At present, there is no report on a polymer containing a triazine skeleton that is polymerized by melamine using bithiophene as a monomer raw material. Summary of the invention
[0004] The object of the present invention is to provide a triazine polymer based on bithiophene and a preparation method thereof, aiming to solve the problem of polymers containing a triazine skeleton being synthesized by melamine polymerization without bithiophene as a monomer raw material.
[0005] To achieve the above objectives, in a first aspect, the present invention provides a method for preparing a triazine polymer based on bithiophene, comprising the following steps:
[0006] 5,5'-dibromo-2,2'-bithiophene and 6.6 molar parts of 4-methoxycarbonylphenylboronic acid pinacol ester are added into a three-necked round-bottom flask, and tetrahydrofuran and an aqueous solution are measured and poured into the three-necked round-bottom flask, and then anhydrous sodium bicarbonate is added into the solution, and tetrakis(triphenylphosphine)palladium is added, and the reaction is carried out under the protection of argon to obtain a first reactant;
[0007] After the reaction was completed, CH 2 Cl 2 Extracting the first reactant and collecting the organic phase, removing the solvent by rotary evaporation to obtain a crude product, and finally purifying by column chromatography to obtain an intermediate;
[0008] Weighing melamine and the intermediate, adding dimethyl sulfoxide to carry out amine-aldehyde condensation reaction, heating and stirring under argon protection for a preset time to obtain a second reactant;
[0009] The second reactant is filtered, subjected to Soxhlet extraction with dichloromethane, acetone and toluene respectively, and then vacuum dried to obtain the target molecule.
[0010] The method comprises adding 5,5'-dibromo-2,2'-bithiophene and 6.6 molar parts of 4-methoxycarbonylphenylboronic acid pinacol ester into a three-necked round-bottom flask, measuring tetrahydrofuran and an aqueous solution and pouring them into the three-necked round-bottom flask, adding anhydrous sodium bicarbonate into the solution, adding tetrakis(triphenylphosphine)palladium, and reacting under argon protection to obtain a first reactant, including:
[0011] 3 molar parts of the raw material 5,5'-dibromo-2,2'-bithiophene and 6.6 molar parts of 4-methoxycarbonylphenylboronic acid pinacol ester were weighed and added into a three-necked round-bottom flask, and appropriate amounts of tetrahydrofuran and aqueous solution were poured into the three-necked round-bottom flask, and then 16.5 molar parts of anhydrous sodium bicarbonate were added to the solution, and 0.1 molar parts of tetrakis(triphenylphosphine)palladium were added, and the reaction was carried out at 80° C. for 12 hours under argon protection to obtain a first reactant.
[0012] The method comprises weighing melamine and the intermediate, adding dimethyl sulfoxide to carry out an amine-aldehyde condensation reaction, and heating and stirring the reaction for a preset time under argon protection to obtain a second reactant, including:
[0013] 2.29 mol parts of melamine and 2.30 mol parts of the intermediate were weighed, 40 mL of dimethyl sulfoxide was added to carry out amine-aldehyde condensation reaction, and the mixture was heated and stirred at 180° C. under argon protection for 72 hours to obtain a second reactant.
[0014] The second reactant is filtered, subjected to Soxhlet extraction with dichloromethane, acetone and toluene respectively, and then vacuum dried to obtain the target molecule, including:
[0015] The second reactant was filtered, subjected to Soxhlet extraction with dichloromethane, acetone and toluene for 48 hours respectively, and then vacuum dried at 130° C. for 24 hours to obtain the target molecule.
[0016] In a second aspect, the present invention provides a triazine polymer based on bithiophene, comprising 5,5'-dibromo-2,2'-bithiophene, 4-methoxycarbonylphenylboronic acid pinacol ester, tetrahydrofuran, an aqueous solution, anhydrous sodium bicarbonate, tetrakis(triphenylphosphine)palladium, melamine and dimethyl sulfoxide.
[0017] The invention discloses a method for preparing a triazine polymer based on bithiophene, comprising the steps of adding 5,5'-dibromo-2,2'-bithiophene and 6.6 molar parts of 4-methoxycarbonylphenylboronic acid pinacol ester into a three-necked round-bottom flask, measuring tetrahydrofuran and an aqueous solution and pouring them into the three-necked round-bottom flask, adding anhydrous sodium bicarbonate into the solution, adding tetrakis(triphenylphosphine)palladium, and reacting under argon protection to obtain a first reactant; after the reaction is completed, using CH 2 Cl 2 The first reactant is extracted and the organic phase is collected, and the solvent is removed by rotary evaporation to obtain a crude product, which is finally purified by column chromatography to obtain an intermediate; melamine and the intermediate are weighed, dimethyl sulfoxide is added to carry out an amine-aldehyde condensation reaction, and the reaction is heated and stirred under argon protection for a preset time to obtain a second reactant; the second reactant is filtered, and Soxhlet extraction is performed with dichloromethane, acetone and toluene respectively, and then vacuum dried to obtain a target molecule, thereby solving the problem of a polymer containing a triazine skeleton that is not polymerized by melamine without using bithiophene as a monomer raw material. BRIEF DESCRIPTION OF THE DRAWINGS
[0018] In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings required for use in the embodiments or the description of the prior art will be briefly introduced below. 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 creative work.
[0019] Figure 1 is the structural diagram of the target molecule.
[0020] Figure 2 It is the synthetic route map of the target molecule.
[0021] Figure 3 It is the infrared image of all compounds.
[0022] Figure 4 It is the selectivity of the target molecule to different reagents.
[0023] Figure 5It is the selectivity of the target molecule to different metals.
[0024] Figure 6 The present invention provides a flow chart of a method for preparing a triazine polymer based on bithiophene. DETAILED DESCRIPTION
[0025] Embodiments of the present invention are described in detail below, 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 should not be construed as limiting the present invention.
[0026] See also Figures 1 to 6 In a first aspect, the present invention provides a method for preparing a triazine polymer based on bithiophene, comprising the following steps:
[0027] S1: 5,5'-dibromo-2,2'-bithiophene and 6.6 mol parts of 4-methoxycarbonylphenylboronic acid pinacol ester are added to a three-necked round-bottom flask, and tetrahydrofuran and an aqueous solution are measured and poured into the three-necked round-bottom flask, and then anhydrous sodium bicarbonate is added to the solution, and tetrakis(triphenylphosphine)palladium is added, and the reaction is carried out under argon protection to obtain a first reactant;
[0028] Specifically, 3 molar parts of the raw material 5,5'-dibromo-2,2'-bithiophene and 6.6 molar parts of 4-methoxycarbonylphenylboronic acid pinacol ester were weighed and added into a three-necked round-bottom flask, and appropriate amounts of tetrahydrofuran and aqueous solution were measured and poured into the three-necked round-bottom flask, and then 16.5 molar parts of anhydrous sodium bicarbonate were added to the solution, and 0.1 molar parts of tetrakis(triphenylphosphine)palladium were added, and the reaction was carried out at 80° C. for 12 hours under argon protection to obtain a first reactant.
[0029] After the S2 reaction is completed, CH 2 Cl 2 Extracting the first reactant and collecting the organic phase, removing the solvent by rotary evaporation to obtain a crude product, and finally purifying by column chromatography to obtain an intermediate (p-1);
[0030] S3 weigh melamine and the intermediate, add dimethyl sulfoxide to carry out amine-aldehyde condensation reaction, heat and stir under argon protection for a preset time to obtain a second reactant;
[0031] Specifically, 2.29 mol parts of melamine and 2.30 mol parts of the intermediate were weighed, 40 mL of dimethyl sulfoxide was added to carry out amine-aldehyde condensation reaction, and the mixture was heated and stirred at 180° C. under argon protection for 72 hours to obtain a second reactant.
[0032] S4: filtering the second reactant, performing Soxhlet extraction with dichloromethane, acetone and toluene respectively, and then vacuum drying to obtain the target molecule.
[0033] Specifically, the second reactant was filtered, subjected to Soxhlet extraction with dichloromethane, acetone and toluene for 48 hours respectively, and then vacuum dried at 130° C. for 24 hours to obtain the target molecule (TP-1).
[0034] Example:
[0035] Synthesis of intermediate product: weigh the raw materials 5,5'-dibromo-2,2'-bithiophene (0.992g, 3mmol) and 4-methoxycarbonylphenylboronic acid pinacol ester (1.730g, 6.6mmol), add them to a 250mL three-necked round-bottom flask, measure 50mL of tetrahydrofuran solution and 10mL of water, pour them into the three-necked round-bottom flask, fully dissolve the mixture, add anhydrous sodium bicarbonate (2.308g, 16.5mmol) to the solution, and then add tetrakis(triphenylphosphine)palladium (0.082g, 0.1mmol), and react at 80°C for 12 hours under argon protection. Post-treatment: After the reaction is completed, extract with CH2Cl2 several times and collect the organic phase, and remove the solvent by rotary evaporation to obtain a crude product. Finally, purify by column chromatography to obtain the intermediate product P (1.07g, yield 81%). 1H NMR(500MHz,Chloroform-d)δ8.11–8.05(m,4H),7.77–7.65(m,9H),7.62–7.54(m,5H),7.53–7.43(m,7H),7.41(d,J=7. 9Hz, 3H), 3.96 (d, J = 5.6Hz, 6H), 2.03 (d, J = 6.5Hz, 1H), 1.29 (s, 4H), 0.90 (t, J = 6.7Hz, 1H), 0.09 (s, 6H). MS: m / z = 434.06
[0036] Synthesis of target molecule: Melamine (0.289 g, 2.29 mmol) and intermediate product 2 (1 g, 2.30 mmol) were mixed, and dimethyl sulfoxide (40 mL) was added to react with amine-aldehyde condensation. The mixture was heated at 180°C under argon protection and stirred on a magnetic heating stirrer for 72 hours to produce the final product polymer TP-1, which was filtered, Soxhlet extracted with dichloromethane, acetone and toluene for 48 hours, and then dried in a vacuum oven at 130°C for 24 hours to obtain the target molecule TP-1 (2.76 g, yield 85%).
[0037] From the infrared test chart ( Figure 3) It can be seen that the disappearance of the absorption peak near 1722.12nm indicates that the carbonyl group almost completely disappears after the reaction with melamine, indicating a high degree of polymerization, while the absorption band appearing at 1560.13nm indicates the formation of triazine ring.
[0038] From the fluorescence spectrum ( Figure 4 ) It can be seen that the fluorescence intensity of the bithiphenyl triazine polymer TP-1 designed in this patent is the highest in tetrahydrofuran solvent, so the experiment was chosen to be carried out in tetrahydrofuran solvent.
[0039] From the fluorescence spectrum ( Figure 5 ) It can be seen that the dithienyl triazine polymer TP-1 designed in this patent can be used as a fluorescent probe to effectively detect Fe3+, and has great potential and application in the field of ion detection.
[0040] In a second aspect, the present invention provides a triazine polymer based on bithiophene, comprising 5,5'-dibromo-2,2'-bithiophene, 4-methoxycarbonylphenylboronic acid pinacol ester, tetrahydrofuran, an aqueous solution, anhydrous sodium bicarbonate, tetrakis(triphenylphosphine)palladium, melamine and dimethyl sulfoxide.
[0041] Specifically, 3 molar parts of the raw material 5,5'-dibromo-2,2'-bithiophene and 6.6 molar parts of 4-methoxycarbonylphenylboronic acid pinacol ester were weighed and added to a three-necked round-bottom flask, and appropriate amounts of tetrahydrofuran and aqueous solution were weighed and poured into the three-necked round-bottom flask, and then 16.5 molar parts of anhydrous sodium bicarbonate were added to the solution, and 0.1 molar parts of tetrakis(triphenylphosphine)palladium were added, and the reaction was carried out at 80°C for 12 hours under argon protection to obtain the first reactant. After the reaction was completed, CH 2 Cl 2 The first reactant is extracted and the organic phase is collected, and the solvent is removed by rotary evaporation to obtain a crude product, which is finally purified by column chromatography to obtain an intermediate (p-1). 2.29 moles of melamine and 2.30 moles of the intermediate are weighed, 40 mL of dimethyl sulfoxide is added to carry out an amine-aldehyde condensation reaction, and the reaction is heated and stirred at 180°C under argon protection for 72 hours to obtain a second reactant. The second reactant is filtered, and Soxhlet extraction is performed with dichloromethane, acetone and toluene for 48 hours, respectively, and then vacuum dried at 130°C for 24 hours to obtain the target molecule (TP-1).
[0042] The above disclosure is only a preferred embodiment of a bithiophene-based triazine polymer and a preparation method of the present invention. Of course, this cannot be used to limit the scope of rights of the present invention. Ordinary technicians in this field can understand that all or part of the processes of the above embodiments and equivalent changes made according to the claims of the present invention still fall within the scope of the invention.
Claims
1. A method for preparing a triazine polymer based on bithiophene, characterized in that: The following steps are involved: Weigh 3 molar parts of the raw material 5,5'-dibromo-2,2'-bithiophene and 6.6 molar parts of 4-methoxycarbonylphenylboronic acid pinacol ester and add them into a three-necked round-bottom flask, and weigh appropriate amounts of tetrahydrofuran and aqueous solution and pour them into the three-necked round-bottom flask, then add 16.5 molar parts of anhydrous sodium bicarbonate to the solution, add 0.1 molar parts of tetrakis(triphenylphosphine)palladium, and react at 80°C for 12 hours under argon protection to obtain a first reactant; After the reaction is completed, the first reactant is extracted with CH2Cl2, and the organic phase is collected, and the solvent is removed by rotary evaporation to obtain a crude product, and finally purified by column chromatography to obtain an intermediate; Weighing melamine and the intermediate, adding dimethyl sulfoxide to carry out amine-aldehyde condensation reaction, heating and stirring under argon protection for a preset time to obtain a second reactant; The second reactant is filtered, subjected to Soxhlet extraction with dichloromethane, acetone and toluene respectively, and then vacuum dried to obtain the target molecule.
2. The method for preparing a triazine polymer based on bithiophene according to claim 1, characterized in that: The method comprises weighing melamine and the intermediate, adding dimethyl sulfoxide to carry out an amine-aldehyde condensation reaction, heating and stirring the reaction for a preset time under argon protection to obtain a second reactant, including: 2.29 mol parts of melamine and 2.30 mol parts of the intermediate were weighed, 40 mL of dimethyl sulfoxide was added to carry out amine-aldehyde condensation reaction, and the mixture was heated and stirred at 180° C. under argon protection for 72 hours to obtain a second reactant.
3. The method for preparing a triazine polymer based on bithiophene according to claim 2, characterized in that: The second reactant is filtered, subjected to Soxhlet extraction with dichloromethane, acetone and toluene respectively, and then vacuum dried to obtain the target molecule, including: The second reactant was filtered, subjected to Soxhlet extraction with dichloromethane, acetone and toluene for 48 hours respectively, and then vacuum dried at 130° C. for 24 hours to obtain the target molecule.
4. A triazine polymer based on bithiophene, prepared by the method for preparing a triazine polymer based on bithiophene as claimed in claim 3, characterized in that: The invention comprises 5,5'-dibromo-2,2'-bithiophene, 4-methoxycarbonylphenylboronic acid pinacol ester, tetrahydrofuran, aqueous solution, anhydrous sodium bicarbonate, tetrakis(triphenylphosphine)palladium, melamine and dimethyl sulfoxide.