Anthracene derivative carbazole polymers, methods of preparation and use

Abstract

The application discloses an anthracene derivative carbazole polymer, a preparation method and application, and belongs to the technical field of ion detection. A chemical general formula of a monomer of the anthracene derivative carbazole polymer is as follows: wherein n is a natural number in 1-100, and R is selected from any one of hydrogen, a straight chain with 1-8 carbon atoms, a branched chain with 1-8 carbon atoms and a cyclic alkyl chain with 1-8 carbon atoms. The anthracene derivative carbazole polymer is used for detecting dihydrogen phosphate anions. After dihydrogen phosphate ions and the anthracene derivative carbazole polymer are mixed, white flocculent substances appear in a solution, and the solution becomes turbid, visual detection of the dihydrogen phosphate anions is realized, and the detection speed and accuracy of the dihydrogen phosphate anions are improved.

Description

Technical Field

[0001] This invention relates to anthracene derivative carbazole polymers, their preparation methods, and applications, belonging to the field of ion detection technology. Background Technology

[0002] Anion acceptor chemistry originated in the late 1960s, with pioneering progress made by the Lehn group in the 1970s and 1980s. However, it wasn't until the 1990s that the field of anion acceptor chemistry, including molecular recognition, sensing, transmembrane anion transport, extraction, crystal engineering, self-assembly, and catalysis, began to flourish, attracting widespread attention. Early developments in anion recognition were limited by the structural characteristics of anions themselves. Compared to cations, anions are larger and carry lower charges, resulting in less pronounced electrostatic properties. Furthermore, anions exhibit significant solvation effects and are greatly influenced by solvents; for example, lower pH values ​​can cause anions to protonate. Therefore, society and various industries will increasingly value efficient anion acceptors, leading to growing demand. Anion extraction and anion recognition technologies have significant practical value and research significance.

[0003] It wasn't until the last two decades that research on macromolecular systems with anion responses began to be reported for applications in medicine, national security, or environmental monitoring. The selective and high-affinity recognition of anions is accomplished by "optimized" macromolecular hosts, and recent research results indicate that the unique characteristics of polymer systems, such as signal amplification, multivalent, and cooperative behavior, can be effectively utilized in anion recognition and sensing. Furthermore, polymers can act as extractants to remove target anions from aqueous phases through three complementary modes: (a) liquid-liquid extraction involving a two-phase organic solvent / water system, where anions are ideally extracted from the aqueous phase into the organic phase; (b) solvent-swelled polymer networks (gels) adsorbing anions from water; and (c) solids directly adsorbing anions. Designing and exploring fast-responding, reusable polymer-sensitive materials and anion sensors has become one of the important research directions in this field in recent years.

[0004] Phosphates are widely present in our daily lives, used extensively in light chemical industries such as food, matches, and detergents, and also in large quantities in agricultural production. The use of polyphosphates in detergents leads to a significant increase in phosphorus content in domestic wastewater. The excessive application of phosphate fertilizers, erosion of arable land, and increased sewage discharge all contribute to a rapid increase in phosphorus concentration in the aquatic environment, resulting in the accumulation of large amounts of phosphorus in some environmental media, such as over-fertilized agricultural soils or phosphorus-rich river sediments. However, current methods for detecting dihydrogen phosphate ions are slow, have low accuracy, and require specific instruments to view the results, making convenient and efficient detection of dihydrogen phosphate ions impossible.

[0005] In view of this, it is indeed necessary to propose a detection material and method for dihydrogen phosphate to solve the above problems. Summary of the Invention

[0006] The purpose of this invention is to provide an anthracene derivative carbazole polymer, its preparation method, and its application, in order to solve the problems of slow detection speed and low efficiency of dihydrogen phosphate ions in the prior art.

[0007] To achieve the above objectives, the present invention provides an anthracene derivative carbazole polymer, wherein the general chemical formula of the anthracene derivative carbazole polymer monomer is:

[0008]

[0009] Where n is a natural number from 1 to 100, and R is selected from any one of hydrogen, a straight chain having 1 to 8 carbon atoms, a branched chain having 1 to 8 carbon atoms, or a cyclic alkyl chain having 1 to 8 carbon atoms.

[0010] To achieve the above objectives, the present invention provides a method for preparing anthracene derivative carbazole polymer, comprising:

[0011] Compounds C and D were added to the third reactor. Under inert gas protection, 1,4-dioxane was added and dissolved while stirring. The temperature was then raised to the first reaction temperature, and boron trifluoride diethyl ether was added. The temperature was then raised to the second reaction temperature and stirred until the reaction was complete. After post-treatment, compound E was obtained. The general reaction formula is:

[0012]

[0013] Where n is a natural number from 1 to 100, and R is selected from any one of hydrogen, a straight chain having 1 to 8 carbon atoms, a branched chain having 1 to 8 carbon atoms, or a cyclic alkyl chain having 1 to 8 carbon atoms.

[0014] As a further improvement of the present invention, the first temperature is 60-90°C, the second temperature is 100-110°C, the reaction time is 48 hours, and the post-treatment includes gravity sedimentation and Soxhlet extraction.

[0015] As a further improvement of the present invention, the equivalent ratio of compound C, compound D and boron trifluoride ether is 1:1:1 to 5.

[0016] As a further improvement of the present invention, the preparation method further includes:

[0017] Magnesium and dihydrogen phosphate were added to the first reactor. Dry tetrahydrofuran and compound B were added in two portions under inert gas protection. The mixture was heated to 55-60°C and stirred until the reaction was complete to obtain the first reactant.

[0018] Under inert gas protection, compound A and dry tetrahydrofuran were added to the second reactor and cooled. Then, the first reactant was added, and the mixture was stirred until the reaction was complete. After post-treatment, compound C was obtained. The general reaction formula is:

[0019]

[0020] As a further improvement of the present invention, a small amount of compound B and tetrahydrofuran are added for the first time, and the reaction solution is yellowish-brown. The mixture is heated and stirred until the reaction solution becomes colorless. The remaining compound B and tetrahydrofuran are added for the second time, and the mixture is stirred until the reaction is complete.

[0021] As a further improvement of the present invention, compound A and dry tetrahydrofuran are added and cooled to -10 to -40°C. The first reactant is added at -10 to -40°C, and then the temperature is raised to -10 to -5°C for stirring reaction.

[0022] As a further improvement of the present invention, the equivalent ratio of compound A, compound B and magnesium is 1:4 to 6:4 to 6, wherein the equivalent ratio of compound B and magnesium is 1:1.

[0023] To achieve the above objectives, this invention provides an application of anthracene derivative carbazole polymer in the detection of dihydrogen phosphate ions. The anthracene derivative carbazole polymer is dissolved in an organic solvent and added to the test solution. If a white flocculent substance is produced in the solution and it becomes turbid, then the test solution contains dihydrogen phosphate ions; if the solution does not change, then the test solution does not contain dihydrogen phosphate ions.

[0024] As a further improvement of the present invention, the organic solvent is one or more of the following: dichloromethane, tetrahydrofuran, toluene, chloroform, 1,4-dioxane, and 1,2-dichloroethane.

[0025] The beneficial effects of this invention are: This invention uses anthracene derivative carbazole polymer to detect dihydrogen phosphate anions. After the dihydrogen phosphate anions and the anthracene derivative carbazole polymer are mixed, white flocculent matter appears in the solution and the solution becomes turbid, thus realizing the visual detection of dihydrogen phosphate anions, thereby improving the detection speed and accuracy of dihydrogen phosphate anions. Attached Figure Description

[0026] Figure 1 This is the 1H NMR spectrum of the anthracene derivative carbazole polymer in this invention.

[0027] Figure 2 This is the UV-fluorescence spectrum of the anthracene derivative carbazole polymer in this invention.

[0028] Figure 3This is the solution emission spectrum of the anthracene derivative carbazole polymer of the present invention for different anions. Detailed Implementation

[0029] To make the objectives, technical solutions, and advantages of this invention clearer, the invention will be described in detail below with reference to the accompanying drawings and specific embodiments.

[0030] This invention provides an anthracene derivative carbazole polymer as a fluorescent probe for the specific detection of dihydrogen phosphate anions. The anthracene derivative carbazole polymer is a polymer molecule with anthracene derivatives and carbazole as building blocks, and its general chemical formula is:

[0031]

[0032] Where n is a natural number from 1 to 100, and R is selected from any one of hydrogen, a straight chain having 1 to 8 carbon atoms, a branched chain having 1 to 8 carbon atoms, or a cyclic alkyl chain having 1 to 8 carbon atoms.

[0033] This invention provides a method for preparing anthracene derivative carbazole polymer, comprising:

[0034] S1. Add magnesium and dihydrogen phosphate to the first reactor. Under inert gas protection, add dry tetrahydrofuran and compound B in two portions. Heat to 55-60°C and stir for 4-6 hours until the reaction is complete to obtain the first reactant.

[0035] In the first step, a small amount of compound B and tetrahydrofuran were added, and the reaction solution turned yellowish-brown. The mixture was heated and stirred until it became colorless. In the second step, the remaining compound B and tetrahydrofuran were added, and the mixture was stirred until the reaction was complete.

[0036] Specifically, after assembling the glassware of the first reactor, Mg (3.48g, 5eq) and iodine (20mg) are added to the first reactor and sealed with vacuum grease and / or sealing tape. The first reactor is then evacuated and replenished with inert gas three times, and balloons filled with inert gas are assembled for protection.

[0037] Tetrahydrofuran (THF) soaked in sodium wire was distilled to obtain dry tetrahydrofuran solvent. 15 ml of compound B was drawn into one syringe, and 144 ml of dry tetrahydrofuran was drawn into another syringe. A small amount of compound B and a small amount of dry tetrahydrofuran were injected into the second reactor through the syringes. Stirring was turned on, and the second reactor was heated with hot air blown from a heating gun to initiate the reaction of the raw materials in the second reactor. The change in the solution in the second reactor was as follows: it initially turned yellowish-brown, and then the color faded to colorless, indicating that the reaction was successfully initiated. Then, the remaining compound B (15 ml, 5 eq) and the remaining dry tetrahydrofuran (144 ml) were slowly added through the two syringes. The reaction was stirred until it was complete, to obtain the first reactant.

[0038] S2. Under inert gas protection, compound A and dry tetrahydrofuran are added to the second reactor and cooled. Then, the first reactant is added, and the mixture is stirred until the reaction is complete. After post-treatment, compound C is obtained. The general reaction formula is:

[0039]

[0040] Wherein, R is selected from any one of hydrogen, a straight chain having 1 to 8 carbon atoms, a branched chain having 1 to 8 carbon atoms, or a cyclic alkyl chain having 1 to 8 carbon atoms. Compound A and dry tetrahydrofuran are added and cooled to -10 to -40°C. The first reactant is added at -10 to -40°C, followed by heating to -10 to -5°C and stirring. In S1 and S2, the equivalent ratio of compound A, compound B, and magnesium is 1:4 to 6:4 to 6, wherein the equivalent ratio of compound B and magnesium is 1:1. Preferably, compound A and dry tetrahydrofuran are added and cooled to -40°C. The first reactant is added at -40°C, followed by heating to -5°C and stirring, wherein the equivalent ratio of compound A, compound B, and magnesium is 1:5:5.

[0041] Specifically, after assembling the glassware of the second reactor, compound A (6g, 1eq) was added to the second reactor. The second reactor was evacuated and inert gas was added three times. A balloon filled with inert gas was assembled for protection. Then, 340ml of dry tetrahydrofuran solvent was added. At this time, a -40℃ low temperature environment was created using dry ice / acetonitrile. After the second reactor and the reaction liquid inside it cooled to -40℃, the first reactant obtained from S1 was added. Then, the temperature was raised to about -5℃ and stirred for 4 hours until the reaction was complete, resulting in a solution containing compound C.

[0042] The reaction solution was quenched with a saturated NH4Cl aqueous solution, tetrahydrofuran was removed by rotary evaporation, and then extracted multiple times with CH2Cl2. The extracted liquid was dried by rotary evaporation and then purified by chromatography using a 100-200 mesh silica gel column. The eluent was petroleum ether:dichloromethane = 1:2-3, preferably petroleum ether:dichloromethane = 1:2.3. After elution, the solvent containing the target product was rotary evaporated to obtain a white crystalline solid, which is compound C, with a yield of 45%.

[0043] In this embodiment, the inert gas is nitrogen. Of course, in other embodiments, the inert gas can also be other inert gases such as argon, and there is no limitation here.

[0044] S3. Compounds C and D are added to the third reactor. Under inert gas protection, 1,4-dioxane is added to dissolve and stirred. The temperature is then raised to the first reaction temperature, and boron trifluoride diethyl ether is added. The temperature is then raised to the second reaction temperature, and the mixture is stirred until the reaction is complete. After post-treatment, compound E is obtained. The general reaction formula is:

[0045]

[0046] Wherein, n is a natural number from 1 to 100, and R is selected from any one of hydrogen, a straight chain having 1 to 8 carbon atoms, a branched chain having 1 to 8 carbon atoms, or a cyclic alkyl chain having 1 to 8 carbon atoms. The first temperature is 60-90°C, the second temperature is 100-110°C, the reaction time is 48 hours, and the post-treatment includes reprecipitation and Soxhlet extraction. The equivalence ratio of compound C, compound D, and boron trifluoride diethyl ether is 1:1:1 to 5. Preferably, the first temperature is 70°C, the second temperature is 105°C, and the equivalence ratio of compound C, compound D, and boron trifluoride diethyl ether is 1:1:1.

[0047] This invention provides a method for preparing anthracene derivative carbazole polymer, as detailed below:

[0048] The molecular formula of the anthracene derivative carbazole polymer is:

[0049]

[0050] The synthetic route is as follows:

[0051]

[0052] The specific preparation method is as follows:

[0053] Before the experiment, all glassware was dried. Magnesium granules (1.74 g) and one iodine grain were added to a two-necked flask, sealed, and protected under a nitrogen atmosphere. Bromobenzene (7.5 mL) was added to 72 mL of tetrahydrofuran (THF), and after complete dissolution, 2 mL was slowly injected into the magnesium-iodine system. The mixture was heated until the grayish-brown color turned colorless. An ice-water bath was prepared during this process to prevent excessive temperature from causing bumping. The remaining solution was then added to the reaction flask, and the reaction was carried out at 60 °C for 3 hours to prepare the first reactant, namely the Grignard reagent.

[0054] Anthraquinone (3g, 170mL THF) was added to another apparatus and stirred at -40℃ for 20min. At this temperature, the Grignard reagent prepared in the first apparatus was extracted and injected into a reaction flask containing anthraquinone solution. The reaction system was carried out under nitrogen protection. Subsequently, the temperature was raised and the reaction system was stirred at -5℃ for 4h to complete the reaction.

[0055] After the reaction was completed, a suitable amount of saturated ammonium chloride aqueous solution was added to the reaction solution to quench the reaction. The mixture was then extracted multiple times with CH2Cl2, and the organic phase was collected. The organic phase was dried over anhydrous sodium sulfate, the desiccant was filtered off, and the solvent was removed by vacuum distillation. The crude product was separated by silica gel column chromatography to obtain a 45% pure product (100-200 mesh silica gel, eluent V). 石油醚 :V 二氯甲烷 =1:2), and then recrystallized from dichloromethane and petroleum ether to give a white flaky solid (2.32 g, 45%).

[0056] The white, flaky solid product was confirmed to be diphenylanthracene ditert-ol by proton NMR spectroscopy. The proton NMR data are as follows: 1 H NMR (400MHz, CDCl3) δ7.68 (dd, J = 3.39, J = 2.50Hz, 4H), 7.38 (dd, J = 3.35, 2.56Hz, 4H), 7.11-7.02 (m, 10H), 6.87 (s, 2H).

[0057] Wash and dry a 10mL two-necked reaction flask and a spherical condenser beforehand. Weigh out 0.623g (1.8mmol) of diphenylanthracene ditert-ol and 0.3g (1.8mmol) of carbazole, dry them, and then add them to the reaction flask. Seal the flask and place it under nitrogen protection. Inject 4mL of 1,4-dioxane into a syringe and heat to 70°C. Then inject 0.2mL of boron trifluoride diethyl ether into the syringe. Connect the flask to a cooling water source and raise the temperature to 105°C under reflux. Stop the reaction after 48 hours.

[0058] The reaction solution was added dropwise to methanol for gravity sedimentation to collect the precipitate. The precipitate was then extracted using acetone via Soxhlet extraction. Specifically, a 500 mL beaker and magnetic stir bar were washed and dried. 400 mL of methanol was added to the beaker, and the stirring was turned on. The reaction solution was added dropwise to the methanol, resulting in the precipitation of a large amount of powder. After standing, the mixture was filtered. The filter residue was collected, dried, and the preliminary product was obtained.

[0059] A fat extractor and its matching condenser, along with a 500mL flat-bottomed single-necked flask, were pre-washed and dried. 300mL of acetone was added to the flask. The preliminary product was wrapped in filter paper and placed in the fat extractor. The apparatus was connected, and cooling water was introduced. The mixture was heated under reflux for 48 hours, after which the process was stopped. The remaining solid was then dried in a vacuum drying oven, yielding 280mg of anthracene derivative carbazole polymer. The molecular weight of the anthracene derivative carbazole polymer was Mn = 5202, and PDI = 1.23.

[0060] Please see Figure 1 As shown, the anthracene derivative carbazole polymer was subjected to 1H NMR spectroscopy. The 1H NMR spectroscopy data are as follows: 1 H NMR (400MHz, DMSO-d6) δ11.03 (s, 11H), 7.65-6.79 (m, 253H).

[0061] Please see Figure 2 As shown, the maximum absorption peak of the anthracene derivative carbazole polymer solution is 303 nm, and the maximum emission peak is 408 nm.

[0062] In this embodiment, unless otherwise specified, the reaction temperature is room temperature.

[0063] In this embodiment, R is hydrogen. Of course, in other embodiments, R can be any one of a straight chain with 1 to 8 carbon atoms, a branched chain with 1 to 8 carbon atoms, or a cyclic alkyl chain with 1 to 8 carbon atoms. The preparation method is the same, and no limitation is made here.

[0064] The present invention also provides an application of anthracene derivative carbazole polymer in the detection of dihydrogen phosphate ions. The anthracene derivative carbazole polymer is dissolved in an organic solvent and added to the test solution. If white flocculent matter is produced in the solution and the solution becomes turbid, the test solution contains dihydrogen phosphate ions; if the solution does not change, the test solution does not contain dihydrogen phosphate ions.

[0065] In this embodiment, the organic solvent is one or more of the following: dichloromethane, tetrahydrofuran, toluene, chloroform, 1,4-dioxane, and 1,2-dichloroethane. Of course, in other embodiments, the organic solvent can be selected according to the actual situation, and there are no restrictions here.

[0066] Specifically, anthracene derivative carbazole polymers are used as specific probes for detecting dihydrogen phosphate anions. The probes described in the following instructions are anthracene derivative carbazole polymers. The specific detection steps are as follows:

[0067] 1) Dissolve the probe in an organic solvent to prepare a concentration of 10. -4 A solution A, with a concentration on the order of mol / L, is divided into multiple equal groups.

[0068] 2) Different types of anionic tetrabutylammonium salts were dissolved in organic solvents to prepare 10 -3 Solution B with a concentration on the order of mol / L 1-10 The equivalence ratio of tetrabutylammonium salt to probe is 10:1. The anionic salt includes HSO4. - ,Br - I - PF6 - NO3 - ClO4 - BF4 - CH3COO - SCN - and H2PO4 - Tetrabutylammonium salt.

[0069] 3) Take equal amounts of solution B respectively 1-10 Mix the solution with an equal volume of solution A, and then add blank solvent to the mixture at a volume ratio of 8:1 to the probe solution to dilute the mixture into solution C. 1-10 .

[0070] Meanwhile, take an equal volume of solution A and dilute it with the blank solvent to prepare solution C. 10 The equivalent ratio of the blank solvent to the fluorescent probe is 9:1.

[0071] 4) Determine the C of different types of anion mixed with fluorescent probe solutions. 1-10 The absorption spectrum and the absorption and emission spectra at an excitation wavelength of 297 nm were obtained, and wavelength-absorption and wavelength-fluorescence intensity curves were plotted.

[0072] In Example 1 of the probe detection of dihydrogen phosphate anion provided by the present invention, the results of whether the fluorescent probe can detect dihydrogen phosphate anion are displayed by absorption spectrum and fluorescence spectrum, specifically as follows:

[0073] The fluorescent probe compound was dissolved in dichloromethane to prepare a concentration of 1×10⁻⁶. -4 Solution B, mol / L, contains HSO4 - ,Br - I - PF6 - NO3- ClO4 - BF4 - COO - SCN - and H2PO4 - Tetrabutylammonium (TBA+) was dissolved in dichloromethane to prepare solutions with a concentration of 1×10 -3 Solution D was prepared at mol / L. Different tetrabutylammonium anions were added to solution B to ensure uniform mixing of the tetrabutylammonium anion with the fluorescent probe compound. The absorption and fluorescence spectra of each mixed solution were then measured.

[0074] Please see Figure 3 As shown, when the equivalence ratio of added tetrabutylammonium dihydrogen phosphate to the fluorescent probe is 10:1, the ratio of the brightness of the 0-0 peak to the brightness of the 0-1 peak in the emission spectrum is observed to become 1.00. Mixing tetrabutylammonium salts with other anions does not lead to a similar change, which indicates that the probe can specifically select for dihydrogen phosphate anions in dichloromethane solvent.

[0075] In Example 2 of the probe detection of dihydrogen phosphate anions provided by the present invention, the result of whether the probe can detect dihydrogen phosphate anions is displayed by observing the solution color, specifically as follows:

[0076] When the probe was dissolved in an organic solvent and tetrabutylammonium dihydrogen phosphate was added, the solution quickly became turbid and produced white flocculent matter.

[0077] Specifically, the fluorescent probe was dissolved in dichloromethane to prepare a solution with a concentration of 5 × 10⁻⁶. -4 A solution A of mol / L was prepared and divided into several equal portions. 5 × 10⁻⁶ different anions were weighed from each portion. -3 When mol of the probe solution was added to solution A, it was observed that the solution containing tetrabutylammonium dihydrogen phosphate quickly became turbid and produced white flocculent matter, while the probe solutions containing other anions remained pale yellow and transparent. This indicates that the probe has a certain visual detection capability for dihydrogen phosphate anions, meaning that operators can quickly determine whether dihydrogen phosphate anions are present in the solution.

[0078] In summary, this invention uses anthracene derivative carbazole polymer to detect dihydrogen phosphate anions. After mixing dihydrogen phosphate ions and the anthracene derivative carbazole polymer, a white flocculent substance appears in the solution, and the solution becomes turbid, thus achieving visual detection of dihydrogen phosphate anions and improving the detection speed and accuracy of dihydrogen phosphate anions.

[0079] The above embodiments are only used to illustrate the technical solutions of the present invention and are not intended to limit it. Although the present invention has been described in detail with reference to preferred embodiments, those skilled in the art should understand that modifications or equivalent substitutions can be made to the technical solutions of the present invention without departing from the spirit and scope of the technical solutions of the present invention.

Claims

1. The application of an anthracene derivative carbazole polymer in the detection of dihydrogen phosphate ions, characterized in that: Dissolve the anthracene derivative carbazole polymer in an organic solvent and add it to the test solution. If a white flocculent substance is formed in the solution and the solution becomes turbid, then the test solution contains dihydrogen phosphate ions; if the solution does not change, then the test solution does not contain dihydrogen phosphate ions. The general chemical formula of the anthracene derivative carbazole polymer is: ； Where n is a natural number from 10 to 100, and R is selected from any one of hydrogen, a straight chain having 1 to 8 carbon atoms, a branched chain having 1 to 8 carbon atoms, or a cyclic alkyl chain having 1 to 8 carbon atoms.

2. The application of the anthracene derivative carbazole polymer according to claim 1 in the detection of dihydrogen phosphate ions, characterized in that: The organic solvent is one or more of the following: dichloromethane, tetrahydrofuran, toluene, chloroform, 1,4-dioxane, and 1,2-dichloroethane.

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