Copper ion scavenging and detecting reagent based on cluster light-emitting polymer microspheres, preparation method and application thereof

Abstract

The application discloses a copper ion removing and detecting reagent based on cluster luminescent polymer microspheres, a preparation method and application thereof, and the reagent is obtained by sulfonating monodisperse porous cross-linked polystyrene microspheres, and the reagent is used for removing and specifically detecting copper ions. The one-step sulfonating monodisperse porous cross-linked polystyrene microsphere method is used to prepare the copper ion removing and detecting reagent based on cluster luminescent polymer microspheres. The polymer fluorescent microspheres based on cluster luminescence have excellent detection capacity for copper ions. Meanwhile, the sulfonic acid groups after the sulfonation treatment make the polymer microspheres have excellent copper ion removing capacity. The application provides a new method for copper ion detection and removal, and the new method has the advantages of simple operation, economy and good stability.

Description

Technical Field

[0001] This invention relates to the field of copper ion removal and detection materials, and particularly to a copper ion removal and detection reagent based on clustered luminescent polymer microspheres, its preparation method, and its application. Background Technology

[0002] Copper, as a typical heavy metal, is widely used in the battery, manufacturing, metal coating and finishing, metallurgy, and chemical industries. Wastewater from these industries contains large amounts of heavy metal ions, especially copper ions, which not only cause serious environmental pollution but also harm human health, causing gastrointestinal disorders, liver and kidney damage, and other adverse effects. Therefore, international drinking water standards impose strict limits on copper ion concentrations.

[0003] The goal is not only to detect copper ions but also to remove them to the greatest extent possible. Currently, methods for treating copper ions in industrial wastewater mainly include membrane filtration, ion exchange, adsorption, chemical precipitation, nanotechnology, electrochemical methods, and advanced oxidation methods. Among these, commonly used electrochemical methods such as electrocoagulation, electroflotation, and electrodeposition have high treatment efficiency but also high energy consumption. Adsorption is a highly efficient, selective, and low-cost method for removing metal ions. Compared to other methods such as chemical precipitation and ion exchange, adsorption typically has lower equipment investment and operating costs. Adsorption materials are generally inexpensive and reusable, further reducing treatment costs. Furthermore, adsorption is relatively simple to operate, requiring no complex equipment or maintenance, which also reduces operating costs.

[0004] Porous polymer microspheres possess unique advantages in adsorption due to their porous structure and large specific surface area. However, detecting copper ions requires the introduction of fluorescent molecules or particles. This undoubtedly increases the difficulty of synthesis, and fluorescent molecules or particles can also cause environmental pollution.

[0005] In summary, current probes for detecting and adsorbing copper ions suffer from problems such as complex processes, poor stability, and high costs. Summary of the Invention

[0006] The technical problem to be solved by the present invention is to provide a copper ion removal and detection reagent based on cluster luminescent polymer microspheres, its preparation method and application, in order to address the shortcomings of the prior art.

[0007] To solve the above-mentioned technical problems, the technical solution adopted by the present invention is as follows: In the first aspect of the present invention, a copper ion removal and detection reagent based on clustered luminescent polymer microspheres is provided, which is obtained by sulfonating monodisperse porous cross-linked polystyrene microspheres. This reagent is used for the removal and specific detection of copper ions.

[0008] A second aspect of the present invention provides the application of the reagent described above in the specific detection of copper ions.

[0009] Preferably, the application method is as follows: after preparing the reagent into a dispersion, it is mixed with the solution to be tested and incubated, and then the fluorescence intensity of the mixture is detected. The concentration of copper ions in the solution to be tested is obtained by analyzing a pre-constructed standard curve characterizing the relationship between copper ion concentration and fluorescence intensity.

[0010] Preferably, the concentration of the dispersion prepared from the detection reagent is 1×10⁻⁶. 4 ~1×10 6 Particles / mL.

[0011] Preferably, the incubation time is 15-60 minutes.

[0012] Preferably, the application method is as follows: the reagent is prepared to a concentration of 3×10 5 A dispersion of 1 particle / mL was prepared, then mixed with the test solution and incubated for 30 min. The fluorescence intensity of the mixture was then detected, and the copper ion concentration in the test solution was obtained by analyzing a pre-constructed standard curve characterizing the relationship between copper ion concentration and fluorescence intensity.

[0013] A third aspect of the present invention provides the application of the reagent described above in the removal of copper ions.

[0014] Preferably, the application method is as follows:

[0015] Add the reagent to the solution containing copper ions, with the addition amount controlled at 10-50 mg per 1 L of solution. Incubate at room temperature for 1.5-6 h, filter, and the resulting filtrate is the solution after copper ions have been removed.

[0016] A fourth aspect of the present invention provides a method for preparing a copper ion scavenging and detection reagent based on cluster-luminescent polymer microspheres as described above, characterized by comprising the following steps:

[0017] 1) Provide monodisperse porous cross-linked polystyrene microspheres;

[0018] 2) Monodisperse porous cross-linked polystyrene microspheres were heated in 95% concentrated sulfuric acid at 70°C for 3 hours. The resulting product was poured into ice water, cooled, filtered, washed with deionized water until neutral, and then dried to constant weight to obtain the copper ion removal and detection reagent based on cluster luminescent polymer microspheres.

[0019] Preferably, step 1) specifically includes:

[0020] 1-1) Preparation of PS seed microspheres:

[0021] 1-1-1) Take 10g of polyvinylpyrrolidone and add it to 300g of anhydrous ethanol. Add the resulting solution to a 500ml reactor and react at 70℃ for 24h.

[0022] 1-1-2) After the reaction is complete, take 40g of styrene and 0.8g of AIBN and add them to a beaker. After ultrasonic dispersion, add them to the reactor and mix with the product obtained in S1-1-1. Then, purge with N2 for 20min and react for 24h.

[0023] 1-1-3) After the reaction is complete, the product is centrifuged at 2000 rpm for 5 min;

[0024] 1-1-4) The solid product after centrifugation was ultrasonically washed three times with ethanol and then dried overnight to obtain PS seed microspheres.

[0025] 1-2) Preparation of monodisperse porous cross-linked polystyrene microspheres:

[0026] 1-2-1) Take 1.2g of the PS seed microspheres prepared in step 1-1) and disperse them in 40mL of deionized water. After ultrasonic dissolution, pour them into the reactor and stir at 250rpm for 60min.

[0027] 1-2-2) Add 5 mL of toluene and 5 mL of dibutyl phthalate to 40 mL of 0.375 wt% sodium dodecyl sulfate aqueous solution, pulverize with a cell disruptor until uniformly dispersed, and then add the resulting mixture to the reactor and mix with the product obtained in step 1-2-1). React at 30 °C for 24 h.

[0028] After the reaction is complete, add 1g of benzoyl peroxide and 10mL of styrene to a beaker and mix well. Then add 4mL of divinylbenzene and 80mL of 0.25wt% sodium dodecyl sulfate aqueous solution to the beaker. Add the resulting mixture to the reactor and mix with the product of step 1-2-2). React at 30℃ for 24h.

[0029] 1-2-4) Add 2 mL of 10 wt% polyvinyl alcohol aqueous solution to the reactor, purge with nitrogen for 15 min, stir, heat to 75 °C, and react for 24 h;

[0030] 1-2-5) The product obtained in step 1-2-4) was washed by centrifugation with distilled water and ethanol in sequence. Then the product was added to tetrahydrofuran and washed at 70°C for 10 h. Finally, it was washed three times with deionized water and ethanol respectively and dried under vacuum to obtain monodisperse porous cross-linked polystyrene microspheres.

[0031] The copper ion scavenging and detection reagent based on clustered luminescent polymer microspheres in this invention is an improvement upon the inventor's previous patent CN115304882B. The difference lies in the fact that the inventor discovered, during research, that monodisperse porous cross-linked polystyrene microspheres, after sulfonic acid treatment, possess the following unique properties: 1. Broad emission (400-700nm) covering the entire visible light region; 2. Specific adsorption with copper ions, enabling specific detection and scavenging of copper ions. Based on this, this invention designs a copper ion scavenging and detection reagent based on clustered luminescent polymer microspheres, its preparation method, and its application method.

[0032] The beneficial effects of this invention are:

[0033] This invention employs a one-step sulfonation method for monodisperse porous polystyrene crosslinked microspheres to prepare a copper ion scavenging and detection reagent based on cluster-luminescent polymer microspheres. The cluster-luminescent polymer fluorescent microspheres exhibit excellent detection capabilities for copper ions, while the sulfonic acid groups after sulfonation treatment endow the polymer microspheres with outstanding copper ion scavenging ability. This invention provides a new method for copper ion detection and scavenging that is simple to operate, economical, and has good stability.

[0034] The reagent of this invention has the following characteristics: (1) Simple synthesis: It can be obtained by one-step sulfonation of porous polystyrene microspheres; (2) Good stability: The intrinsic fluorescence generated by the non-conjugated, clustered luminescence system has excellent fluorescence stability; (3) Excellent detection performance: The detection limit is 13.6 nM, which is better than most copper ion sensors; (4) Excellent copper ion adsorption capacity: The copper ion adsorption capacity is 55 mg / g, which can quickly remove copper ions. Attached Figure Description

[0035] Figure 1 This is a schematic diagram illustrating the principle of copper ion removal and detection based on the cluster-luminescent polymer microspheres of the present invention.

[0036] Figure 2 Fluorescence spectra of the reagent prepared in Example 1 at different excitation wavelengths;

[0037] Figure 3 The results are for the specificity detection of the reagent prepared in Example 1;

[0038] Figure 4 The results show the detection performance of the reagent prepared in Example 1 for copper ions.

[0039] Figure 5 The results of the test on the copper ion removal performance of the reagent prepared in Example 1 are shown. Detailed Implementation

[0040] The present invention will be further described in detail below with reference to embodiments, so that those skilled in the art can implement it based on the description.

[0041] It should be understood that terms such as “having,” “comprising,” and “including” as used herein do not exclude the presence or addition of one or more other elements or combinations thereof.

[0042] Unless otherwise specified, the experimental methods used in the following examples are conventional methods. Unless otherwise specified, the materials and reagents used in the following examples are commercially available. For examples where specific conditions are not specified, conventional conditions or conditions recommended by the manufacturer are followed. For reagents or instruments whose manufacturers are not specified, they are all commercially available products.

[0043] Example 1

[0044] A copper ion scavenging and detection reagent based on clustered luminescent polymer microspheres is prepared by the following steps:

[0045] 1) Provide monodisperse porous cross-linked polystyrene microspheres:

[0046] 1-1) Preparation of PS seed microspheres:

[0047] 1-1-1) Take 10g of polyvinylpyrrolidone and add it to 300g of anhydrous ethanol. Add the resulting solution to a 500ml reactor and react at 70℃ for 24h.

[0048] 1-1-2) After the reaction is complete, take 40g of styrene and 0.8g of AIBN and add them to a beaker. After ultrasonic dispersion, add them to the reactor and mix with the product obtained in S1-1-1. Then, purge with N2 for 20min and react for 24h.

[0049] 1-1-3) After the reaction is complete, the product is centrifuged at 2000 rpm for 5 min;

[0050] 1-1-4) The solid product after centrifugation was ultrasonically washed three times with ethanol and then dried overnight to obtain PS seed microspheres.

[0051] 1-2) Preparation of monodisperse porous cross-linked polystyrene microspheres:

[0052] 1-2-1) Take 1.2g of the PS seed microspheres prepared in step 1-1) and disperse them in 40mL of deionized water. After ultrasonic dissolution, pour them into the reactor and stir at 250rpm for 60min.

[0053] 1-2-2) Add 5 mL of toluene and 5 mL of dibutyl phthalate to 40 mL of 0.375 wt% sodium dodecyl sulfate aqueous solution, pulverize with a cell disruptor until uniformly dispersed, and then add the resulting mixture to the reactor and mix with the product obtained in step 1-2-1). React at 30 °C for 24 h.

[0054] After the reaction is complete, add 1g of benzoyl peroxide and 10mL of styrene to a beaker and mix well. Then add 4mL of divinylbenzene and 80mL of 0.25wt% sodium dodecyl sulfate aqueous solution to the beaker. Add the resulting mixture to the reactor and mix with the product of step 1-2-2). React at 30℃ for 24h.

[0055] 1-2-4) Add 2 mL of 10 wt% polyvinyl alcohol aqueous solution to the reactor, purge with nitrogen for 15 min, stir, heat to 75 °C, and react for 24 h;

[0056] 1-2-5) The product obtained in step 1-2-4) was washed by centrifugation with distilled water and ethanol in sequence. Then the product was added to tetrahydrofuran and washed at 70°C for 10 h. Finally, it was washed three times with deionized water and ethanol respectively and dried under vacuum to obtain monodisperse porous cross-linked polystyrene microspheres, or porous polystyrene microspheres.

[0057] 2) Monodisperse porous cross-linked polystyrene microspheres were heated in 95% concentrated sulfuric acid at 70°C for 3 hours. The resulting product was poured into ice water, cooled, filtered, washed with deionized water until neutral, and then dried to constant weight to obtain a copper ion scavenging and detection reagent based on cluster luminescent polymer microspheres, or cluster luminescent broadband fluorescent microspheres.

[0058] This invention synthesizes a copper ion scavenging and detection reagent based on cluster-luminescent polymer microspheres through a one-step sulfonation porous polystyrene microsphere synthesis. A broad-emission fluorescent microsphere is constructed using a non-conjugated, cluster-luminescent system. The presence of copper ions affects the luminescent clusters, leading to a decrease in fluorescence, thus enabling the formation of a copper ion detection and scavenging reagent. (Refer to...) Figure 1 The mechanism for copper ion detection and removal.

[0059] Reference Figure 2 The fluorescence spectra of the reagent prepared in this embodiment at different excitation wavelengths show that its spectrum covers a wide emission range (400-700 nm) across the entire visible light region.

[0060] Example 2

[0061] The application of the reagent prepared in Example 1 in the specific detection of copper ions is as follows: the reagent is prepared to a concentration of 3×10⁻⁶. 5A dispersion of 1 particle / mL was prepared, then mixed with the test solution and incubated for 30 min. The fluorescence intensity of the mixture was then detected, and the copper ion concentration in the test solution was obtained by analyzing a pre-constructed standard curve characterizing the relationship between copper ion concentration and fluorescence intensity.

[0062] Performance testing:

[0063] 1. Specific detection

[0064] Multiple metal ion solutions were respectively mixed with the dispersion of the reagent prepared in Example 1 (concentration 3 × 10⁻⁶). 5 Each particle (mL) -1 Incubate at room temperature for 30 minutes. Metal ions include: Na + K + Mg 2+ Fe 2+ Fe 3+ Hg 2+ Cu 2+ Hg 2+ Pb 2+ Ba 2+ Mn 2+ and Zn 2+ (10 μmol); then the fluorescence intensity (FITC) was measured by flow cytometry, and the number of spheres was recorded. 5 indivual.

[0065] Test results are as follows Figure 3 As shown in the figure, it can be seen that it has better detection sensitivity for copper ions.

[0066] 2. Detection performance test

[0067] Cu of different concentrations 2+ A dispersion of the reagent prepared in Example 1 (concentration 3 × 10⁻⁶) 5 Each particle (mL) -1 Incubate at room temperature for 30 min, then measure the average fluorescence intensity in the FITC channel of a flow cytometer and record the number of spheres (10). 5 indivual.

[0068] Reference Figure 4 ,from Figure 4 As shown in Figure A, within a certain range, the fluorescence intensity gradually decreases with increasing copper ion concentration. A standard curve is obtained by plotting the decrease in fluorescence intensity (initial fluorescence intensity F0 - fluorescence intensity F after the addition of copper ions) on the ordinate and the logarithm of the copper ion concentration on the abscissa, as shown in Figure A. Figure 4 B, the linear equation is y = 0.374x + 0.167, R 2 =0.983, and the detection limit for copper ions is 13.6 nM, indicating that this reagent has excellent copper ion detection performance.

[0069] Example 3

[0070] The application of the reagent prepared in Example 1 in copper ion scavenging is as follows:

[0071] Add the reagent to the solution containing copper ions, with the addition amount controlled at 25 mg per 1 L of solution. Incubate at room temperature for 3 h, filter, and the resulting filtrate is the solution after copper ions have been removed.

[0072] Cleanup performance test:

[0073] 1 mg of the reagent prepared in Example 1 was mixed with 40 mL of different copper ion solutions (0-500 mg / L); the mixture was incubated at room temperature for 3 h to allow adsorption to reach equilibrium; finally, the remaining copper ion content in the supernatant was measured by ICP-MS.

[0074] Reference Figure 5 The results are shown in the copper ion scavenging performance test, where Ce represents the initial concentration of copper ions and Q is the adsorption amount per unit of reagent at equilibrium adsorption. It can be seen that the reagent has excellent copper ion scavenging performance.

[0075] Although the embodiments of the present invention have been disclosed above, they are not limited to the applications listed in the specification and embodiments. They can be applied to various fields suitable for the present invention. For those skilled in the art, other modifications can be easily made. Therefore, without departing from the general concept defined by the claims and their equivalents, the present invention is not limited to the specific details.

Claims

1. A cluster-based luminescent polymer microsphere copper ion scavenging and detection reagent for use in copper ion-specific detection or copper ion scavenging, characterized in that, The reagent is obtained by sulfonating monodisperse porous crosslinked polystyrene microspheres, and the preparation method of the monodisperse porous crosslinked polystyrene microspheres is as follows: 1-1) Preparation of PS seed microspheres: 1-1-1) 10 g of polyvinylpyrrolidone was added to 300 g of anhydrous ethanol, and the obtained solution was added to a 500 ml reactor, and reacted at 70 DEG C for 24 h; 1-1-2) After the reaction was completed, 40 g of styrene and 0.8 g of AIBN were added to a beaker, ultrasonically dispersed, then added to the reactor to mix with the product obtained in step 1-1-1), then N2 was introduced for 20 min, and reacted for 24 h; 1-1-3) After the reaction was completed, the obtained product was centrifuged at 2000 rpm for 5 min; 1-1-4) The solid product after centrifugation was washed with ethanol by ultrasonic for 3 times, and then dried overnight to obtain PS seed microspheres; 1-2) Preparation of monodisperse porous crosslinked polystyrene microspheres: 1-2-1) 1.2 g of PS seed microspheres prepared in step 1-1) was dispersed in 40 mL of deionized water, ultrasonically dissolved, then poured into a reactor, and stirred at 250 rpm for 60 min; 1-2-2) 5 mL of toluene, 5 mL of dibutyl phthalate were added to 40 mL of 0.375 wt% sodium dodecyl sulfate aqueous solution, and then crushed by a cell crusher until uniformly dispersed, then the obtained mixture was added to the reactor to mix with the product obtained in step 1-2-1), and reacted at 30 DEG C for 24 h; 1-2-3) After the reaction was completed, 1 g of benzoyl peroxide and 10 mL of styrene were added to a beaker and mixed uniformly, then 4 mL of divinylbenzene and 80 mL of 0.25 wt% sodium dodecyl sulfate aqueous solution were added to the beaker, and the obtained mixture was added to the reactor to mix with the product of step 1-2-2), and reacted at 30 DEG C for 24 h; 1-2-4) 2 mL of 10 wt% polyvinyl alcohol aqueous solution was added to the reactor, nitrogen was filled for 15 min, stirred, heated to 75 DEG C, and reacted for 24 h; 1-2-5) The product obtained in step 1-2-4) was washed with distilled water and ethanol by centrifugation in turn, then the product was added to tetrahydrofuran, washed at 70 DEG C for 10 h, and finally washed with deionized water and ethanol for three times respectively, and vacuum dried to obtain monodisperse porous crosslinked polystyrene microspheres.

2. Use according to claim 1, characterized in that, The method for applying the reagent to specific detection of copper ions is as follows: the reagent is prepared into a dispersion liquid, then mixed with a to-be-detected solution for incubation, then the fluorescence intensity of the mixture is detected, and the concentration of copper ions in the to-be-detected solution is obtained according to the standard curve representing the relationship between the concentration of copper ions and the fluorescence intensity.

3. Use according to claim 2, characterized in that, The reagent is formulated into a dispersion having a concentration of 1 x 10 4 particles / mL. 6 particles / mL.

4. Use according to claim 3, characterized in that, The time for mixed incubation is 15-60 min.

5. Use according to claim 4, characterized in that, The reagent is applied to a method for specific detection of copper ions: the reagent is prepared into a dispersion solution with a concentration of 3x10 5 particles / mL, and then incubated with a to-be-detected solution for 30 min, and then the fluorescence intensity of the mixture is detected, and the concentration of copper ions in the to-be-detected solution is obtained according to a standard curve representing the relationship between the concentration of copper ions and the fluorescence intensity.

6. The use according to claim 1, characterized in that, The method for applying the reagent to specific removal of copper ions is as follows: The reagent is added to a to-be-treated solution containing copper ions, and the addition amount is controlled to be 10-50 mg of the reagent per 1 L of the to-be-treated solution, and incubated at room temperature for 1.5-6 h, and filtered, and the obtained filtrate is a solution after removal of copper ions.

7. Use according to claim 1, characterized in that, The preparation method of the reagent comprises the following steps: 1) providing monodisperse porous crosslinked polystyrene microspheres; 2) The monodisperse porous crosslinked polystyrene microspheres were heated in concentrated sulfuric acid with a mass concentration of 95% at 70°C for 3 h, and the obtained product was poured into ice water, cooled, filtered, washed with deionized water until neutral, and then dried to constant weight to obtain the copper ion removal and detection reagent based on the cluster luminescent polymer microspheres.

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