Macromolecule for detecting heavy metal ions as well as preparation and application thereof
By using polyoxourethane material containing heavy metal ions in a triboelectric nanogenerator to increase the potential difference and generate an electrical signal, the reliability and environmental protection issues of petroleum-based material detection are solved, and efficient detection of heavy metal ions is achieved.
Patent Information
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2026-01-21
- Publication Date
- 2026-04-07
AI Technical Summary
In existing technologies, petroleum-based heavy metal ion detection materials are difficult to achieve reliable, rapid, and environmentally friendly detection, and do not conform to the concept of sustainable development for environmental protection.
A polyoxourethane material containing heavy metal ions was designed. By using triboelectric nanogenerator technology, heavy metal ions were enriched on the surface of the polyoxourethane to increase the potential difference and generate an electrical signal for the detection of heavy metal ion pollution.
It achieves efficient detection of heavy metal ions at room temperature, with distinct output electrical signal characteristics, and is suitable for heavy metal ion pollution detection devices and equipment.
Smart Images
Figure CN121801033A_ABST
Abstract
Description
Technical Field
[0001] This invention belongs to the field of polymer materials, and specifically relates to a polyoxime ester containing heavy metal ions and its preparation and application. Background Technology
[0002] Heavy metal ions generated by industrial, transportation, and waste pollution have a fatal impact on the environment and human health. Therefore, in recent years, the reliable and rapid detection of heavy metal ions in liquid environments has received widespread attention.
[0003] Compared to complex instrument detection techniques such as infrared and Raman spectroscopy, and methods that rely on long-term cultivation of biological organisms like bacteria to detect specific heavy metal ions, material-based heavy metal ion adsorption and response signal detection technologies hold immense potential in overcoming limitations in convenience, efficiency, and lifespan. Among these, polymeric materials that exhibit specific interactions with heavy metal ions and possess responsive properties play an irreplaceable and crucial role in the detection of heavy metal ion pollution.
[0004] However, the application of most petroleum-based devices and materials contradicts the concept of sustainable development and environmental protection due to their non-degradable or non-recyclable characteristics, which is an urgent problem to be solved in the field of materials science. Therefore, designing new green, environmentally friendly, and sustainable heavy metal ion detection materials and devices has become an urgent challenge, and this challenge is closely related to the application of multifunctional response materials in the field of heavy metal ion detection.
[0005] Triboelectric nanogenerators, as a novel energy harvesting and sensing device that converts mechanical energy into electrical energy, show great potential in high-temperature environments because they do not require an external power source. Polymer-based triboelectric nanomaterials have simple fabrication processes and good output electrical performance stability, resulting in significant achievements in the field of triboelectric nanogenerator technology. Therefore, it is necessary to invent an information technology design to solve the above problems. Summary of the Invention
[0006] The technical problem to be solved by the present invention is to provide a polyoxime urethane containing heavy metal ions, and its preparation and application.
[0007] This invention provides a metal ion-containing polyoxime urethane, wherein the metal ion-containing polyoxime urethane is a metal ion-coordinated polyoxime urethane, with the following structural formula: , Wherein R is a polyester polyol residue; and the HMIs are at least one of the heavy metal ions.
[0008] The R is: , The HMIs are at least one of cesium, copper, chromium, and nickel ions.
[0009] Furthermore, m=1, n=1, v=1.
[0010] The metal ion is 1-4% of the molar amount of the oxime group.
[0011] This invention provides a method for preparing a polyoxime urethane containing metal ions, comprising: Polyester polyol, solvent, and catalyst are mixed and then added to isocyanate for reaction. Oxime is then added for addition reaction, followed by the addition of metal salt solution and post-treatment to obtain polyoxime urethane containing metal ions.
[0012] The preferred embodiment of the above preparation method is as follows: The polyester polyol is ; The isocyanate is diphenylmethane diisocyanate; The oxime is dimethylglyoxime; The metal salt is one or more of cesium, copper, chromium, and nickel; The solvent includes N,N-dimethylformamide; The catalyst is dibutyltin dilaurate; The solvent for the metal salt solution includes N,N-dimethylformamide.
[0013] The catalyst is 0.1-0.5% of the total mass of the isocyanate monomer; the oxime is 2-4 times the molar amount of the polyester polyol; the metal salt is 1-4% of the molar amount of the oxime; and the isocyanate is 3-5 times the molar amount of the polyester polyol.
[0014] The preparation process includes: heating the polyester polyol and then evacuating it under vacuum; cooling it down and then adding solvent and catalyst to mix; then adding isocyanate dropwise and observing the viscosity change; adding solvent dropwise and reacting for 1-4 hours; then adding oxime solution for addition reaction; then adding metal salt solution for coordination reaction; the entire reaction is carried out under protective gas conditions; and finally, post-treatment is performed.
[0015] The process of heating up and then vacuuming is carried out for 0.5-3 hours after heating up to 115-125 ℃; the process of mixing is carried out by cooling down to 80-89 ℃ and magnetically stirring at 300-500 r / min for 10-20 minutes; the process of addition reaction is carried out at 58-65 ℃ for 18-25 hours. The post-treatment involves reacting at 58-65℃ for 12-24 h, followed by vacuum treatment at 78-85℃ for 24-48 h.
[0016] The post-processing is performed by importing the material into the mold.
[0017] The present invention provides a triboelectric material, wherein the triboelectric material contains any of the metal ion-containing polyoxime esters.
[0018] The present invention provides a triboelectric nanogenerator, which includes a positive triboelectric layer, a negative triboelectric layer, and a conductive layer; wherein the positive triboelectric layer contains any of the metal ion-containing polyoxime esters.
[0019] The positive electrode triboelectric layer is disposed between the negative electrode triboelectric layer and the conductive layer.
[0020] The negative electrode triboelectric layer material is a polydimethylsiloxane film; the conductive layer is a copper foil.
[0021] This invention provides an application of any of the metal ion-containing polyoxime esters, the triboelectric material, or the triboelectric nanogenerator in flexible electronic wearable devices.
[0022] Compared with the prior art, the technical effects and advantages provided by the present invention in the above technical solution are as follows: This invention provides a polyoxime-urethane elastomer coordinated with heavy metal ions (HMIs) and uses it as a triboelectric nanogenerator for the detection of heavy metal ion contamination. Under coordination, heavy metal ions accumulate on the polyoxime-urethane surface, increasing the potential difference between the heavy metal ion-polyoxime-urethane complex and polydimethylsiloxane, thereby generating a higher output voltage signal. This signal exhibits good matching with the various heavy metal ion solutions used for immersion, and can be used for voltage detection. This coordination system not only has unique applications in electrical engineering, but its complexation also enhances dynamic performance.
[0023] This invention introduces different heavy metal ions into polyoxourethane to obtain positive electrode triboelectric materials with significant differences in electrical signals. Then, using copper foil as the conductive layer and polydimethylsiloxane film as the negative electrode triboelectric material, the prepared triboelectric nanogenerators containing different heavy metal ions have different electrical output signal characteristics at room temperature, which can meet the needs of heavy metal ion pollution detection devices and equipment at room temperature. Attached Figure Description
[0024] To more clearly illustrate the technical solutions in the embodiments of this application or the prior art, the drawings used in the embodiments will be briefly introduced below. Obviously, the drawings described below are only some embodiments recorded in this invention. For those skilled in the art, other drawings can be obtained based on these drawings.
[0025] Figure 1 The sample from Example 1 did not break when stretched nine times after healing at 55 °C for 24 hours; Figure 2These are the peak signals of the triboelectric output voltage, current, and charge of Examples 1-4 and Comparative Example 1 at 25 °C over 5 cycles. Detailed Implementation
[0026] The present invention will be further illustrated below with reference to specific embodiments. It should be understood that these embodiments are for illustrative purposes only and are not intended to limit the scope of the invention. Furthermore, it should be understood that after reading the teachings of this invention, those skilled in the art can make various alterations or modifications to the invention, and these equivalent forms also fall within the scope defined by the appended claims.
[0027] Table 1 Experimental Materials and Reagents
[0028] Example 1 Alcohololysis of polyester polyol (1.1PEO-360W, 3.093 g, 0.500 mmol) was added to a reaction flask, and the mixture was heated to 120 °C and vacuum-treated to remove water and residual anhydrous ethanol for 2 h. The mixture was then cooled to 85 °C under a nitrogen atmosphere. N,N-dimethylformamide (DMF, 3 mL) and dibutyltin dilaurate (DBTDL, 0.5 wt%, 0.019 g) were added to the reaction flask, and the mixture was magnetically stirred at 350 r / min for 20 min. Then, diphenylmethane diisocyanate (MDI, 0.526 g, 2.1 mmol) was added dropwise using a syringe, with 5 mL of DMF added in portions according to viscosity changes during the dropwise addition. The reaction was allowed to proceed for 3 h after the addition was complete. Subsequently, the temperature was lowered to 60°C, and a solution of dimethylglyoxime (DMG, 0.174 g, 1.5 mmol) dissolved in 17.5 mL of DMF was slowly added to the flask. The reaction continued for 23 h, followed by the addition of 1 mL of copper chloride in DMF solution (CuCl2, 0.006 g, 0.045 mmol). Finally, the product was poured into a polytetrafluoroethylene mold and transferred to a 60°C vacuum oven for another 24 h. The oven was then heated to 80°C and subjected to vacuum treatment for 48 h to obtain a yellow solid, which was Cu-POU.
[0029] The prepared polyoxime urethane film containing 3 wt% Cu ions was cut into rectangular films with dimensions of 20 × 20 × 0.3 mm³ as the friction layer. Copper foil as the conductive layer and polydimethylsiloxane film as the friction substrate, with the same dimensions, were also selected for later use. Finally, the copper foil, friction layer, and friction substrate were assembled to obtain a room-temperature self-healing triboelectric nanogenerator.
[0030] Example 2 Alcohololysis of polyester polyol (1.1PEO-360W, 3.093 g, 0.500 mmol) was added to a reaction flask, and the mixture was heated to 120 °C and vacuum-treated to remove water and residual anhydrous ethanol for 2 h. The mixture was then cooled to 85 °C under a nitrogen atmosphere. N,N-dimethylformamide (DMF, 3 mL) and dibutyltin dilaurate (DBTDL, 0.5 wt%, 0.019 g) were added to the reaction flask, and the mixture was magnetically stirred at 350 r / min for 20 min. Then, diphenylmethane diisocyanate (MDI, 0.526 g, 2.1 mmol) was added dropwise using a syringe, with 5 mL of DMF added in portions according to viscosity changes during the dropwise addition. The reaction was allowed to proceed for 3 h after the addition was complete. Subsequently, the temperature was lowered to 60 °C, and a solution of dimethylglyoxime (DMG, 0.174 g, 1.5 mmol) dissolved in 17.5 mL of DMF was slowly added to the flask. The reaction continued for 23 h, followed by the injection of 1 mL of cesium chloride DMF solution (CsCl2, 0.008 g, 0.045 mmol). Finally, the product was poured into a polytetrafluoroethylene mold and transferred to a 60 °C vacuum oven for another 24 h. The oven was then heated to 80 °C and subjected to vacuum treatment for 48 h to obtain a yellow solid, which was Cs-POU.
[0031] The prepared polyoxime urethane film containing 3 wt% Cs ions was cut into rectangular films with dimensions of 20 × 20 × 0.3 mm³ as the friction layer. Copper foil as the conductive layer and polydimethylsiloxane film as the friction substrate, with the same dimensions, were also selected for later use. Finally, the copper foil, friction layer, and friction substrate were assembled to obtain a room-temperature self-healing triboelectric nanogenerator.
[0032] Example 3 Alcohololysis of polyester polyol (1.1PEO-360W, 3.093 g, 0.500 mmol) was added to a reaction flask, and the mixture was heated to 120 °C and vacuum-treated to remove water and residual anhydrous ethanol for 2 h. The mixture was then cooled to 85 °C under a nitrogen atmosphere. N,N-dimethylformamide (DMF, 3 mL) and dibutyltin dilaurate (DBTDL, 0.5 wt%, 0.019 g) were added to the reaction flask, and the mixture was magnetically stirred at 350 r / min for 20 min. Then, diphenylmethane diisocyanate (MDI, 0.526 g, 2.1 mmol) was added dropwise using a syringe, with 5 mL of DMF added in portions according to viscosity changes during the dropwise addition. The reaction was allowed to proceed for 3 h after the addition was complete. Subsequently, the temperature was lowered to 60 °C, and a solution of dimethylglyoxime (DMG, 0.174 g, 1.5 mmol) dissolved in 17.5 mL of DMF was slowly added to the flask. After reacting for 23 h, 1 mL of nickel sulfate in DMF solution (NiSO4, 0.007 g, 0.045 mmol) was injected. Finally, the product was poured into a polytetrafluoroethylene mold and transferred to a vacuum oven at 60 °C to continue the reaction for 24 h. The oven was then heated to 80 °C and vacuum-treated for 48 h to obtain a yellow solid, which is Ni-POU.
[0033] The prepared polyoxime urethane film containing 3 wt% Ni ions was cut into rectangular films with dimensions of 20 × 20 × 0.3 mm³ as the friction layer. Copper foil as the conductive layer and polydimethylsiloxane film as the friction substrate, with the same dimensions, were also selected for later use. Finally, the copper foil, friction layer, and friction substrate were assembled to obtain a room-temperature self-healing triboelectric nanogenerator.
[0034] Example 4 Alcohololysis of polyester polyol (1.1PEO-360W, 3.093 g, 0.500 mmol) was added to a reaction flask, and the mixture was heated to 120 °C and vacuum-treated to remove water and residual anhydrous ethanol for 2 h. The mixture was then cooled to 85 °C under a nitrogen atmosphere. N,N-dimethylformamide (DMF, 3 mL) and dibutyltin dilaurate (DBTDL, 0.5 wt%, 0.019 g) were added to the reaction flask, and the mixture was magnetically stirred at 350 r / min for 20 min. Then, diphenylmethane diisocyanate (MDI, 0.526 g, 2.1 mmol) was added dropwise using a syringe, with 5 mL of DMF added in portions according to viscosity changes during the dropwise addition. The reaction was allowed to proceed for 3 h after the addition was complete. Subsequently, the temperature was lowered to 60 °C, and a solution of dimethylglyoxime (DMG, 0.174 g, 1.5 mmol) dissolved in 17.5 mL of DMF was slowly added to the flask. The reaction continued for 23 h, followed by the injection of 1 mL of chromium chloride in DMF solution (CrCl2, 0.012 g, 0.045 mmol). Finally, the product was poured into a polytetrafluoroethylene mold and transferred to a 60 °C vacuum oven for another 24 h. The oven was then heated to 80 °C and subjected to vacuum treatment for 48 h to obtain a yellow solid, which was Cr-POU.
[0035] The prepared polyoxime urethane film containing 3 wt% Cr ions was cut into rectangular films with a length, width, and thickness of 20 × 20 × 0.3 mm3 as the friction layer. A conductive copper foil of the same dimensions and a polydimethylsiloxane film as the friction substrate were also selected for later use. Finally, the copper foil, friction layer, and friction substrate were assembled to obtain a room-temperature self-healing triboelectric nanogenerator.
[0036] Comparative Example 1 Alcohololyzed polyester polyol (1.1PEO-360W, 3.093 g, 0.500 mmol) was added to a reaction flask, and the mixture was heated to 120 °C and vacuum-treated to remove water and residual anhydrous ethanol for 2 h. The mixture was then cooled to 85 °C under a nitrogen atmosphere. N,N-dimethylformamide (DMF, 3 mL) and dibutyltin dilaurate (DBTDL, 0.5 wt%, 0.019 g) were added to the reaction flask, and the mixture was magnetically stirred at 350 r / min for 20 min. Diphenylmethane diisocyanate (MDI, 0.526 g, 2.1 mmol) was then added dropwise using a syringe, with 5 mL of DMF added in portions according to viscosity changes. After the addition was complete, the reaction proceeded for 3 h. Subsequently, the temperature was lowered to 60 °C, and a solution of dimethylglyoxime (DMG, 0.174 g, 1.5 mmol) dissolved in 17.5 mL of DMF was slowly added to the flask, and the reaction continued for 23 h. Finally, the product was poured into a polytetrafluoroethylene mold and transferred to a 60 °C vacuum oven to continue the reaction for 24 h. The oven was then heated to 80 °C and vacuumed for 48 h to obtain a yellow solid, which is 0%-POU.
[0037] The prepared polyoxime urethane film containing 0 wt% heavy metal ions was cut into rectangular films with a length, width, and thickness of 20 × 20 × 0.3 mm3 as the friction layer. A conductive copper foil of the same dimensions and a polydimethylsiloxane film as the friction substrate were also selected for later use. Finally, the copper foil, friction layer, and friction substrate were assembled to obtain a room-temperature self-healing triboelectric nanogenerator.
[0038] Performance tests were conducted on Examples 1-4 and Comparative Example 1. 1) Uniaxial tensile test: The test procedure was as follows: the tensile properties of POU were characterized using a universal testing machine. The sample was a rectangular strip of 15×3×0.5mm3, the tensile rate was 50 mm / min, and the result was the average of three data points.
[0039] 2) Triboelectric output performance The test procedure is as follows: The test sample is a rectangular thin sheet with a length of (20±0.1) mm, (20±0.1) mm and (0.3±0.01) mm. The impact frequency is 2 Hz. The voltage, current and charge are measured at a temperature of 25 ℃.
[0040] Example 1: After healing at 55 °C for 24 h, the sample could be stretched to 9 times its original length without breaking. Figure 1 As shown, Example 1 demonstrates good self-healing ability.
[0041] Examples 1-4 and Comparative Example 1 were tested using an electronic universal testing machine to measure triboelectric open-circuit voltage, charge, and current. Figure 2As shown, Example 1 achieves the highest electrical output signal, with VOC, ISC, and QSC of 12.5V, 707.2 nA, and 7.5 nC, respectively. The voltage output signal values of the examples, from lowest to highest, are as follows: Example 2 (Voc=6V)
Claims
1. A polymer for detecting heavy metal ions, characterized in that, The metal ion-containing polyoxime ester is a metal ion-coordinated polyoxime ester, with the structural formula: ， Wherein R is a polyester polyol residue; and the HMIs are at least one of the heavy metal ions.
2. The polyoxime urethane containing metal ions according to claim 1, characterized in that, The R is ； The HMIs are at least one of cesium, copper, chromium, and nickel ions.
3. A method for preparing a metal ion-containing polyoxime urethane, comprising: Polyester polyol, solvent, and catalyst are mixed and then added to isocyanate for reaction. Oxime is then added for addition reaction, followed by the addition of metal salt solution and post-treatment to obtain polyoxime urethane containing metal ions.
4. The preparation method according to claim 3, characterized in that, The polyester polyol is ； The isocyanate is diphenylmethane diisocyanate; The oxime is dimethylglyoxime; The metal salt is one or more of cesium, copper, chromium, and nickel; The solvent includes N,N-dimethylformamide; The catalyst is dibutyltin dilaurate; The solvent for the metal salt solution includes N,N-dimethylformamide.
5. The preparation method according to claim 3, characterized in that, The catalyst is 0.1-0.5% of the total mass of the monomer isocyanate; the oxime is 2-4 times the molar amount of the polyester polyol; the metal salt is 1-4% of the molar amount of the oxime; and the isocyanate is 3-5 times the molar amount of the polyester polyol.
6. The preparation method according to claim 3, characterized in that, Preparation includes: After heating the polyester polyol and evacuating it, the solvent and catalyst were added and mixed after cooling. Then, isocyanate was added dropwise and the viscosity change was observed. The solvent was added dropwise and the reaction was carried out for 1-4 hours. Then, an oxime solution was added for addition reaction, followed by the addition of a metal salt solution. The entire reaction was carried out under protective gas conditions. It is best to perform post-treatment. The post-treatment involves reacting at 58-65℃ for 12-24 h, followed by vacuum treatment at 78-85℃ for 24-48 h.
7. A triboelectric material, characterized in that, The triboelectric material comprises the polyoxourethane containing metal ions as described in any one of claims 1-2.
8. A triboelectric nanogenerator, characterized in that, The triboelectric nanogenerator comprises a positive triboelectric layer, a negative triboelectric layer, and a conductive layer; wherein the positive triboelectric layer contains the polyoxourethane containing metal ions as described in any one of claims 1-2.
9. The triboelectric nanogenerator according to claim 7, characterized in that, The positive electrode triboelectric layer is disposed between the negative electrode triboelectric layer and the conductive layer; The negative electrode triboelectric layer material is a polydimethylsiloxane film; the conductive layer is a copper foil.
10. The application of the metal ion-containing polyoxourethane of any one of claims 1-2, the triboelectric material of claim 7, or the triboelectric nanogenerator of claim 8 in a flexible electronic wearable device.