Polyoxime urethane containing heavy metal ions and preparation and application thereof
By preparing polyoxime urethane materials containing heavy metal ions, and using triboelectric nanogenerators to detect heavy metal ion contamination at room temperature, the problem of non-degradability of existing materials is solved, and rapid and reliable heavy metal ion detection is achieved.
Patent Information
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- DONGHUA UNIV
- Filing Date
- 2025-12-04
- Publication Date
- 2026-04-24
AI Technical Summary
Existing petroleum-based heavy metal ion detection materials are non-degradable or non-recyclable, which contradicts the concept of environmental protection. Furthermore, the detection methods are complex and inefficient, making it impossible to quickly and reliably detect heavy metal ions in liquid environments.
Polyoxime urethane materials containing heavy metal ions were prepared. Mechanical energy was converted into electrical energy by a triboelectric nanogenerator. The difference in electrical signal generated at room temperature by the coordination of heavy metal ions with polyoxime urethane was utilized to achieve the detection of heavy metal ion pollution.
This invention provides a green and environmentally friendly heavy metal ion detection material that can achieve rapid and reliable detection at room temperature through differences in electrical signals, meeting environmental protection requirements and enhancing dynamic performance.
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Figure CN121914360A_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 from industrial, transportation, and waste pollution have a deadly impact on the environment and human health. Furthermore, heavy metal ion incidents have led to numerous tragedies, such as the Fukushima nuclear wastewater discharge incident—this wastewater contained isotopes of heavy metal ions such as cesium, which will have long-term adverse effects on the Pacific waters along the coast of Fukushima Prefecture. 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. 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:
[0008] Where m = 1-4; n = 15~25;
[0009] Where R represents a polyester polyol residue; where the polyester polyol residue is the remaining group after the hydroxyl group of the polyester polyol has been removed.
[0010] The HMIs are at least one of the heavy metal ions.
[0011] Furthermore, m is selected from 1, 2, 3, or 4.
[0012] The HMIs are at least one of cesium, copper, chromium, and nickel ions.
[0013] The polyester polyol is
[0014] Where p = 1-3; x = 6~8.
[0015] Furthermore, p is 1, 2, or 3.
[0016] The metal ion is 1-4% of the molar amount of the oxime group.
[0017] This invention provides a method for preparing a polyoxime urethane containing metal ions, comprising:
[0018] Polyester polyol, solvent, and catalyst are mixed and then added to diphenylmethane diisocyanate 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.
[0019] The polyester polyol is an alcoholysis polyester polyol, such as an alcoholysis polyester polyol obtained by alcoholysis of waste PET.
[0020] The alcoholysis polyester polyol described above is prepared by alcoholysis of waste PET, including: mixing and reacting pretreated waste PET, ethylene glycol and zinc acetate of PET, then adding adipic acid for esterification and chain extension, taking a sample to measure the acid value, continuing the reaction, and obtaining alcoholysis polyester polyol after the reaction is completed.
[0021] The oxime is dimethylglyoxime; the metal salt is one or more salts of cesium, copper, chromium, and nickel; the solvent includes N,N-dimethylformamide; and the catalyst is dibutyltin dilaurate.
[0022] The solvent for the metal salt solution includes N,N-dimethylformamide.
[0023] The catalyst is 0.4-5% of the total mass of the monomers (diphenylmethane diisocyanate, oxime, and polyester polyol); 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 3-6 times the molar amount of the polyester polyol.
[0024] 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 to perform an addition reaction; then adding metal salt solution; the entire reaction is carried out under protective gas conditions; and finally, post-treatment is performed.
[0025] 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.
[0026] The post-treatment involves reacting at 58-65℃ for 12-24 h, followed by vacuum treatment at 78-85℃ for 24-48 h.
[0027] The post-processing is performed by importing the material into the mold.
[0028] The present invention provides a triboelectric material, wherein the triboelectric material contains any of the aforementioned metal ion-containing polyoxime esters.
[0029] 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.
[0030] The positive electrode triboelectric layer is disposed between the negative electrode triboelectric layer and the conductive layer.
[0031] The negative electrode triboelectric layer material is a polydimethylsiloxane film; the conductive layer is a copper foil.
[0032] 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.
[0033] Beneficial effects
[0034] This invention provides a polyoxime-urethane elastomer coordinated with heavy metal ions (HMIs) and used as a triboelectric nanogenerator. The difference in its output voltage signal value enables 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 in which it is immersed, 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.
[0035] This invention introduces different heavy metal ions into polyoxime urethane 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
[0036] Figure 1 The sample from Example 1 did not break when stretched nine times after healing at 55 °C for 24 hours;
[0037] Figure 2 These 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
[0038] 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.
[0039] Table 1 Experimental Materials and Reagents
[0040]
[0041] Preparation of polyester polyols by alcoholysis: PET bottle flakes were washed three times with anhydrous ethanol and dried in a 60 ℃ forced-air oven for later use. When ready for use, waste PET bottle flakes, ethylene glycol, and 0.5 wt% PET zinc acetate were added to a three-necked flask and placed in an oil bath. The mixture was heated to 220 ℃, and the equipped mechanical stirrer and oil-sealed condenser were started. The reaction was carried out, and the hydroxyl value was measured. The temperature was then lowered to 170 ℃, and adipic acid was added at a molar ratio of n(ethylene glycol):n(adipic acid) = 1:0.65 for esterification and chain extension. After 60 min of reaction, the acid value was measured again. Simultaneously, the reaction system was heated back to 220 ℃, and the apparatus was changed. A straight condenser was replaced with a spherical condenser, and the reaction continued. A vacuum was then applied to the system, and the vacuum level was adjusted to 0.1 MPa. Finally, the reaction was completed, yielding a brown paste-like product.
[0042] Example 1
[0043] The alcoholysis polyester polyol (3.093 g, 0.500 mmol) was added to the 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.
[0044] The prepared polyoxime-urethane film containing 3% Cu ions of dimethylglyoxime was cut into lengths, widths, and thicknesses of 20 × 20 × 0.3 mm. 3 A rectangular thin film was used as the friction layer, and a conductive copper foil and a polydimethylsiloxane film as the friction substrate were selected for later use. Finally, the copper foil, friction layer and friction substrate were assembled to obtain a room temperature self-healing triboelectric nanogenerator.
[0045] Example 2
[0046] The alcoholysis polyester polyol (3.093 g, 0.500 mmol) was added to the 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.
[0047] The prepared polyoxime-urethane film containing 3% Cs ions of dimethylglyoxime was cut into lengths, widths, and thicknesses of 20 × 20 × 0.3 mm. 3 A rectangular thin film was used as the friction layer, and a conductive copper foil and a polydimethylsiloxane film as the friction substrate were selected for later use. Finally, the copper foil, friction layer and friction substrate were assembled to obtain a room temperature self-healing triboelectric nanogenerator.
[0048] Example 3
[0049] The alcoholysis polyester polyol (3.093 g, 0.500 mmol) was added to the 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.
[0050] The prepared polyoxime-urethane film containing 3% Ni ions of dimethylglyoxime was cut into lengths, widths, and thicknesses of 20 × 20 × 0.3 mm. 3 A rectangular thin film was used as the friction layer, and a conductive copper foil and a polydimethylsiloxane film as the friction substrate were selected for later use. Finally, the copper foil, friction layer and friction substrate were assembled to obtain a room temperature self-healing triboelectric nanogenerator.
[0051] Example 4
[0052] The alcoholysis polyester polyol (3.093 g, 0.500 mmol) was added to the 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.
[0053] The prepared polyoxime-urethane film containing 3% Cr ions of dimethylglyoxime was cut into lengths, widths, and thicknesses of 20 × 20 × 0.3 mm. 3 A rectangular thin film was used as the friction layer, and a conductive copper foil and a polydimethylsiloxane film as the friction substrate were selected for later use. Finally, the copper foil, friction layer and friction substrate were assembled to obtain a room temperature self-healing triboelectric nanogenerator.
[0054] Comparative Example 1
[0055] Alcohololysis of polyester polyol (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 was allowed to proceed 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.
[0056] The prepared polyoxime-urethane film containing 0% heavy metal ions was cut into dimensions of 20 × 20 × 0.3 mm. 3 A rectangular thin film was used as the friction layer, and a conductive copper foil and a polydimethylsiloxane film as the friction substrate were selected for later use. Finally, the copper foil, friction layer and friction substrate were assembled to obtain a room temperature self-healing triboelectric nanogenerator.
[0057] Performance tests were conducted on Examples 1-4 and Comparative Example 1.
[0058] 1) Uniaxial tensile test:
[0059] The testing procedure was as follows: the tensile properties of POU were characterized using a universal testing machine. The sample size was 15×3×0.5mm. 3 The rectangular spline was stretched at a rate of 50 mm / min, and the result was the average of three data points.
[0060] 2) Triboelectric output performance
[0061] 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 ℃.
[0062] Example 1: After healing at 55 °C for 24 hours, the sample could be stretched to 9 times its original length without breaking. Figure 1 As shown, Example 1 demonstrates good self-healing ability.
[0063] 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 2 As shown, it can be seen that Example 1 achieves the highest electrical output signal, its V OC I SC and Q SC The values are 12.5V, 707.2 nA, and 7.5 nC, respectively. The voltage output signal values of the embodiments, from low to high, are as shown in Embodiment 2 (Voc=6V).
Claims
1. A polyoxime urethane containing metal ions, characterized in that, The metal ion-containing polyoxime ester is a metal ion-coordinated polyoxime ester, with the structural formula: ， Where m = 1-4; n = 15~25; Wherein R is a polyester polyol residue; and the HMIs are at least one of the heavy metal ions.
2. The polyester polyol according to claim 1, characterized in that, The polyester polyol is Where p = 1-3; x = 6~8; The heavy metal ion is at least one of cesium, copper, chromium, and nickel ions.
3. A method for preparing a polyoxime urethane containing metal ions, comprising: Polyester polyol, solvent, and catalyst are mixed and then added to diphenylmethane diisocyanate 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 oxime is dimethylglyoxime; the metal salt is one or more salts of cesium, copper, chromium, and nickel; the solvent includes N,N-dimethylformamide; the catalyst is dibutyltin dilaurate; and the solvent of the metal salt solution includes N,N-dimethylformamide.
5. The preparation method according to claim 3, characterized in that, The catalyst is 0.4% to 5% of the total mass of the monomers; the oxime is 2 to 4 times the molar amount of the polyester polyol; the metal salt is 1 to 4% of the molar amount of the oxime; and the isocyanate is 3 to 6 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 to carry out the addition reaction. Then, a metal salt solution was added. The entire reaction was carried out under protective gas conditions. Finally, post-treatment was performed. The post-treatment involves reacting at 58-65°C for 12-24 hours, followed by vacuum treatment at 78-85°C for 24-48 hours.
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 8, 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.