Preparation method and application of a kind of poly-amidoxime semi-interpenetrating network hydrogel membrane
The preparation of agarose gel and poly(amine oxime) semi-interpenetrating network hydrogel membrane solved the problem of poor heavy metal adsorption in the decoction of Chinese medicinal materials, and achieved efficient and safe heavy metal removal and adsorption, which is suitable for environmental and Chinese medicine extracts.
Patent Information
- Application Number
- CN202410655524.8
- Authority / Receiving Office
- CN · China
- Patent Type
- Patents(China)
- Current Assignee / Owner
- Filing Date
- 2024-05-24
- Publication Date
- 2026-01-27
- Estimated Expiration
- 2044-05-24
AI Technical Summary
Existing materials have poor adsorption effects on heavy metals in the decoction of Chinese medicinal herbs and pose a risk of secondary pollution, making it difficult to meet the requirements for efficient removal of complex matrices and trace heavy metals from Chinese medicinal herbs.
A method for preparing agarose gel and poly(ammonia oxime) semi-interpenetrating network hydrogel membrane was adopted. Poly(ammonia oxime) was immobilized by the biocompatibility and hydrophilic 3D network structure of agarose to form a poly(ammonia oxime) semi-interpenetrating network hydrogel membrane. The temperature response characteristics of the membrane were used for selective adsorption and removal of heavy metals.
It achieves efficient, safe, and environmentally friendly heavy metal adsorption and removal, and is especially suitable for aqueous extracts of Chinese medicinal materials. It improves adsorption capacity and selectivity, reduces adsorption of active ingredients in Chinese medicinal materials, and is easy to separate and recycle.
Smart Images
Figure CN118577257B_ABST
Abstract
Description
Technical Field
[0001] This invention belongs to the field of heavy metal removal technology, specifically relating to a method for preparing and applying a poly(ammonia oxime) semi-interpenetrating network hydrogel membrane. Background Technology
[0002] Adsorption is the most commonly used method for heavy metal removal, and the preparation of economical and widely applicable adsorption materials is of great significance. Currently, most materials are not suitable for the adsorption and removal of heavy metals from decoctions of traditional Chinese medicine (TCM). For example, different temperatures and pH values affect the adsorption of heavy metals; most TCM decoctions are neutral, which limits the functional groups of the materials; the matrix composition of TCM is complex, requiring attention to the influence of the adsorption material on the effective components during the removal process; TCM contains many types of heavy metals, which are present in trace amounts, resulting in low adsorption efficiency of natural materials, necessitating modification to improve removal efficiency; furthermore, the toxicity of the materials and the potential for secondary pollution must be considered.
[0003] Agarose gel, a natural polysaccharide polymer hydrogel, is low-cost, environmentally friendly, and exhibits low non-specific adsorption. This gel is soluble in hot water and gels at low temperatures, demonstrating temperature-responsiveness. Its hydrophilic 3D network facilitates the diffusion and capture of heavy metal ions. Therefore, incorporating agarose gel into heavy metal removal materials can reduce toxicity and achieve green and efficient adsorption and removal of heavy metals.
[0004] Currently, there are no reports on poly(ammoxime) semi-interpenetrating network hydrogel membranes. Summary of the Invention
[0005] To overcome the shortcomings of the existing methods, the present invention aims to provide a method for preparing and applying a poly(amine oxime) semi-interpenetrating network hydrogel membrane. This preparation method is simple, has high heavy metal adsorption efficiency, and the heavy metal adsorption material prepared by this method has high stability, wide application range, high selectivity, and is safe and environmentally friendly. Therefore, it can be applied to the selective adsorption and removal of heavy metals in the environment, traditional Chinese medicine extracts, etc.
[0006] To achieve the above objectives, the present invention employs the following technical solution:
[0007] This invention discloses a method for preparing a poly(ammamine oxime) semi-interpenetrating network hydrogel membrane, comprising the following steps:
[0008] 1) Add agarose powder to deionized water, heat to dissolve until transparent, place in a constant temperature water bath to obtain an agarose hydrogel system;
[0009] 2) Dissolve the poly(ammonia oxime) powder in sodium hydroxide and add it to the agarose hydrogel system prepared in step 1). Keep it in a liquid state at a constant temperature and then perform ultrasonic dispersion treatment to obtain a uniform dispersion.
[0010] 3) Transfer the dispersion obtained in step 2) to a reaction plate, cool and gel, and wash to obtain a polyamine oxime semi-interpenetrating network hydrogel membrane.
[0011] Preferably, in step 1), the agarose is dissolved by microwave heating.
[0012] Preferably, in step 1), the final concentration of the agarose hydrogel system is 1% (W / V).
[0013] Preferably, in step 2), the concentration of the sodium hydroxide aqueous solution is 2–6 mg / mL. -1 .
[0014] Preferably, in step 2), the ratio of poly(ammonia oxime) powder to hydrogel solution is (2.0–6.0) mg:(1.0–6.0) mg.
[0015] Preferably, in step 2), the constant temperature ultrasonic temperature is 38–55°C, the ultrasonic power is 100–150W, and the ultrasonic time is 5–30 minutes.
[0016] Preferably, in step 3), the reaction plate is pre-cooled to 0-20°C, the gelation environment temperature is 0-30°C, and the gelation time is 0.2-2.0h.
[0017] Preferably, in step 3), the gel is washed using a shaking rinsing method at a frequency of 10–150 rpm. The washing solvent is deionized water, and the washing time is 0.5–6 hours. The gel is washed until neutral (pH 6–8).
[0018] Another aspect of the present invention provides a heavy metal adsorbent material, which is prepared using the preparation method of the heavy metal adsorbent material described in the present invention.
[0019] This invention also discloses the application of the above-mentioned poly(amine oxime) semi-interpenetrating network hydrogel membrane as a material for the adsorption and removal of heavy metals.
[0020] In some embodiments of the present invention, the metal ion is selected from Cd. 2+ As 3- Pb 2+ Ni 2+ Zn 2+ Co 2+ Ce 3+ Cr 2+ Cr 3+ Cr 6+ Au + Cu 2+ K + Ca 2+ Mg 2+ Na +Fe 2+ Fe 3+ One or more combinations thereof.
[0021] Compared with the prior art, the present invention has the following beneficial effects:
[0022] The present invention provides a method for preparing poly(ammonia oxime) semi-interpenetrating network hydrogel membranes. By utilizing the biocompatibility and hydrophilic 3D network structure of agarose, poly(ammonia oxime) with significant adsorption effect on heavy metals is fixed and uniformly dispersed. This method prepares a highly efficient, pollution-free, selectively adsorbing, low-cost, easily separable, and recyclable poly(ammonia oxime) semi-interpenetrating network agarose gel membrane material. It is not only suitable for the adsorption of heavy metals in wastewater and organic phases, but also particularly suitable for the removal of heavy metals from traditional Chinese medicine, achieving a dual improvement in adsorption capacity and adsorption selectivity.
[0023] The method for preparing poly(ammoxime) semi-interpenetrating network hydrogel membrane provided by the present invention controls the network structure formed by the change of agarose concentration, thereby improving the capture of heavy metal ions by the prepared poly(ammoxime) semi-interpenetrating network agarose gel membrane material and reducing the adsorption of active ingredients of traditional Chinese medicine.
[0024] The method for preparing poly(ammoxime) semi-interpenetrating network hydrogel membrane provided by this invention utilizes the temperature response characteristics of agarose gel, making it easy to separate from wastewater or solution, thus providing conditions for the recovery of other precious heavy metals. Attached Figure Description
[0025] Figure 1 Scanning electron microscope image of a poly(ammylamine oxime) semi-interpenetrating network hydrogel membrane;
[0026] Figure 2 Scanning electron microscope image of a poly(ammoxime) semi-interpenetrating network hydrogel membrane after lead adsorption;
[0027] Figure 3 XPS spectra of poly(ammoxime) semi-interpenetrating network hydrogel membrane and lead adsorption. Detailed Implementation
[0028] To enable those skilled in the art to better understand the present invention, the technical solutions in the embodiments of the present invention are clearly and completely described below. Obviously, the described embodiments are merely one embodiment of the present invention, and not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those skilled in the art without creative effort should fall within the scope of protection of the present invention.
[0029] Reference Figure 1 — Figure 3 The embodiments of the present invention include:
[0030] A method for preparing a poly(ammamine oxime) semi-interpenetrating network hydrogel membrane includes the following steps:
[0031] 1) Synthesis of polyamine oxime
[0032] Weigh 5.56 g of NH₂OH·HCl into a 250 mL three-necked flask, add 40 mL of DMF, heat and stir at 45 °C to dissolve, then add 0.96 g of NaOH and 3.82 g of Na₂CO₃ sequentially, stir vigorously for 4 h to neutralize the free hydrochloric acid, and after the pH of the system is neutral to weakly alkaline, slowly add 4.24 g of polyacrylonitrile solution dissolved in 20 mL of DMF, react at 65 °C for 24 h, after which add 0.48 g of NaOH and 1.91 g of Na₂CO₃, and continue the reaction for 12 h. After completion, replace DMF dropwise with deionized water, and white flocculent precipitate can be seen in the solution. Filter through a Buchner funnel and vacuum dry for 8 h to obtain crude poly(amine oxime).
[0033] 2) Preparation of poly(ammamine oxime) semi-interpenetrating network hydrogel membrane
[0034] Add 200 mg of agarose powder to 10 mL of deionized water, microwave on high for 2 minutes until dissolved and transparent, then place in a 45°C water bath to obtain an agarose concentration of 20 mg / mL. -1 Agarose hydrogel system; weigh out crude poly(ammonia oxime) and dissolve it in 4 mg / mL solution. -1 Prepare a 20 mg / mL solution in NaOH. -1 The poly(ammonia) oxime solution was preheated at 45°C for later use. The preheating temperature was maintained at 45°C with ultrasonication at a power of 150W. 2 mL of the poly(ammonia) oxime solution was mixed into 2 mL of agarose hydrogel system and ultrasonically dispersed at 45°C for 20 min to obtain a uniform dispersion. The reaction plate was precooled to 10°C, and 0.2 mL of the uniform dispersion was transferred to the reaction plate and allowed to gel at room temperature for 1 h. The poly(ammonia) oxime semi-interpenetrating network hydrogel membrane was washed with deionized water at a shaking frequency of 80 rpm until neutral (pH 6–8).
[0035] 3) Poly(amine oxime) semi-interpenetrating network hydrogel membrane adsorbs Pb 2+
[0036] The prepared poly(ammonia oxime) semi-interpenetrating network hydrogel membrane was immersed in 1.0 mL of a solution containing 20 mg·mL⁻¹. -1 In a lead ion solution, adsorption was performed at 25°C for 12 hours to achieve the removal of heavy metal lead. Under neutral conditions, the lead removal rate reached 78.62%, and under alkaline conditions, the lead removal rate was nearly 100%.
[0037] Example 1
[0038] A method for preparing a poly(ammamine oxime) semi-interpenetrating network hydrogel membrane includes the following steps:
[0039] 1) Add 200 mg of agarose powder to 10 mL of deionized water, microwave on high for 2 minutes until dissolved and transparent, then place in a 55°C constant temperature water bath to obtain an agarose concentration of 20 mg / mL. -1 Agarose hydrogel system;
[0040] 2) Weigh out crude poly(ammonia oxime) and dissolve it in 4 mg / mL solution. -1 Prepare a 20 mg / mL solution in NaOH. -1 The poly(ammonia) oxime solution was preheated at 55°C for later use. The preheating constant temperature ultrasonic temperature was 55°C and the ultrasonic power was set to 100W. 1 mL of poly(ammonia) oxime solution was mixed into 1 mL of agarose hydrogel system and ultrasonically dispersed at 55°C for 20 min to obtain a uniform dispersion.
[0041] 3) Pre-cool the reaction plate to 10°C, take 0.2 mL of uniform dispersion and transfer it to the reaction plate, cool and gel at 15°C for 2 h; wash the poly(ammonia oxime) semi-interpenetrating network hydrogel membrane with deionized water at a shaking frequency of 80 rpm, and wash the gel until neutral (pH 6-8) to obtain the poly(ammonia oxime) semi-interpenetrating network hydrogel membrane.
[0042] Example 2
[0043] A method for preparing a poly(ammamine oxime) semi-interpenetrating network hydrogel membrane includes the following steps:
[0044] 1) Add 200 mg of agarose powder to 10 mL of deionized water, microwave on high for 2 minutes until dissolved and transparent, then place in a 45°C constant temperature water bath to obtain an agarose concentration of 20 mg / mL. -1 Agarose hydrogel system;
[0045] 2) Weigh out crude poly(ammonia oxime) and dissolve it in 4 mg / mL solution. -1 Prepare a 30 mg / mL solution in NaOH. -1 The poly(ammonia) oxime solution was preheated at 45°C for later use. The preheating constant temperature ultrasonic temperature was 45°C and the ultrasonic power was set to 120W. 1 mL of poly(ammonia) oxime solution was mixed into 1 mL of agarose hydrogel system and ultrasonically dispersed at 45°C for 20 min to obtain a uniform dispersion.
[0046] 3) Pre-cool the reaction plate to 4°C, transfer 0.2 mL of uniform dispersion to the reaction plate, and allow it to gel at room temperature for 2 h. Rinse the poly(ammonia oxime) semi-interpenetrating network hydrogel membrane with deionized water at a shaking frequency of 80 rpm until the gel is neutral (pH 6-8) to obtain the poly(ammonia oxime) semi-interpenetrating network hydrogel membrane.
[0047] Example 3
[0048] A method for preparing a poly(ammamine oxime) semi-interpenetrating network hydrogel membrane includes the following steps:
[0049] 1) Add 200 mg of agarose powder to 10 mL of deionized water, microwave on high for 2 minutes until dissolved and transparent, then place in a 45°C constant temperature water bath to obtain an agarose concentration of 20 mg / mL. -1 Agarose hydrogel system;
[0050] 2) Weigh out crude poly(ammonia oxime) and dissolve it in 4 mg / mL solution. -1 Prepare a 20 mg / mL solution in NaOH. -1 The poly(ammonia) oxime solution was preheated at 45°C for later use. The preheating constant temperature ultrasonic temperature was 45°C and the ultrasonic power was set to 120W. 1 mL of poly(ammonia) oxime solution was mixed into 1 mL of agarose hydrogel system and ultrasonically dispersed at 45°C for 20 min to obtain a uniform dispersion.
[0051] 3) Pre-cool the reaction plate to 4°C, take 0.2 mL of uniform dispersion and transfer it to the reaction plate, cool and gel at 4°C for 1 h; wash the poly(ammonia oxime) semi-interpenetrating network hydrogel membrane with deionized water at a shaking frequency of 140 rpm, and wash the gel until neutral (pH 6-8) to obtain the poly(ammonia oxime) semi-interpenetrating network hydrogel membrane.
[0052] Using the poly(ammonia oxime) semi-interpenetrating network hydrogel membrane prepared in Example 3 as an example, the application of the poly(ammonia oxime) semi-interpenetrating network hydrogel membrane as described in claim 1 in the field of heavy metal removal and adsorption is as follows:
[0053] (1) Using polyamine oxime semi-interpenetrating network hydrogel membrane to adsorb Pb in aqueous solution 2+
[0054] The prepared poly(ammonia oxime) semi-interpenetrating network hydrogel membrane was immersed in 1.0 mL of a solution containing 20 mg·mL⁻¹. -1 In a lead ion solution, after adsorption at 25°C for 12 hours, the lead removal rate reached 78.62% under pH 6–8 conditions, and nearly 100% under pH > 8 conditions, indicating that the poly(amine oxime) semi-interpenetrating network hydrogel membrane prepared in this invention has good lead adsorption and removal performance.
[0055] (2) Removal of Pb from Alpinia galanga aqueous extract using polyamine oxime semi-interpenetrating network hydrogel membrane 2+
[0056] Weigh 5g of galangal, add 50ml of drinking water and decoct for 30 minutes. Repeat the process once, filter and collect the filtrate to obtain galangal aqueous extract. Immerse the prepared poly(xylene oxime) semi-interpenetrating network hydrogel membrane in 5ml of galangal aqueous extract at 40℃ for 2 hours. Remove the poly(xylene oxime) semi-interpenetrating network hydrogel membrane, and analyze the lead-free galangal aqueous extract using atomic absorption spectrophotometry to calculate the lead removal rate of the poly(xylene oxime) semi-interpenetrating network hydrogel membrane. The results show that when the lead concentration in the galangal aqueous extract is 0.75ppm, the removal rate can reach 83.14%, indicating that the poly(xylene oxime) semi-interpenetrating network hydrogel membrane prepared in this invention has good lead adsorption and removal performance.
[0057] High performance liquid chromatography (HPLC) was used to detect the aqueous extract of Alpinia galanga and the aqueous extract of Alpinia galanga after lead removal by poly(ethylene glycol) oxime semi-interpenetrating network hydrogel membrane. The changes in the chromatograms were slight, indicating that the poly(ethylene glycol) oxime semi-interpenetrating network hydrogel membrane prepared in this invention is suitable for the removal of heavy metal lead from aqueous extracts of traditional Chinese medicine.
[0058] The above content is only for illustrating the technical concept of the present invention and should not be construed as limiting the scope of protection of the present invention. Any modifications made to the technical solution based on the technical concept proposed in this invention shall fall within the scope of protection of the claims of this invention.
Claims
1. A method for preparing a poly(ammamine oxime) semi-interpenetrating network hydrogel membrane, characterized in that, Includes the following steps: 1) Add agarose powder to deionized water, heat to dissolve until transparent, and place in a constant temperature water bath to obtain an agarose hydrogel system; the dissolution temperature of agarose is 55~120 ℃; the constant temperature water bath temperature is 40~70 ℃; the final concentration of the agarose hydrogel system is 0.1% ~ 4% W / V; 2) Poly(ammonia oxime) powder was dissolved in sodium hydroxide aqueous solution and added to the agarose hydrogel system. The mixture was kept at a constant temperature in a liquid state and then ultrasonically dispersed to obtain a uniform dispersion. The concentration of the sodium hydroxide aqueous solution was 0.01–10 mg / mL. -1 The ratio of poly(ammonia oxime) powder to agarose hydrogel was (2.0~6.0) mg: (1.0~6.0) mg; the constant temperature ultrasonic temperature was 38~55℃, the ultrasonic power was 100~150 W, and the ultrasonic time was 5~30 min. 3) Transfer the dispersion to a reaction plate, cool and gel, and wash to obtain a poly(amine oxime) semi-interpenetrating network hydrogel membrane; pre-cool the reaction plate to 0~20℃, gelation environment temperature 0~30℃, gelation time 0.2~2.0 h; use deionized water for washing, washing time is 0.5~6 h, washing methods include soaking, rinsing, and shaking rinsing, shaking frequency is 10~150 rpm.
2. The method for preparing the poly(amine oxime) semi-interpenetrating network hydrogel membrane according to claim 1, characterized in that, Agarose can be dissolved by microwave heating, water bath heating, or oil bath heating.
3. The method for preparing the poly(amine oxime) semi-interpenetrating network hydrogel membrane according to claim 1, characterized in that, In step 3), wash the gel until it is neutral.
4. The poly(amine oxime) semi-interpenetrating network hydrogel membrane prepared by the preparation method described in claim 1.
5. The application of the poly(amine oxime) semi-interpenetrating network hydrogel membrane as described in claim 4 in the field of heavy metal removal.
6. The application according to claim 5, characterized in that, Heavy metal ions selected from Cd 2+ Pb 2+ Ni 2+ Zn 2+ Co 2+ Ce 3+ Cr 2+ Cr 3+ Au + Cu 2+ Fe 2+ Fe 3+ One or more combinations thereof.