A pyridine-polyethersulfone organic polymer and its preparation method and application

Abstract

The present invention belongs to the technical field of adsorption materials, and specifically relates to a pyridine-polyethersulfone organic polymer and a preparation method and application thereof. The pyridine-polyethersulfone organic polymer of the present invention has a structure as shown in Formula 1, R is a carboxyl pyridine group, and n is an integer of 30 to 100. The pyridine-polyethersulfone organic polymer of the present invention is embedded into the macromolecular skeleton of the amino polyethersulfone through the organic ligand of the acylated pyridine, thereby improving the molecular weight and structural stability of the single pyridine. At the same time, the hyperconjugated system formed by the pyridine group in the acylated pyridine and the benzene ring in the amino polyethersulfone enhances the coordination stability between the pyridine-polyethersulfone organic polymer and the heavy metal ions, and improves its adsorption efficiency for heavy metal ions. .

Description

Technical Field

[0001] The invention belongs to the technical field of adsorption materials, and in particular relates to a pyridine-polyether sulfone organic polymer and a preparation method and application thereof. Background Art

[0002] With the rapid development of industrialization and the intensification of environmental pollution, heavy metals such as lead, mercury, cadmium and arsenic are widely present in the environment. After entering the human body, these heavy metals tend to accumulate in the liver, kidneys and blood, and even penetrate into the bones and nervous system, causing serious health problems. For example, individuals who are exposed to heavy metal environments for a long time may suffer from diseases such as kidney damage, nervous system damage, and osteoporosis. Heavy metal poisoning not only affects the health of individuals, but also brings a huge burden to the social medical system.

[0003] At present, the clinical treatment of heavy metal poisoning mainly relies on chemical methods such as chelating agents to help patients excrete heavy metals from their bodies. However, these methods usually have certain side effects and may cause further damage to the patient's kidneys and liver during long-term treatment. In addition, existing treatments have limited effects on the removal of some heavy metals and cannot fully solve the problem of heavy metal poisoning.

[0004] Heavy metal adsorption technology based on organic ligand materials has received widespread attention. Common organic ligand materials include organic acid ligands, pyridine ligands, amine ligands, thiophene ligands and thiol compounds.

[0005] Pyridyl metal complexes formed with pyridine ligands are widely used in water treatment and environmental pollution control because of their remarkable effects in the adsorption and removal of heavy metal ions. Common pyridyl metal complexes include: pyridine-copper (II) complex, pyridine-zinc (II) complex and pyridine-nickel (II) complex. When pyridine is used as a ligand, its coordination mode is often simple and weak, especially when the metal center is small or the electron cloud density is high; pyridyl metal complexes often present a single coordination or a small number of ligands. This coordination environment may lead to insufficient stability of the metal center, making the complex easily dissociated or undergoing coordination exchange due to external factors such as temperature, solvent or other ions. In addition, due to the weak coordination of pyridine ligands, thermal decomposition or thermal excitation may cause dissociation between metal ions and ligands, making the complex easy to decompose or lose stability at high temperature or in a changing environment. The simple structure of the pyridine group makes the complex molecular weight small, especially in complexes with a small amount of pyridine, the structure may lack sufficient rigidity or be relatively loose.

[0006] Based on this, pyridine-based metal complexes still have problems such as small molecular weight, difficult control and poor stability, which leads to poor adsorption of heavy metal ions in the blood. Summary of the invention

[0007] In order to solve the above technical problems, the present invention provides a pyridine-polyethersulfone organic polymer and a preparation method and application thereof.

[0008] The present invention uses polyethersulfone as a skeleton structure, and obtains amino polyethersulfone by performing an amination treatment on polyethersulfone; and uses pyridine as an organic ligand, and obtains acylated pyridine by performing an acyl chloride treatment on pyridine. Through a substitution reaction, the acyl chloride group of the acylated pyridine is grafted and polymerized with the amino group of the amino polyethersulfone, so that the organic ligand of the acylated pyridine is embedded in the macromolecular skeleton of the amino polyethersulfone, thereby obtaining a pyridine-polyethersulfone organic polymer. First, the molecular weight and structural stability of a single pyridine as an organic ligand are improved by embedding the organic ligand of the acylated pyridine into the macromolecular skeleton of the amino polyethersulfone. At the same time, the amide bond system formed by the grafting of the acylated pyridine and the polyethersulfone can be self-degraded in an acid-base environment, which is beneficial to the recovery and reuse of the pyridine-polyethersulfone organic polymer as a heavy metal adsorbent. Secondly, a hyperconjugated system is formed through the coupling structure of the pyridine in the acylated pyridine and the benzene ring in the amino polyether sulfone; compared with the conjugated system of a single pyridine, the formed hyperconjugated system significantly extends the conjugation length and improves the stability and coordination ability of the pyridine-polyether sulfone organic polymer molecule.

[0009] The first object of the present invention is to provide a pyridine-polyether sulfone organic polymer; the pyridine-polyether sulfone organic polymer of the present invention has a structure as shown in Formula 1:

[0010] ;

[0011] In Formula 1, R is a carboxyl pyridine group, and n is an integer of 30 to 100.

[0012] It should be noted that the pyridine compound has strong nucleophilicity, easy modifiability and excellent coordination ability due to the pyridine ring in its structure, and can form a stable heavy metal complex. In addition, the pyridine group has good solubility and chemical stability in water and is an ideal heavy metal adsorption functional group. Preferably, the pyridine compound is carboxypyridine, and the carboxypyridine is one of carboxy monopyridine, carboxy bispyridine and carboxy terpyridine.

[0013] Polyethersulfone has excellent chemical stability, mechanical properties and biocompatibility, and is widely used in a variety of high-performance materials, especially in the fields of membrane materials and separation materials.

[0014] A second object of the present invention is to provide a method for preparing the above-mentioned pyridine-polyether sulfone organic polymer, comprising the following steps:

[0015] Step 1: performing amination treatment on polyether sulfone to obtain amination polyether sulfone.

[0016] It should be emphasized that the present invention first subjects the polyethersulfone to an amination treatment, so as to introduce an amino group into the polyethersulfone molecule to achieve an amination modification treatment of the polyethersulfone molecule, so as to achieve graft polymerization of the amination polyethersulfone and the acylated pyridine through an acyl chloride reaction, thereby embedding the organic ligand of pyridine into the polyethersulfone macromolecular skeleton.

[0017] It should be noted that, in the preparation of the amino polyether sulfone of the present invention, the polyether sulfone is first subjected to nitration treatment under the catalysis and dehydration of concentrated sulfuric acid, and then the nitro group in the nitrated polyether sulfone is reduced to an amino group using tin chloride to obtain the amino polyether sulfone. The specific preparation process of the amino polyether sulfone is as follows: the polyether sulfone is dissolved in a first solvent, stirred evenly, to obtain a polyether sulfone solution; concentrated sulfuric acid and concentrated nitric acid are added to the polyether sulfone solution, and heated at 200°C for 22h~24h to obtain the nitrated polyether sulfone; tin chloride, ethanol and concentrated hydrochloric acid are added to the nitrated polyether sulfone, and heated at 60°C~70°C for 6h~7h to obtain the amino polyether sulfone.

[0018] Preferably, the nitrated polyethersulfone has a structure as shown in Formula 2:

[0019] ;

[0020] In Formula 2, n is an integer ranging from 30 to 100.

[0021] Preferably, the amino polyethersulfone has a structure as shown in Formula 3:

[0022] ;

[0023] In Formula 3, n is an integer ranging from 30 to 100.

[0024] In order to separate and purify the amino polyether sulfone, the present invention cools the reaction solution after the heating reaction to room temperature, and then repeatedly washes the reaction product with double distilled water to remove excess concentrated sulfuric acid, concentrated hydrochloric acid, tin chloride and solvent. Then, the washed precipitate is vacuum dried for 12h to 24h to obtain a solid amino polyether sulfone.

[0025] Preferably, when preparing the nitrated polyethersulfone, the amount ratio of the polyethersulfone, concentrated sulfuric acid and concentrated nitric acid used in the present invention is 10 g: 40 mL: 20 mL to 40 mL.

[0026] Preferably, when preparing the amino polyether sulfone, the mass ratio of the nitrated polyether sulfone, tin chloride and concentrated hydrochloric acid used in the present invention is 2.9-3.1:20:20.

[0027] Preferably, the first solvent is N-methylpyrrolidone.

[0028] Step 2: Carboxyl pyridine is subjected to acyl chloride treatment to obtain acylated pyridine.

[0029] It should be emphasized that the present invention uses pyridine as an organic ligand, and the pyridine needs to be acylated, so as to introduce an acyl chloride group into the pyridine molecule to achieve the acylation modification of the pyridine molecule, so as to realize the graft polymerization of the acylated pyridine and the amino polyether sulfone through the acyl chloride reaction, thereby embedding the organic ligand of pyridine into the macromolecular skeleton of the polyether sulfone.

[0030] It should be noted that the acylated pyridine described in the present invention is one of acylated monopyridine, acylated bispyridine and acylated terpyridine. The present invention takes the synthesis of acylated terpyridine as an example. When preparing acylated terpyridine, p-formylbenzoic acid and 2-acetylpyridine are first used as raw materials, and OH is used to react with 2-acetylpyridine in an alkaline environment. - It takes away the H of the methyl group in 2-acetylpyridine to form a nucleophile -CH2 - , an aldol condensation reaction occurs to obtain 4-carboxyl terpyridine; then 4-carboxyl terpyridine and dithionyl chloride are used for chlorination reaction to obtain acylated terpyridine. The specific preparation process of the acylated terpyridine of the present invention is: under a protective atmosphere, p-formylbenzoic acid and 2-acetylpyridine are dissolved in ethanol, and heated at 80°C for 12h~16h in an alkaline environment; then ammonia water is added and refluxed for 16h~20h to obtain 4-carboxyl terpyridine; 4-carboxyl terpyridine and dithionyl chloride are dissolved in a second solvent under a vacuum, anhydrous and nitrogen filling system, and heated at 100°C~120°C for 2h~6h to obtain acylated terpyridine.

[0031] In order to separate and purify the acylated terpyridine, the present invention cools the reaction solution after the heating reaction to room temperature, and repeatedly washes the reaction product with double distilled water; then, the washed precipitate is vacuum dried for 12h to 24h to obtain solid acylated terpyridine.

[0032] Preferably, the 4-carboxyl terpyridine has a structure as shown in Formula 4:

[0033] .

[0034] Preferably, the acylated monopyridine has a structure as shown in Formula 5, the acylated bispyridine has a structure as shown in Formula 6, and the acylated terpyridine has a structure as shown in Formula 7:

[0035] .

[0036] Preferably, when preparing 4-carboxyl terpyridine, the dosage ratio of p-formylbenzoic acid, 2-acetylpyridine and alkaline solution used in the present invention is 5g:100mL~200mL:10g.

[0037] Preferably, when preparing the acylated terpyridine, the amount ratio of 4-carboxyl terpyridine, thionyl chloride and the second solvent used in the present invention is 1.9 g to 2.1 g: 20 mL: 1 mL.

[0038] Preferably, the second solvent is anhydrous N,N-dimethylformamide.

[0039] Preferably, the alkaline solution is one of sodium hydroxide, potassium hydroxide and ammonia water.

[0040] Step 3: Under a protective atmosphere, the aminated polyethersulfone and the acylated pyridine are dissolved in a solvent, and a substitution reaction is carried out under the action of a dehydrating agent to graft the acyl chloride group on the acylated pyridine onto the amino group of the aminated polyethersulfone to obtain a pyridine-polyethersulfone organic polymer.

[0041] It should be noted that, in the preparation of the pyridine-polyethersulfone organic polymer, the present invention uses aminated polyethersulfone and acylated pyridine as raw materials under a protective atmosphere, dissolves the aminated polyethersulfone and acylated pyridine in a solvent, reacts at room temperature for 14 to 16 hours under the action of a dehydrating agent to carry out a substitution reaction, and the acyl chloride on the acylated pyridine is grafted onto the amino group of the aminated polyethersulfone through nucleophilic substitution to obtain the pyridine-polyethersulfone organic polymer.

[0042] Preferably, the mass ratio of the amino polyethersulfone to the acylated pyridine is 1-2:0.3-0.6.

[0043] Preferably, the mass ratio of the amino polyethersulfone to the dehydrating agent is 1-2:0.5-1.

[0044] Preferably, the usage ratio of the dehydrating agent to the solvent is 0.5 g~1 g: 50 mL~100 mL.

[0045] Preferably, the dehydrating agent is 1-(3-dimethylpropyl)-3-ethylcarbodiimide hydrochloride.

[0046] Preferably, the solvent is one of dichloromethane solution, ethanol and N,N-dimethylformamide.

[0047] The third object of the present invention is to provide the use of the above pyridine-polyethersulfone organic polymer in the preparation of blood heavy metal ion adsorption materials.

[0048] Compared with the prior art, the present invention has the following beneficial effects:

[0049] The pyridine-polyethersulfone organic polymer of the present invention provides efficient heavy metal ion adsorption capacity through the pyridine group, and provides mechanical and chemical stability of the polymer structure through the polyethersulfone skeleton. Compared with general pyridine organic ligands, the pyridine organic ligand is embedded in the macromolecular skeleton of polyethersulfone, and the formed pyridine-polyethersulfone organic polymer has a higher molecular weight and stronger structural stability; the amide bond system formed by the grafting of acylated pyridine and polyethersulfone can be self-degraded in an acid-base environment, which is conducive to the recovery and reuse of the pyridine-polyethersulfone organic polymer as an adsorbent.

[0050] The present invention uses polyethersulfone as a skeleton structure, and obtains amino polyethersulfone by performing an amination treatment on polyethersulfone; uses pyridine as an organic ligand, and obtains acylated pyridine by performing an acyl chloride treatment on pyridine. Acylated pyridine and amino polyethersulfone are grafted and polymerized by a substitution reaction to obtain a pyridine-polyethersulfone organic polymer. The pyridine-polyethersulfone organic polymer of the present invention adopts a coupling structure of a pyridine group in the acylated pyridine and a benzene ring in the amino polyethersulfone to form a hyperconjugated system. Compared with a single pyridine conjugated system, the hyperconjugated system formed by the pyridine-polyethersulfone organic polymer prepared by the present invention significantly prolongs the conjugation length, and improves the stability and coordination ability of the molecule. At the same time, the hyperconjugated system reacts with heavy metals to form a coordination structure, which greatly enhances the coordination stability between the pyridine-polyethersulfone organic polymer and heavy metal ions, thereby improving its adsorption efficiency for heavy metal ions. BRIEF DESCRIPTION OF THE DRAWINGS

[0051] Figure 1 This is the H-NMR spectrum of the aminated polyethersulfone prepared in Example 1 of the present invention.

[0052] Figure 2 The H NMR spectrum of 4-carboxyl terpyridine prepared in Example 1 of the present invention; wherein (a) is a H NMR spectrum with a chemical shift of 0-14, (b) is an enlarged H NMR spectrum with a chemical shift of 12.4-14, and (c) is an enlarged H NMR spectrum with a chemical shift of 7.5-8.85.

[0053] Figure 3 The H NMR spectrum of the acylated pyridine prepared in Example 1 of the present invention; wherein (a) is a H NMR spectrum with a chemical shift of 0-14, and (b) is an enlarged H NMR spectrum with a chemical shift of 9.4-7.9.

[0054] Figure 4 The H NMR spectrum of the pyridine-polyethersulfone organic polymer prepared in Example 1 of the present invention; wherein (a) is a H NMR spectrum with a chemical shift of 0 to 14, (b) is an enlarged H NMR spectrum with a chemical shift of 7 to 8.9, and (c) is an enlarged H NMR spectrum with a chemical shift of 6.74 to 7.43.

[0055] Figure 5 The infrared spectra of the polyethersulfone of the present invention under different chemical modifications; wherein, PES is polyethersulfone; PES-NO2 is the nitroated polyethersulfone prepared in Example 1; PES-NH2 is the amino polyethersulfone prepared in Example 1; PES-Tpy is the pyridine-ethersulfone organic polymer prepared in Example 1.

[0056] Figure 6 The scanning electron microscope images of the pyridine-polyethersulfone organic polymer prepared in Example 1 of the present invention are shown in FIG. 1 , wherein (a) is a scanning electron microscope image at 200 μm, and (b) is a scanning electron microscope image at 5 μm.

[0057] Figure 7 The adsorption amounts of mercury ions and cadmium ions by the pyridine-ether sulfone organic polymer prepared in Example 1 of the present invention under different pH conditions are shown.

[0058] Figure 8 The adsorption of Hg² by the pyridine-ether sulfone organic polymer prepared in Example 1 of the present invention + and Cd² + Ions are exchanged with ions in sodium chloride and no Hg² is adsorbed + and Cd² + XPS spectrum of ions directly exchanged with ions in sodium chloride; (a) is unadsorbed Hg² + and Cd² + The ions are directly exchanged with the ions in sodium chloride, (b) is the adsorption of Hg² + and Cd² + The ions are then exchanged with the ions in sodium chloride. DETAILED DESCRIPTION

[0059] In order to enable those skilled in the art to better understand and implement the technical solution of the present invention, the present invention is further described below in conjunction with specific embodiments and drawings.

[0060] In the description of the present invention, unless otherwise specified, all reagents used are commercially available and all methods used are conventional techniques in the art.

[0061] It should be noted that the full English name of 1-(3-dimethylpropyl)-3-ethylcarbodiimide hydrochloride is 1-(3-Dimethylaminopropyl)-3-ethylcarbodiimide hydrochloride, abbreviated as EDC in English, and the full English name of N,N-dimethylformamide is N,N-Dimethylformamide, abbreviated as DMF in English.

[0062] Example 1

[0063] This embodiment provides a method for preparing a pyridine-polyethersulfone organic polymer.

[0064] Step 1: performing amination treatment on polyether sulfone to obtain amination polyether sulfone.

[0065] 1.1) Preparation of nitrated polyethersulfone: 10 g of polyethersulfone was dissolved in 20 mL of N-methylpyrrolidone and stirred to obtain a polyethersulfone solution; 40 mL of concentrated nitric acid and 20 mL of concentrated sulfuric acid were added to the polyethersulfone solution, and the mixture was stirred at 200°C for 22 h to obtain a reaction product; the reaction product was repeatedly washed with double distilled water and vacuum dried for 12 h to constant weight to obtain nitrated polyethersulfone, which was recorded as PES-NO2; the preparation reaction route is shown in Reaction Formula 1:

[0066]

[0067] Reaction formula 1.

[0068] 1.2) Preparation of amino polyethersulfone: Dissolve 3g of nitrated polyethersulfone in 50mL of ethanol to obtain a nitrated polyethersulfone solution; add 20g of tin chloride and 20g of concentrated hydrochloric acid to the nitrated polyethersulfone solution, stir well, and heat at 65°C for 6h to obtain a reaction product; repeatedly wash the reaction product with double distilled water, vacuum dry for 12h to constant weight, and obtain 2.8g of amino polyethersulfone, recorded as PES-NH2. The yield of PES-NH2 is 94%, and the preparation reaction route is shown in Reaction Formula 2:

[0069]

[0070] Reaction formula 2.

[0071] The H NMR spectrum of amino polyethersulfone is as follows Figure 1 As shown, the data of nuclear magnetic hydrogen spectrum are as follows: 1 HNMR (400 MHz, CDCl3) δ7.26 (s, 2nH), 6.99 (d, 2nH), 6.81 (d, 2nH), indicating that the amino polyethersulfone was successfully synthesized in the present invention.

[0072] Step 2: Carboxyl pyridine is subjected to acyl chloride treatment to obtain acylated pyridine.

[0073] 2.1) Preparation of 4-carboxyl terpyridine: Dissolve 5 g of p-formylbenzoic acid in 150 mL of ethanol to obtain a mixed solution; add 100 mL of 2-acetylpyridine and 10 g of sodium hydroxide solution to the mixed solution, and stir at 80 ° C for 16 hours under a nitrogen atmosphere to obtain a 4-carboxyl terpyridine precursor; then add 200 mL of ammonia water to the 4-carboxyl terpyridine precursor, reflux for 20 hours under a nitrogen atmosphere, cool to room temperature, filter, take the solid, reflux with ethanol 2 to 3 times, filter, and vacuum dry at 50 ° C for 24 hours to obtain 4.2 g of white solid, which is 4-carboxyl terpyridine. The yield of 4-carboxyl terpyridine is 84%, and the preparation reaction route is shown in Reaction Formula 3:

[0074]

[0075] Reaction formula 3.

[0076] The H NMR spectrum of 4-carboxyl terpyridine is as follows Figure 2 As shown, the data of nuclear magnetic hydrogen spectrum are as follows: 1 HNMR (400MHz,CDCl3)δ13.24(s,1H),8.78(d,4H),8.76(s,2H),8.69(d,2H),8.16(d,2H),8.07(d,2H),8.05(t,2H),7.55(t,2H), indicating that 4-carboxyl terpyridine was successfully synthesized by the present invention.

[0077] 2.2) Preparation of acylated pyridine: Set up a vacuum, anhydrous reaction system, fill with nitrogen, dissolve 2g of 4-carboxyl terpyridine in 20mL of dichlorothionyl, stir thoroughly for 1h to obtain a 4-carboxyl terpyridine solution; add 1mL of anhydrous N,N-dimethylformamide to the 4-carboxyl terpyridine solution, heat at 120°C for 4h to obtain a reaction product, repeatedly wash the reaction product with double distilled water, and vacuum dry to constant weight to obtain 1.64g of a white solid, which is acylated pyridine. The yield of acylated pyridine is 82%, and the preparation reaction route is shown in Reaction Formula 4:

[0078]

[0079] Reaction formula 4.

[0080] The H NMR spectrum of acylated pyridine is as follows Figure 3 As shown, the data of nuclear magnetic hydrogen spectrum are as follows: 1HNMR (400MHz, CDCl3)δ9.25(d,4H),9.11(s,2H),9.06(d,2H),8.63(t,2H),8.31(d,2H),8.17(d,2H),8.07(t,2H), indicating that the present invention successfully synthesized acylated pyridine.

[0081] Step 3, preparation of pyridine-polyethersulfone organic polymer: 2g of the amino polyethersulfone obtained in step 1 and 500mg of acylated terpyridine are dissolved in 100mL of dichloromethane to obtain a mixed solution; 1g of EDC is added to the mixed solution, and the mixture is stirred at room temperature for 16h under a nitrogen atmosphere to obtain a reaction product; the precipitate is extracted with ether, and the precipitate is repeatedly washed with double distilled water to obtain 1.86g of a white solid, which is a pyridine-polyethersulfone organic polymer, recorded as PES-Tpy. The yield of the pyridine-polyethersulfone organic polymer is 93%, and the preparation reaction route is shown in Reaction Formula 5:

[0082]

[0083] Reaction formula 5.

[0084] The H NMR spectrum of pyridine-polyethersulfone organic polymer is as follows Figure 4 As shown, the data of nuclear magnetic hydrogen spectrum are as follows: 1 HNMR (400MHz, CDCl3)δ8.84(s,2H),8.79(d,4H),8.72(d,2H),8.31(d,2H),8.25(d,2H),8.07(t,2H),7.56(t,2H),7.26(s,2nH),6.99(d,2nH),6.81(d,2nH), indicating that the present invention successfully synthesized the pyridine-polyethersulfone organic polymer.

[0085] Example 2

[0086] This embodiment provides a method for preparing a pyridine-polyethersulfone organic polymer.

[0087] 1 g of amino polyethersulfone and 300 mg of acylated monobipyridine were dissolved in 50 mL of dichloromethane solvent to obtain a transparent colorless solution; 0.5 g of EDC was added to the transparent colorless solution, and the mixture was stirred and reacted at room temperature for 16 hours under a nitrogen atmosphere to obtain a reaction product; the precipitate in the reaction product was extracted with ether, and the precipitate was repeatedly washed with double distilled water to obtain 0.75 g of a white solid, which was a pyridine-polyethersulfone organic polymer.

[0088] The difference between this embodiment and embodiment 1 is:

[0089] The acylated pyridine used in this embodiment is acylated monopyridine.

[0090] Example 3

[0091] This embodiment provides a method for preparing a pyridine-polyethersulfone organic polymer.

[0092] 1.5 g of amino polyethersulfone and 600 mg of acylated bipyridine were dissolved in 100 mL of dichloromethane solvent to obtain a transparent red solution; 1 g of EDC was added to the transparent red solution, and the mixture was stirred and reacted at room temperature for 16 h under a nitrogen atmosphere to obtain a reaction product; the precipitate in the reaction product was extracted with ether, and the precipitate was repeatedly washed with double distilled water to obtain 1.05 g of a brown solid, which was a pyridine-polyethersulfone organic polymer.

[0093] The difference between this embodiment and embodiment 1 is:

[0094] The acylated pyridine used in this embodiment is acylated bispyridine.

[0095] Experimental testing

[0096] Examples 1 to 3 of the present invention are all prepared under a simulated blood environment to detect Cd² + Ions and Hg² + The pyridine-polyethersulfone organic polymer has a high adsorption capacity for ions. The pyridine-polyethersulfone organic polymer prepared in Example 1 is used as an example for research. The specific research method and results are as follows:

[0097] 1. MRI test

[0098] The aminated polyethersulfone core, 4-carboxyl terpyridine, acylated pyridine and pyridine-polyethersulfone organic polymer prepared in Example 1 were subjected to nuclear magnetic resonance testing. The results are as follows: Figure 1~Figure 4 shown.

[0099] 2. Infrared test

[0100] The aminated polyethersulfone and pyridine-polyethersulfone organic polymers prepared in Example 1 were subjected to infrared spectroscopy testing. The results are as follows: Figure 5 shown.

[0101] Figure 5 ] are infrared spectra of polyethersulfone under different chemical modifications; wherein, PES is polyethersulfone; PES-NO2 is the nitroated polyethersulfone prepared in Example 1; PES-NH2 is the amino polyethersulfone prepared in Example 1; and PES-Tpy is the pyridine-ethersulfone organic polymer prepared in Example 1. Figure 5 The infrared spectrum of PES in the medium mainly shows the characteristic absorption peaks of the basic skeleton of PES, but there is no obvious absorption band of functional groups. Compared with the infrared spectrum of PES, the absorption band of the functional group at 1590cm -1 and 1530cm -1Characteristic absorption peaks appeared, which were the symmetric and asymmetric stretching vibration peaks of the nitro group, indicating that the nitro group was introduced into PES. -1 A new absorption peak appeared at 1621cm, which may be related to the vibration of the amino group, indicating the formation of the amino group. -1 and 1430cm -1 Characteristic absorption peaks appeared at , which are the vibrations of the C=N or C=C skeleton of pyridine, indicating that pyridine groups were introduced into PES-NH2. These infrared spectra clearly show the influence of different chemical modifications on the structure of PES. The chemical structure of amino polyethersulfone was changed by introducing nitro, amino and pyridine groups.

[0102] 3. Surface morphology test

[0103] The pyridine-polyethersulfone organic polymer prepared in Example 1 was fixed with a conductive adhesive, and the surface morphology of the pyridine-polyethersulfone organic polymer was observed by scanning electron microscopy. The results are as follows: Figure 6 shown.

[0104] Figure 6 The surface morphology of the pyridine-polyethersulfone organic polymer prepared in Example 1 is shown in Figure 1; (a) is a surface morphology at 200 μm, and (b) is a surface morphology at 5 μm. Figure 6 It can be seen that the surface of the pyridine-polyethersulfone organic polymer has an obvious pore or network structure. The network or fibrous structure provides a larger specific surface area, which makes the pyridine-polyethersulfone organic polymer have good adsorption performance and interfacial reaction.

[0105] 4. Adsorption test

[0106] Formulating Cd² + and Hg² + The ion concentration is 5×10 -6 mol / L of the test solution, 4 portions of the test solution were measured; the pH of the 4 portions of the test solution was adjusted to 1, 3, 5 and 7 respectively to obtain a test solution with a pH of 1, a test solution with a pH of 3, a test solution with a pH of 5 and a test solution with a pH of 7; 4 portions of 0.5 g of the pyridine-polyethersulfone organic polymer prepared in Example 1 were weighed and placed in the above test solutions with pH values ​​of 1, 3, 5 and 7 respectively. The effect of the pyridine-polyethersulfone organic polymer on the Cd² in the test solution under different pH conditions was determined. + and Hg² + The concentration change after ion adsorption is calculated to determine the effect of pyridine-polyethersulfone organic polymer on Cd2 in the test solution. + and Hg² + The amount of ion adsorption.

[0107] The present invention tests the adsorption of heavy metal ions in blood by pyridine-polyethersulfone organic polymer by simulating the pH environment in blood, and the pH value in blood is maintained at 7.35-7.45. Figure 7 It can be seen that Cd² + The adsorption of ions increases significantly with the increase of pH value. At pH = 1, the adsorption is low, while at pH = 7, the maximum adsorption is close to 100μg / g. + The adsorption of ions also increases with the increase of pH value. The adsorption is almost zero at pH = 1, and reaches the maximum adsorption at pH = 7. + Ions and Hg² + The adsorption capacity of ions reached 95% of that of the pyridine-polyethersulfone organic polymer prepared in Example 1; the pyridine-polyethersulfone organic polymer prepared in Example 3 had a high adsorption capacity for Cd2 + Ions and Hg² + The adsorption amount of ions reached 96% of that of the pyridine-polyethersulfone organic polymer prepared in Example 1. This shows that the pyridine-polyethersulfone organic polymer prepared in the present invention has a good adsorption capacity for Cd2 + Ions and Hg² + The ions have high adsorption capacity, achieving the effect of adsorbing and removing heavy metal ions in the blood.

[0108] 5. Stability test

[0109] Weigh 0.5g of the pyridine-polyethersulfone organic polymer prepared in Example 1, and soak one portion in a solution containing Hg² + and Cd² + ion solution for 4 hours, Hg² + and Cd² + Ion adsorption was performed to obtain the adsorbed pyridine-polyethersulfone organic polymer; one portion was used as a reference; the control pyridine-polyethersulfone organic polymer and the adsorbed pyridine-polyethersulfone organic polymer were immersed in a saturated sodium chloride solution for sodium ion and chloride ion exchange for 2 hours to obtain the ion-exchanged pyridine-polyethersulfone organic polymer. The XPS test of the ion-exchanged pyridine-polyethersulfone organic polymer was performed. The results are as follows: Figure 8 shown.

[0110] from Figure 8 It can be seen that without Hg² + and Cd² + After the ion-adsorbed pyridine-polyethersulfone organic polymer directly exchanges with the ions in the sodium chloride solution, the main elements contained in its XPS spectrum are N and S. + and Cd²+ After the ion-adsorbed pyridine-polyethersulfone organic polymer exchanges with the ions in the sodium chloride solution, the main elements contained in its XPS spectrum are still N and S. Compared with the pyridine-polyethersulfone organic polymer that directly exchanges with the ions in the sodium chloride solution, + and Cd² + The main elements contained in the pyridine-polyethersulfone organic polymer that adsorbs mercury ions and cadmium ions and then exchanges with the ions in the sodium chloride solution are basically unchanged. This shows that the pyridine-polyethersulfone organic polymer that adsorbs mercury ions and cadmium ions does not exchange with the ions in the sodium chloride solution. In other words, the pyridine-polyethersulfone organic polymer modified by pyridine has a strong complexing ability for mercury ions and cadmium ions; at the same time, the modified pyridine-polyethersulfone organic polymer is not easily disturbed by external factors and dissociated. The pyridine-polyethersulfone organic polymer adsorption material prepared by the present invention can react with mercury ions and cadmium ions to form a coordination structure due to the presence of conjugated pyridine groups, thereby achieving the effect of selective adsorption of heavy metal ions; at the same time, the hyperconjugated system formed by the coupling structure of pyridine and benzene ring improves the structural stability of the pyridine-polyethersulfone organic polymer molecules.

[0111] Obviously, those skilled in the art can make various changes and modifications to the present invention without departing from the spirit and scope of the present invention. If these modifications and variations of the present invention fall within the scope of the equivalent technology of the present invention, the present invention is also intended to include these modifications and variations.

Claims

1. A pyridine-polyethersulfone organic polymer, characterized in that: The pyridine-polyethersulfone organic polymer has a structure as shown in Formula 1: In Formula 1, R is a pyridine group, and n is an integer of 30 to 100; The pyridine-polyethersulfone organic polymer is prepared by the following steps: Amination treatment is performed on the polyethersulfone to obtain the amination polyethersulfone; Carboxyl pyridine is subjected to acyl chloride treatment to obtain acylated pyridine; Under a protective atmosphere, the aminated polyethersulfone and the acylated pyridine are dissolved in a solvent, and a substitution reaction is carried out under the action of a dehydrating agent, so that the acyl chloride group on the acylated pyridine is grafted onto the amino group of the aminated polyethersulfone to obtain a pyridine-polyethersulfone organic polymer; The acylated pyridine is one of acylated monopyridine, acylated bispyridine and acylated terpyridine; the acylated monopyridine has a structure as shown in Formula 5, the acylated bispyridine has a structure as shown in Formula 6, and the acylated terpyridine has a structure as shown in Formula 7:

2. A method for preparing the pyridine-polyethersulfone organic polymer according to claim 1, characterized in that: The following steps are involved: Amination treatment is performed on the polyethersulfone to obtain the amination polyethersulfone; Carboxyl pyridine is subjected to acyl chloride treatment to obtain acylated pyridine; Under a protective atmosphere, the aminated polyethersulfone and the acylated pyridine are dissolved in a solvent, and a substitution reaction is carried out under the action of a dehydrating agent, so that the acyl chloride group on the acylated pyridine is grafted onto the amino group of the aminated polyethersulfone to obtain a pyridine-polyethersulfone organic polymer.

3. The method for preparing the pyridine-polyethersulfone organic polymer according to claim 2, characterized in that: The mass ratio of the amino polyethersulfone to the acylated pyridine is 1-2:0.3-0.

6.

4. The method for preparing the pyridine-polyethersulfone organic polymer according to claim 2, characterized in that: The mass ratio of the amino polyethersulfone to the dehydrating agent is 1-2:0.5-1.

5. The method for preparing the pyridine-polyethersulfone organic polymer according to claim 2, characterized in that: The substitution reaction time is 14 h to 16 h.

6. The method for preparing the pyridine-polyethersulfone organic polymer according to claim 2, characterized in that: The amino polyethersulfone has a structure as shown in Formula 3: In Formula 3, n is an integer of 30 to 100.

7. The method for preparing the pyridine-polyethersulfone organic polymer according to claim 4, characterized in that: The dehydrating agent is 1-(3-dimethylpropyl)-3-ethylcarbodiimide hydrochloride.

8. Use of the pyridine-polyethersulfone organic polymer according to claim 1 in preparing a blood heavy metal ion adsorption material.

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