Two-dimensional polymer brush with a two-dimensional porous organic polymer based on γ-cyclodextrin as the main chain
By using γ-cyclodextrin two-dimensional porous organic polymer as the main chain, a high-density modified and biocompatible two-dimensional polymer brush was prepared, which solved the toxicity problem of inorganic two-dimensional materials and the problem of limited modificationability of organic two-dimensional materials, and achieved widespread application in the field of biomedicine.
Patent Information
- Application Number
- CN202510209495.7
- Authority / Receiving Office
- CN · China
- Patent Type
- Patents(China)
- Current Assignee / Owner
- Filing Date
- 2025-02-25
- Publication Date
- 2025-05-30
- Estimated Expiration
- 2045-02-25
AI Technical Summary
In the prior art, the long-term latent toxicity of inorganic two-dimensional materials in biological bodies and the limited modificationability of organic two-dimensional materials is not uniformly and high-density modification, which limits its application in biomedicine, biosensing and bioimaging.
A two-dimensional porous organic polymer of γ-cyclodextrin was used as the main chain, and a two-dimensional polymer brush with high modification density and good biocompatible was prepared through surface functionalization and polymerization.
It realizes high-density modification of two-dimensional polymer brushes, enhances its contact ability with biological tissues, shows good antibacterial effects and protein adsorption effects, and has a wide range of application value for biomedical and medical coatings.
Smart Images

Figure CN119684524B_ABST
Abstract
Description
Technical Field
[0001] The present invention belongs to the technical field of the preparation of polysaccharide polymer materials, and specifically relates to a two-dimensional polymer brush with a γ-cyclodextrin two-dimensional porous organic polymer as the main chain. Background Art
[0002] Modifying the surface of two-dimensional materials with polymer chains through covalent or non-covalent bonds has become an effective method to change their chemical and physical properties. At present, the substrates mainly studied for forming polymer brushes on the surface of two-dimensional materials are inorganic two-dimensional materials (such as graphene, hexagonal boron nitride, and antimonene, etc.). However, the long-term potential toxicity of inorganic two-dimensional materials in the body limits their applications in biomedicine, biosensing, and bioimaging. For the modification of organic two-dimensional materials (such as COF polymer nanosheets and two-dimensional nanomaterials composed of sequences derived from DNA / RNA, proteins, and peptoids), it is mainly small molecules, coordinated metal atoms, nanoparticles, macrocyclic molecules, etc. There are limited studies on the modification with polymer chains. Therefore, how to rationally design the building units and polymerize them to obtain organic two-dimensional polymer materials that can graft polymer chains is still a challenge.
[0003] The covalent bonding of one-dimensional brush-like polymers often involves various controlled living radical polymerization processes, such as reversible addition-fragmentation chain transfer (RAFT) polymerization, atom transfer radical polymerization (ATRP), anionic polymerization, ring-opening metathesis polymerization (ROMP), and cationic polymerization. Therefore, it becomes feasible to graft long polymer chains onto different carriers. Compared with macroscopic gels, microgels have obvious advantages in interacting with biomolecules, cells, and soft tissues due to their high surface area to volume ratio and injectability. Modifying the surface of microgels with grafted polymer chains and studying their interfacial properties, such as hydration, adhesion, and friction, has great guiding significance for applications in antibacterial, drug carriers, biomedicine, and other fields. Two-dimensional materials have a larger surface area to volume ratio than spherical particle microgels. Therefore, synthesizing two-dimensional brush-like polymers to study their interfacial properties and developing subsequent applications has great value. Summary of the Invention
[0004] The purpose of the present invention is to address the problems existing in the above-mentioned prior art (such as the long-term latent toxicity of inorganic two-dimensional materials in the body, and the limited modifiability of organic two-dimensional materials, which cannot be uniformly and highly densely modified, etc.), and provide a preparation method of a two-dimensional polymer brush with a γ-cyclodextrin two-dimensional porous organic polymer as the main chain, making it have the characteristics of high modification density, good biocompatibility, and being able to fully contact with biological tissues, so that it can be applied to fields such as biomedicine and medical coatings.
[0005] In order to solve the technical problems, the present invention adopts the following technical solutions:
[0006] Preparation method of two-dimensional polymer brush with γ-cyclodextrin two-dimensional porous organic polymer as main chain, characterized in that: using γ-cyclodextrin two-dimensional porous organic polymer as raw material, through surface functionalization reaction, γ-cyclodextrin two-dimensional porous organic polymer modified with initiating groups is obtained, and then polymerized with ionic monomers to obtain two-dimensional polymer brush with γ-cyclodextrin two-dimensional porous organic polymer as main chain. Specifically, it includes the following steps:
[0007] Step 1: Using at least one of acetone, chloroform, toluene, acetonitrile and dimethyl sulfoxide and a mixed solution of dichloromethane and N,N-dimethylformamide as reaction solvent, adding γ-cyclodextrin two-dimensional porous organic polymer, molecule containing initiating group and first catalyst, after ultrasonic dispersion and uniform mixing, carry out reaction, the obtained product is centrifuged, washed and freeze-dried to obtain γ-cyclodextrin two-dimensional porous organic polymer modified with initiating groups;
[0008] Step 2: Using at least one of ethanol, acetonitrile, N,N-dimethylformamide and dimethyl sulfoxide and a mixed solution of water and methanol as reaction solvent, adding γ-cyclodextrin two-dimensional porous organic polymer modified with initiating groups obtained in Step 1, and adding ionic monomer, second catalyst and third catalyst, after ultrasonic dispersion and uniform mixing, carry out polymerization reaction, the obtained product is centrifuged, washed and freeze-dried to obtain two-dimensional polymer brush with γ-cyclodextrin two-dimensional porous organic polymer as main chain.
[0009] Furthermore, in Step 1, the molecule containing initiating group is at least one of dopamine, 4-bromostyrene, succinic anhydride, acetic anhydride, 2-bromoisobutyryl bromide, acryloyl chloride and 2-chloroisobutyryl chloride, and the molecule containing initiating group and the γ-cyclodextrin two-dimensional porous organic polymer are fed in a mass ratio of 1~40:1.
[0010] Furthermore, the ionic monomer is at least one of anionic monomer (acrylic acid, methacrylic acid, 2-acrylamido-2-methylpropanesulfonic acid, sodium styrenesulfonate), cationic monomer (methacryloyloxyethyl trimethylammonium chloride, acryloyloxyethyl trimethylammonium chloride) and zwitterionic monomer (2-methacryloyloxyethyl phosphorylcholine, 3-[N,N-dimethyl-[2-(2-methylprop-2-enoyloxy)ethyl]ammonium] propane-1-sulfonate inner salt); the ionic monomer and the γ-cyclodextrin two-dimensional porous organic polymer modified with initiating groups are fed in a mass ratio of 1~100:1.
[0011] Furthermore, in Step 1, the reaction temperature of the molecule containing initiating group and the γ-cyclodextrin two-dimensional porous organic polymer is -10~50°C, and the reaction time is 0.5~5 days.
[0012] Further, the polymerization reaction temperature of the ionic monomer and the γ-cyclodextrin two-dimensional porous organic polymer with a modified initiating group is 30-90 °C, and the reaction time is 0.5-7 days.
[0013] Further: in step 1, the first catalyst is at least one of triethylamine and 4-dimethylaminopyridine, and the mass ratio of the first catalyst to the γ-cyclodextrin two-dimensional porous organic polymer is 0.01-1:1; in step 2, the second catalyst is at least one of ferrous chloride, ferric chloride, cuprous chloride, copper chloride, cuprous bromide, and copper bromide, and the mass ratio of the second catalyst to the γ-cyclodextrin two-dimensional porous organic polymer with a modified initiating group is 0.01-1:1; the third catalyst is at least one of tris(2-dimethylaminoethyl)amine, 2,2'-bipyridine, and 4,4'-bipyridine, and the mass ratio of the third catalyst to the γ-cyclodextrin two-dimensional porous organic polymer with a modified initiating group is 0.01-1:1.
[0014] Further: in step 1, dichloromethane and N,N-dimethylformamide respectively account for 20%-80% and 20%-60% of the total volume of the reaction solvent; in step 2, water and methanol respectively account for 20%-80% and 20%-70% of the total volume of the reaction solvent.
[0015] In the present invention, the γ-cyclodextrin two-dimensional porous organic polymer is used as a sheet-shaped main chain, and surface functionalization reactions can be carried out on both the upper and lower surfaces thereof, so that initiating active sites are formed on both the upper and lower surfaces of the main chain. Then, through a polymerization reaction, a large number of polymer long chains are formed at the initiating active sites, and a two-dimensional polymer brush is obtained.
[0016] The present invention further provides the following several applications of the two-dimensional polymer brush with the γ-cyclodextrin two-dimensional porous organic polymer as the main chain:
[0017] Application 1: The two-dimensional polymer brush formed by polymerizing a cationic monomer can be used for antibacterial.
[0018] Application 2: The two-dimensional polymer brush formed by polymerizing an anionic monomer, a cationic monomer, or an amphoteric ion monomer can be used for protein adsorption.
[0019] Compared with the prior art, the beneficial effects of the present invention are reflected in:
[0020] 1. Compared with inorganic two-dimensional main chains such as graphene, the two-dimensional polymer brush prepared in the present invention with the γ-cyclodextrin two-dimensional porous organic polymer as the main chain uses a sheet-shaped main chain that is a cyclodextrin polymer with high biocompatibility and a two-dimensional morphological structure, which can effectively avoid its long-term latent toxicity in the organism.
[0021] 2. Compared with organic two-dimensional nanomaterials such as COF, the γ-cyclodextrin two-dimensional porous organic polymer used in the present invention has a high degree of modifiability. A large number of polymer chains can be grafted onto its surface at a high density, making full use of the large surface area of the two-dimensional material to fully contact with biological tissues, cells, etc., showing good antibacterial effects and protein adsorption effects, which fully proves its application value in the fields of biomedicine and medical coatings.
[0022] 3. The preparation method of the present invention has the advantages of simple steps and low cost. The prepared two-dimensional polymer brush has the advantages of good dispersibility, good uniformity, customizable hydrophilicity and hydrophobicity, and good biocompatibility. BRIEF DESCRIPTION OF THE DRAWINGS
[0023] Figure 1 Scanning electron microscope image ((a) in Figure 1 )), atomic force microscope image ((b) in Figure 1 )), and thickness curve ((c) in Figure 1 ) of 2D-CD-POPs-In prepared in Example 1;
[0024] Figure 2 Infrared spectra of 2D-CD-POPs and 2D-CD-POPs-In in Example 1;
[0025] Figure 3 Scanning electron microscope image ((a) in Figure 3 ), atomic force microscope image ((b) in Figure 3 ), and thickness curve ((c) in Figure 3 ) of 2D-CD-POPs-PSSNa prepared in Example 1;
[0026] Figure 4 Scanning electron microscope image ((a) in Figure 4 ), atomic force microscope image ((b) in Figure 4 ), and thickness curve ((c) in Figure 4 ) of 2D-CD-POPs-PDMC prepared in Example 2;
[0027] Figure 5 Scanning electron microscope image ((a) in Figure 5 ), atomic force microscope image ((b) in Figure 5 ), and thickness curve ((c) in Figure 5 ) of 2D-CD-POPs-PSBMA prepared in Example 3;
[0028] Figure 6 Infrared spectra of the two-dimensional polymer brushes prepared in Examples 1, 2, and 3;
[0029] Figure 7Zeta potential diagrams of the two-dimensional polymer brushes prepared in Examples 1, 2, and 3, where (a), (b), and (c) correspond to samples 2D-CD-POPs-PSSNa, 2D-CD-POPs-PDMC, and 2D-CD-POPs-PSBMA, respectively;
[0030] Figure 8 Water contact angle test diagrams of the two-dimensional polymer brushes prepared in Examples 1, 2, and 3, where (a), (b), and (c) correspond to samples 2D-CD-POPs-PSSNa, 2D-CD-POPs-PDMC, and 2D-CD-POPs-PSBMA, respectively;
[0031] Figure 9 In (a) and (b) are the coating results of 2D-CD-POPs-PDMC and sterile water in Example 4, Figure 9 In (c) are the colony counting results;
[0032] Figure 10 Protein adsorption amount comparison diagrams of the two-dimensional polymer brushes in Example 5. Detailed implementation manners
[0033] The present invention will be further described below in conjunction with the accompanying drawings and examples.
[0034] I. Preparation of two-dimensional polymer brushes with γ-cyclodextrin two-dimensional porous organic polymer as the main chain
[0035] The γ-cyclodextrin two-dimensional porous organic polymer (2D-CD-POPs) used in the following examples was prepared according to the process method in Example 3 of the specification of Patent CN116284507 A, with a size of 10 - 20 μm and a thickness of 20 nm.
[0036] Example 1
[0037] This example prepares a two-dimensional polymer brush with γ-cyclodextrin two-dimensional porous organic polymer as the main chain according to the following steps:
[0038] Step 1: Disperse 0.1 g of 2D-CD-POPs in 10 mL of reaction solvent (prepared by mixing acetone, dimethyl sulfoxide, dichloromethane, and N,N-dimethylformamide in a volume ratio of 1:1:1:1), add 0.5 g of 2-bromoisobutyryl bromide, 0.3 g of dopamine, and 0.05 g of triethylamine. After ultrasonic dispersion, react at 30 °C for 24 h. The obtained product is centrifuged, washed successively with acetone and water, and freeze-dried to obtain γ-cyclodextrin two-dimensional porous organic polymer modified with initiating groups (denoted as 2D-CD-POPs-In) for standby. Its scanning electron microscope image, atomic force microscope image, and thickness curve are respectively as Figure 1As shown in (a), (b), and (c) therein, it can be seen from the figure that 2D-CD-POPs-In still maintains a two-dimensional sheet-like morphology, with a size of 10 - 20 μm and a thickness of 20 nm. The infrared spectra of 2D-CD-POPs and 2D-CD-POPs-In are as shown in Figure 2 , and it can be seen from the figure that there is an obvious strong peak near 1736 cm -1 , indicating that the initiator active sites containing carbonyl C=O are successfully modified.
[0039] Step 2: Disperse 0.1 g of 2D-CD-POPs-In in 10 mL of reaction solvent (prepared by mixing ethanol, dimethyl sulfoxide, water, and methanol in a volume ratio of 1:1:1:1), add 1.0 g of anionic monomer sodium styrene sulfonate, then add 0.1 g of copper chloride and 0.1 g of tris(2-dimethylaminoethyl)amine. After ultrasonic dispersion, react at 30 °C for 24 h. The obtained product is centrifuged, washed alternately with deionized water and absolute ethanol, and freeze-dried to obtain the target product, a two-dimensional polymer brush with a γ-cyclodextrin two-dimensional porous organic polymer as the main chain, denoted as 2D-CD-POPs-PSSNa. Its scanning electron microscopy image, atomic force microscopy image, and thickness curve are respectively as shown in Figure 3 in (a), (b), and (c). It can be seen from the figure that 2D-CD-POPs-PSSNa still maintains a two-dimensional sheet-like morphology, and there are rough protrusions, with a size of 10 - 20 μm and a thickness of 134 nm, and the thickness increases significantly.
[0040] Example 2
[0041] This example prepares a two-dimensional polymer brush with a γ-cyclodextrin two-dimensional porous organic polymer as the main chain according to the following steps:
[0042] Step 1: Disperse 0.1 g of 2D-CD-POPs in 10 mL of reaction solvent (prepared by mixing acetone, dimethyl sulfoxide, dichloromethane, and N,N-dimethylformamide in a volume ratio of 1:1:1:1), add 0.5 g of 2-bromoisobutyryl bromide, 0.3 g of dopamine, and 0.05 g of triethylamine. After ultrasonic dispersion, react at 30 °C for 24 h. The obtained product is centrifuged, washed successively with acetone and water, and freeze-dried to obtain the γ-cyclodextrin two-dimensional porous organic polymer modified with initiating groups (denoted as 2D-CD-POPs-In) for standby.
[0043] Step 2: Disperse 0.1 g of 2D-CD-POPs-In in 10 mL of reaction solvent (a mixture of ethanol, dimethyl sulfoxide, water, and methanol in a volume ratio of 1:1:1:1), add 1.0 g of cationic monomer methacryloyloxyethyltrimethylammonium chloride, then add 0.1 g of copper chloride and 0.1 g of tris(2-dimethylaminoethyl)amine. After ultrasonic dispersion until uniform, react at 30 °C for 24 h. The obtained product is centrifuged, washed alternately with deionized water and absolute ethanol, and freeze-dried to obtain the target product, a two-dimensional polymer brush with γ-cyclodextrin two-dimensional porous organic polymer as the main chain, denoted as 2D-CD-POPs-PDMC. Its scanning electron microscopy image, atomic force microscopy image, and thickness curve are respectively as shown in Figure 4 (a), (b), and (c) in it. It can be seen from the figure that 2D-CD-POPs-PDMC still maintains a two-dimensional sheet-like morphology, and rough protrusions appear, with a size of 10 - 20 μm and a thickness of 170 nm, and the thickness has increased significantly.
[0044] Example 3
[0045] This example prepares a two-dimensional polymer brush with γ-cyclodextrin two-dimensional porous organic polymer as the main chain according to the following steps:
[0046] Step 1: Disperse 0.1 g of 2D-CD-POPs in 10 mL of reaction solvent (a mixture of acetone, dimethyl sulfoxide, dichloromethane, and N,N-dimethylformamide in a volume ratio of 1:1:1:1), add 0.5 g of 2-bromoisobutyryl bromide, 0.3 g of dopamine, and 0.05 g of triethylamine. After ultrasonic dispersion until uniform, react at 30 °C for 24 h. The obtained product is centrifuged, washed successively with acetone and water, and freeze-dried to obtain γ-cyclodextrin two-dimensional porous organic polymer modified with an initiating group (denoted as 2D-CD-POPs-In) for standby.
[0047] Step 2: Disperse 0.1 g of 2D-CD-POPs-In in 10 mL of reaction solvent (a mixture of ethanol, dimethyl sulfoxide, water, and methanol in a volume ratio of 1:1:1:1), add 1.0 g of zwitterionic monomer 3-[N,N-dimethyl-[2-(2-methylprop-2-enoyloxy)ethyl]ammonium] propane-1-sulfonate inner salt, then add 0.1 g of copper chloride and 0.1 g of tris(2-dimethylaminoethyl)amine. After ultrasonic dispersion until uniform, react at 30 °C for 24 h. The obtained product is centrifuged, washed alternately with deionized water and absolute ethanol, and freeze-dried to obtain the target product, a two-dimensional polymer brush with γ-cyclodextrin two-dimensional porous organic polymer as the main chain, denoted as 2D-CD-POPs-PSBMA. Its scanning electron microscopy image, atomic force microscopy image, and thickness curve are respectively as shown in Figure 5As shown in (a), (b), and (c) therein, it can be seen from the figure that 2D-CD-POPs-PDMC still maintains a two-dimensional flaky morphology, and rough protrusions appear, with a size of 10 - 20 μm and a thickness of 163 nm, and the thickness has increased significantly.
[0048] The infrared spectra of the two-dimensional polymer brushes prepared in Examples 1, 2, and 3 are as Figure 6 shown. By comparing the infrared spectra of the monomers in the literature, it can be seen that the two-dimensional polymer brushes such as 2D-CD-POPs-PSSNa, 2D-CD-POPs-PDMC, and 2D-CD-POPs-PSBMA have been successfully synthesized, proving that the synthesis method of the present invention has successfully grafted different long-chain polymers while maintaining the two-dimensional morphology.
[0049] The Zeta potential diagrams of the two-dimensional polymer brushes prepared in Examples 1, 2, and 3 are as Figure 7 shown in (a), (b), and (c) therein. It can be seen from the figure that the potentials of 2D-CD-POPs-PSSNa, 2D-CD-POPs-PDMC, and 2D-CD-POPs-PSBMA are -31.5 mV, +9.18 mV, and -2.05 mV, respectively.
[0050] The water contact angle test diagrams of the two-dimensional polymer brushes prepared in Examples 1, 2, and 3 are as Figure 8 shown in (a), (b), and (c) therein. It can be seen from the figure that the water contact angles of 2D-CD-POPs-PSSNa, 2D-CD-POPs-PDMC, and 2D-CD-POPs-PSBMA are 40°, 52°, and 24°, respectively, fully proving the change in hydrophilicity and hydrophobicity.
[0051] II. Applications of Two-Dimensional Polymer Brushes with γ-Cyclodextrin Two-Dimensional Porous Organic Polymer as the Main Chain
[0052] Example 4. Antibacterial Experiment against Escherichia coli
[0053] Adjust the concentration of Escherichia coli (CMCC(B)44102 strain) to 1×10 6 CFU mL -1 (OD 600 = 0.1) by the turbidimetric method. Dilute the sterile aqueous dispersion of 2D-CD-POPs-PDMC to 1 mg / mL, take 200 μL, add 20 μL of Escherichia coli solution and 200 μL of LB broth medium thereto. Use sterile water as the negative control, take 200 μL, add 20 μL of Escherichia coli solution and 200 μL of LB broth medium thereto. Incubate the two groups of samples at 37 °C for 24 hours, dilute and plate them on LB agar medium, and calculate the number of colonies.
[0054] In this embodiment, the results of coating plates with 2D-CD-POPs-PDMC and sterile water are respectively as shown in Figure 9 Figure (a) and (b) in Figure 9 , and the results of colony counting are as shown in Figure 9 Figure (c) in Figure 9 . It can be seen that the sample with 2D-CD-POPs-PDMC has 17×10 7 cells / cm 2 colonies, and the negative control has 123×10 7 cells / cm 2 colonies. Compared with the negative control, the number of colonies of 2D-CD-POPs-PDMC is reduced by 86%, and the colonies of the negative control cover the entire culture medium. This proves that 2D-CD-POPs-PDMC has excellent antibacterial effects. At the same time, after testing, 2D-CD-POPs has no antibacterial effect.
[0055] Example 5. Adsorption experiment on proteins
[0056] Add 20 mg of two-dimensional polymer brushes 2D-CD-POPs-PSSNa, 2D-CD-POPs-PDMC, and 2D-CD-POPs-PSBMA into 50 mL beakers respectively, and then add 20 mL of 1 mg / mL bovine hemoglobin solution (dissolved in PBS solutions with pH values of 4, 8, and 7) respectively. Place the beakers at 30 °C and stir magnetically (500 r / min) for 0.5 h. Take out 1 mL of the above solution, centrifuge to obtain the supernatant, and measure the absorbance at the maximum absorption wavelength of the protein with a UV-visible spectrophotometer to determine the protein concentration in the solution after adsorption, and calculate the adsorption amount. The results are as shown in Figure 10 . The adsorption amounts of 2D-CD-POPs-PSSNa, 2D-CD-POPs-PDMC, and 2D-CD-POPs-PSBMA for bovine hemoglobin are 0.17 mg / mg, 0.05 mg / mg, and 0.011 mg / mg respectively. At the same time, after testing, 2D-CD-POPs has no adsorption effect on bovine hemoglobin.
[0057] The above are only exemplary embodiments of the present invention and are not intended to limit the present invention. Any modifications, equivalent replacements, and improvements made within the spirit and principle of the present invention shall be included within the protection scope of the present invention.
Claims
1. A method for preparing a two-dimensional polymer brush with a γ-cyclodextrin two-dimensional porous organic polymer as the main chain, characterized in that: Using γ-cyclodextrin two-dimensional porous organic polymer as raw material, a surface functionalization reaction is performed to obtain a γ-cyclodextrin two-dimensional porous organic polymer modified with an initiating group, and then a polymerization reaction is performed with an ionic monomer to obtain a two-dimensional polymer brush with the γ-cyclodextrin two-dimensional porous organic polymer as the main chain, specifically comprising the following steps: Step 1, using a mixture of at least one of acetone, chloroform, toluene, acetonitrile and dimethyl sulfoxide and dichloromethane and N,N-dimethylformamide as a reaction solvent, adding a γ-cyclodextrin two-dimensional porous organic polymer, a molecule containing an initiating group and a first catalyst, and reacting after ultrasonic dispersion. The obtained product is centrifuged, washed and freeze-dried to obtain a γ-cyclodextrin two-dimensional porous organic polymer modified with an initiating group; wherein the molecule containing the initiating group is dopamine and 2-bromoisobutyryl bromide, and the molecule containing the initiating group and the γ-cyclodextrin two-dimensional porous organic polymer are fed in a mass ratio of 1 to 40:1; the first catalyst is at least one of triethylamine and 4-dimethylaminopyridine, and the mass ratio of the first catalyst to the γ-cyclodextrin two-dimensional porous organic polymer is 0.01 to 1:1; Step 2, using a mixture of at least one of ethanol, acetonitrile, N,N-dimethylformamide and dimethyl sulfoxide and water and methanol as a reaction solvent, adding the γ-cyclodextrin two-dimensional porous organic polymer modified with an initiating group obtained in step 1, and adding an ionic monomer, a second catalyst and a third catalyst, and conducting a polymerization reaction after ultrasonic dispersion. The obtained product is centrifuged, washed and freeze-dried to obtain a two-dimensional polymer brush with the γ-cyclodextrin two-dimensional porous organic polymer as the main chain; wherein the ionic monomer is at least one of acrylic acid, methacrylic acid, 2-acrylamide-2-methylpropane sulfonic acid, sodium styrene sulfonate, methacryloyloxyethyl trimethylammonium chloride, acryloyloxyethyl trimethylammonium chloride, 2-methacryloyloxyethyl phosphorylcholine and 3-[N,N-dimethyl-[2-(2-methylprop-2-enoyloxy)ethyl]ammonium]propane-1-sulfonic acid inner salt, and the ionic monomer and the γ-cyclodextrin two-dimensional porous organic polymer modified with an initiating group are fed in a mass ratio of 1 to 100:
1.
2. The method for preparing a two-dimensional polymer brush with a γ-cyclodextrin two-dimensional porous organic polymer as the main chain according to claim 1, characterized in that: In step 1, the reaction temperature of the molecule containing the initiating group and the γ-cyclodextrin two-dimensional porous organic polymer is -10 to 50° C., and the reaction time is 0.5 to 5 days.
3. The method for preparing a two-dimensional polymer brush with a γ-cyclodextrin two-dimensional porous organic polymer as the main chain according to claim 1, characterized in that: The polymerization reaction temperature of the ionic monomer and the gamma-cyclodextrin two-dimensional porous organic polymer with modified initiating groups is 30-90° C., and the reaction time is 0.5-7 days.
4. The method for preparing a two-dimensional polymer brush with a γ-cyclodextrin two-dimensional porous organic polymer as the main chain according to claim 1, characterized in that: In step 2, the second catalyst is at least one of ferrous chloride, ferric chloride, cuprous chloride, cupric chloride, cuprous bromide, and cupric bromide, and the mass ratio of the second catalyst to the modified initiating group γ-cyclodextrin two-dimensional porous organic polymer is 0.01~1:1; the third catalyst is at least one of tris(2-dimethylaminoethyl)amine, 2,2'-bipyridine and 4,4'-bipyridine, and the mass ratio of the third catalyst to the modified initiating group γ-cyclodextrin two-dimensional porous organic polymer is 0.01~1:
1.
5. The method for preparing a two-dimensional polymer brush with a γ-cyclodextrin two-dimensional porous organic polymer as the main chain according to claim 1, characterized in that: In step 1, dichloromethane and N,N-dimethylformamide account for 20% to 80% and 20% to 60% of the total volume of the reaction solvent, respectively; in step 2, water and methanol account for 20% to 80% and 20% to 70% of the total volume of the reaction solvent, respectively.
6. A two-dimensional polymer brush with γ-cyclodextrin two-dimensional porous organic polymer as the main chain, obtained by the preparation method according to any one of claims 1 to 5.
7. Use of the two-dimensional polymer brush with γ-cyclodextrin two-dimensional porous organic polymer as the main chain as claimed in claim 6 in the preparation of antibacterial agents or protein adsorbents.
Citation Information
Patent Citations
Antibacterial micro-nano gel and fiber with protein adsorption function and preparation methods of gel and fiber
CN110028614A