阅读说明：本技术 一种磁性可再生抗菌剂及其制备方法 (Magnetic renewable antibacterial agent and preparation method thereof ) 是由 *** 于 2020-06-17 设计创作，主要内容包括：本发明公开一种磁性可再生抗菌剂及其制备方法；通过可逆加成-断裂链转移反应将具有磁效应的Fe<Sub>3</Sub>O<Sub>4</Sub>接枝到氧化石墨烯负载有机抗菌剂的嵌段共聚物上,制备得到的磁性可再生抗菌剂,该磁性可再生抗菌剂克服了普通抗菌剂分散不均匀及易流失的缺点,解决抗菌剂流失后处理困难的问题,同时,将具有磁效应的无机纳米粒子接枝到有机抗菌剂上,不存在两者不相容的情况。(The invention discloses a magnetic reproducible antibacterial agent and a preparation method thereof; fe to have magnetic effect by reversible addition-fragmentation chain transfer reaction 3 O 4 The magnetic renewable antibacterial agent is grafted to the graphene oxide-loaded organic antibacterial agent block copolymer, and overcomes the defects that the common antibacterial agent is not uniformly dispersed and is easy to run offThe method solves the problem of difficult treatment after the loss of the antibacterial agent, and simultaneously, the inorganic nano particles with magnetic effect are grafted on the organic antibacterial agent, so that the situation of incompatibility of the inorganic nano particles and the organic antibacterial agent does not exist.)

1. A magnetic, regenerable antimicrobial agent, said magnetic regenerable antimicrobial agent having the structure of formula (I):

wherein n is 50-200, and m is 10-5000.

2. The method of preparing a magnetic regenerable antimicrobial agent of claim 1, comprising the steps of:

(1) dissolving 4-cyano-4- (thiobenzoyl) pentanoic acid and 1-hydroxybenzotriazole in dichloromethane, and adding aminated Fe dissolved in dichloromethane₃O₄Stirring the nano particles at room temperature for 30min, slowly dripping 1-ethyl- (3-dimethylaminopropyl) carbonyldiimine hydrochloride dissolved in dichloromethane into the mixed solution, and reacting at room temperature for 36h to obtain Fe₃O₄A surface reversible addition-fragmentation chain transfer agent;

(2) mixing the above Fe₃O₄Dissolving a surface reversible addition-fragmentation chain transfer agent and 4-vinylbenzaldehyde in dioxane, adding azodiisobutyronitrile, and reacting at 70-80 ℃ for 3-6 hours under the conditions of no water, no oxygen and nitrogen protection to obtain Fe₃O₄Grafted poly 4-vinylbenzaldehyde hybrid;

(3) mixing the above Fe₃O₄The graft poly-4-vinylbenzaldehyde heterozygote and 4- (vinyl phenyl) methanol are dissolved in dioxane, azodiisobutyronitrile is added, and the mixture reacts for 2 to 6 hours at 70 to 80 ℃ under the conditions of no water, no oxygen and nitrogen protection to obtain Fe₃O₄Grafting 4-vinylbenzaldehyde antibacterial block copolymer;

(4) under acidic condition, toluene is used as solvent, Fe₃O₄Grafting 4-vinylbenzaldehyde antibacterial block copolymer and 3-Aminopropyltriethoxysilane (APTES) as raw materials, and reacting at 130 ℃ for 10 hours to prepare a silane coupling agent modified magnetic antibacterial agent;

(5)N₂under protection, ethanol is used as a solvent, a silane coupling agent modified magnetic antibacterial agent and graphene oxide are used as raw materials, and the reaction is carried out for 10 hours at 80 ℃ to prepare the magnetic renewable antibacterial agent.

3. The method of claim 2, wherein the step (1) of aminating Fe is performed by₃O₄The molar ratio of the nanoparticles to 1-hydroxybenzotriazole, 4-cyano-4- (thiobenzoyl) pentanoic acid, 1-ethyl- (3-dimethylaminopropyl) carbonyldiimine hydrochloride was 2:3:4: 8.

4. The method of claim 2, wherein the Fe in step (2) is₃O₄The molar ratio of the surface reversible addition-fragmentation chain transfer agent to the azobisisobutyronitrile and the 4-vinylbenzaldehyde is 1:5:300, and the molar concentration of the 4-vinylbenzaldehyde in the reaction system is 1 mol/L.

5. The method of claim 2, wherein the Fe in step (3) is₃O₄The molar ratio of the grafted poly-4-vinylbenzaldehyde heterozygote to azobisisobutyronitrile and 4- (vinylphenyl) methanol is 1:5:500, and the molar concentration of the 4- (vinylphenyl) methanol in the reaction system is 1 mol/L.

6. The method of claim 2, wherein the Fe in step (4) is₃O₄The molar ratio of the grafted 4-vinylbenzaldehyde antibacterial block copolymer to 3-Aminopropyltriethoxysilane (APTES) was 1: 1.

Technical Field

The invention belongs to the field of polymer chemical synthesis, and particularly relates to a magnetic renewable antibacterial agent and a preparation method thereof.

Background

The organic antibacterial agent not only has broad-spectrum and efficient sterilization capability, but also has wide source, low cost and simple processing technology. The antibacterial mechanism of the organic antibacterial agent is as follows: (1) inactivating microbial metabolic enzyme to influence metabolism of microorganism, thereby achieving the purpose of sterilization; (2) reacting with intracellular protease to destroy cell function; (3) blocking DNA synthesis and inhibiting microorganism propagation; (4) promote redox reaction and disturb cell growth; (5) inhibiting the amino acid from transforming into lipid.

The production of the natural selenium-enriched water usually needs the steps of water diversion, aeration, filtration, disinfection, encapsulation and the like, wherein the purpose of filtration is to remove impurities such as insoluble particles, colloidal particles, microorganisms and the like in the natural selenium-enriched water, so that the water quality is clear and transparent, clean and sanitary. In order to better remove the impurities, filtration is generally divided into two modes of rough filtration and fine filtration, wherein large particulate matters are removed through rough filtration, particles with small particles and microorganisms are removed through fine filtration, and fine filtration is further divided into micro filtration and ultra filtration so as to ensure that inorganic mineral ions in the natural selenium-enriched water are not influenced while most of the impurities are removed. CN109534564B discloses a natural selenium-enriched water filtration method, which is characterized in that a magnetic antibacterial agent with the particle size smaller than the pore size of a microfiltration membrane but larger than the pore size of an ultrafiltration membrane is added into water after rough filtration, so that the magnetic antibacterial agent can pass through the pore path of the microfiltration membrane and exist in the water after microfiltration filtration; the magnetic antibacterial agent is intercepted on the water inlet side of the membrane by the ultrafiltration membrane, and the magnetic antibacterial agent is obtained by backwashing and magnetic separation of the ultrafiltration membrane and is recycled for application in microfiltration. The method overcomes the problem that bacteria and viruses in natural selenium-enriched water breed polluted membranes and water quality on rough filtration, micro filtration and ultrafiltration membranes in the prior art, can realize antibiosis while filtering, prevents pollution of filtration membranes at all levels, and ensures long-term stability of water quality. But the magnetic antibacterial agent is prepared by physically mixing an antibacterial component Ag with a magnetic carrier Fe₂O₃Combined together, the antimicrobial component Ag and the carrier Fe₂O₃The chemical bond effect does not exist between the antibacterial agent and the antibacterial agent, the dispersion uniformity of the antibacterial agent is not easy to ensure, and in addition, the loss problem of the antibacterial component is difficult to avoid, and the long-term antibacterial performance of the product is directly influenced. Based on the above statement, the present invention proposes a magnetic renewable antimicrobial agent and a method for preparing the same.

Disclosure of Invention

In order to solve the defects of the prior art, the invention provides a magnetic reproducible antibacterial agent and a preparation method thereof. Fe to have magnetic effect by reversible addition-fragmentation chain transfer reaction₃O₄Grafting to graphene oxide SupportsThe block copolymer of the organic antibacterial agent overcomes the defects of uneven dispersion and easy loss of the common antibacterial agent; the problem of difficult treatment after the loss of the antibacterial agent is solved, and meanwhile, the inorganic nano particles with magnetic effect are grafted to the organic antibacterial agent, so that the situation of incompatibility of the inorganic nano particles and the organic antibacterial agent is avoided.

The invention aims to provide a magnetic renewable antibacterial agent.

Another object of the present invention is to provide a method for preparing the above-mentioned magnetic renewable antibacterial agent.

The above purpose of the invention is realized by the following technical scheme:

a magnetic regenerable antimicrobial agent of the formula (I):

wherein n is 50-200, and m is 10-5000.

The reaction process and the preparation method of the magnetic reproducible antibacterial agent are as follows:

1.Fe₃O₄preparation of a surface reversible addition-fragmentation chain transfer agent.

Dissolving 4-cyano-4- (thiobenzoyl) pentanoic acid and 1-hydroxybenzotriazole in dichloromethane, and adding aminated Fe dissolved in dichloromethane₃O₄Nanoparticles were stirred at room temperature for 30min, and 1-ethyl- (3-dimethylaminopropyl) carbonyldiimine hydrochloride (0.1608g, 0.8388mmol) dissolved in 10mL of dichloromethane was slowly added dropwise to the above mixed solution, and after reacting at room temperature for 36h, Fe was obtained₃O₄Surface reversible addition-fragmentation chain transfer agents.

2.Fe₃O₄Preparation of grafted poly-4-vinylbenzaldehyde hybrids.

Mixing the above Fe₃O₄Dissolving surface reversible addition-fragmentation chain transfer agent, 4-vinylbenzaldehyde in bisAdding azodiisobutyronitrile into the hexacyclo-oxygen, and reacting for 3-6 hours at 70-80 ℃ under the conditions of no water, no oxygen and nitrogen protection to obtain Fe₃O₄Grafted poly 4-vinylbenzaldehyde hybrids.

3.Fe₃O₄Preparing the grafted 4-vinyl benzaldehyde antibacterial block copolymer.

Mixing the above Fe₃O₄The graft poly-4-vinylbenzaldehyde heterozygote and 4- (vinyl phenyl) methanol are dissolved in dioxane, azodiisobutyronitrile is added, and the mixture reacts for 2 to 6 hours at 70 to 80 ℃ under the conditions of no water, no oxygen and nitrogen protection to obtain Fe₃O₄4-vinyl benzaldehyde antibacterial block copolymer is grafted.

4. Preparing the silane coupling agent modified magnetic antibacterial agent.

Under acidic condition, toluene is used as solvent, Fe₃O₄The grafted 4-vinyl benzaldehyde antibacterial block copolymer and 3-Aminopropyltriethoxysilane (APTES) are used as raw materials and react for 10 hours at 130 ℃ to prepare the silane coupling agent modified magnetic antibacterial agent.

5. Preparation of magnetic renewable antibacterial agent.

N₂Under protection, ethanol is used as a solvent, a silane coupling agent modified magnetic antibacterial agent and graphene oxide are used as raw materials, and the reaction is carried out for 10 hours at 80 ℃ to prepare the magnetic renewable antibacterial agent.

Compared with the prior art, the invention has the following advantages and beneficial effects:

(1) fe to have magnetic effect by reversible addition-fragmentation chain transfer reaction₃O₄Grafting the graphene oxide-loaded organic antibacterial agent block copolymer to prepare the magnetic renewable antibacterial agent.

(2) The prepared magnetic renewable antibacterial agent overcomes the defects of uneven dispersion and easy loss of a common antibacterial agent, solves the problem of difficult treatment after the antibacterial agent is lost, and simultaneously, the inorganic nano particles with magnetic effect are grafted on the organic antibacterial agent without the condition of incompatibility of the two.

Drawings

FIG. 1 is an infrared spectrum of a magnetic regenerable antimicrobial agent.

Detailed Description

The present invention will be described in further detail with reference to specific examples, which are not intended to limit the present invention in any manner. Reagents, methods and apparatus used in the present invention are conventional in the art unless otherwise indicated.