阅读说明：本技术 一种缓释型抗菌分子簇树脂及其制备方法和应用 (slow-release antibacterial molecular cluster resin and preparation method and application thereof ) 是由 肖凯军 张雨涵 银玉容 于 2019-07-30 设计创作，主要内容包括：本发明属于抗菌材料领域,公开了一种缓释型抗菌分子簇树脂及其制备方法和应用。将氨基聚苯乙烯微球与聚丙烯酸加入到乙醇溶液中,惰性气氛下搅拌回流反应,产物经洗涤、干燥,得到PS-PAA分子簇树脂；然后与硝酸银溶液混合,加入还原剂反应,将已经接枝在PS-PAA分子簇树脂上的银还原得纳米银,得到缓释型抗菌分子簇树脂。本发明通过分子簇树脂中树状活性基团与纳米银定向紧密结合,所得产物具有极好的抗菌性和缓释性,可应用于饮用水抗菌。(The invention belongs to the field of antibacterial materials, and discloses a slow-release antibacterial molecular cluster resin, and a preparation method and application thereof. Adding amino polystyrene microspheres and polyacrylic acid into an ethanol solution, stirring and refluxing the mixture under an inert atmosphere for reaction, and washing and drying a product to obtain PS-PAA molecular cluster resin; and then mixing with a silver nitrate solution, adding a reducing agent for reaction, and reducing the silver grafted on the PS-PAA molecular cluster resin to obtain nano silver to obtain the slow-release antibacterial molecular cluster resin. According to the invention, through the directional close combination of the dendritic active groups in the molecular cluster resin and the nano silver, the obtained product has excellent antibacterial property and slow release property, and can be applied to drinking water antibacterial.)

1. A preparation method of a slow-release antibacterial molecular cluster resin is characterized by comprising the following steps:

(1) Adding amino polystyrene microspheres and polyacrylic acid into an ethanol solution, stirring and refluxing the mixture under an inert atmosphere for reaction, and washing and drying a product to obtain PS-PAA molecular cluster resin;

(2) mixing the PS-PAA molecular cluster resin obtained in the step (1) with a silver nitrate solution, adding a reducing agent for reaction, and reducing the silver grafted on the PS-PAA molecular cluster resin to obtain nano silver, thereby obtaining the slow-release antibacterial molecular cluster resin.

2. The method for preparing a sustained-release antibacterial molecular cluster resin according to claim 1, characterized in that: the mass ratio of the amino polystyrene microspheres to the polyacrylic acid in the step (1) is 1 (1-4).

3. The method for preparing a sustained-release antibacterial molecular cluster resin according to claim 1, characterized in that: the reducing agent in the step (2) is sodium borohydride.

4. The method for preparing the slow-release antibacterial molecular cluster resin according to claim 1, wherein the amino polystyrene microspheres are prepared by the following method:

Adding the dried polystyrene microspheres into a mixed solution consisting of concentrated nitric acid and concentrated sulfuric acid, stirring for reaction to obtain nitro polystyrene microspheres, adding the dried product into a NaOH aqueous solution containing Na ₂ S ₂ O ₄, and reacting to obtain the amino polystyrene microspheres.

5. The method for preparing a sustained-release antibacterial molecular cluster resin according to claim 4, characterized in that: in the mixed solution composed of the concentrated nitric acid and the concentrated sulfuric acid, the concentrated nitric acid and the concentrated sulfuric acid are composed according to the volume ratio of 2: 3; the stirring reaction is carried out at the temperature of 40 ℃ and the speed of 400r/min for 2-3 h.

6. The method for preparing a sustained-release antibacterial molecular cluster resin according to claim 4, characterized in that: the reaction temperature in the NaOH aqueous solution is 75 ℃, and the reaction time is 4 h.

7. The method for preparing the slow-release antibacterial molecular cluster resin according to claim 4, wherein the polystyrene microspheres are prepared by the following method:

Adding monomer styrene, a dispersing agent and an initiator into an ethanol water solution, and stirring and reacting at the temperature of 65-70 ℃ to obtain the polystyrene microsphere.

8. the method for preparing a sustained-release antibacterial molecular cluster resin according to claim 7, characterized in that: the particle size of the polystyrene microsphere is 2-5 mu m.

9. A slow-release antibacterial molecular cluster resin is characterized in that: prepared by the method of any one of claims 1 to 8.

10. The use of a slow release antibacterial molecular cluster resin according to claim 9 for the antibacterial treatment of drinking water.

Technical Field

The invention belongs to the field of antibacterial materials, and particularly relates to a slow-release antibacterial molecular cluster resin, and a preparation method and application thereof.

Background

with the improvement of life of people, the requirement on drinking water is higher and higher. At present, drinking water for people is generally tap water or barreled water, and although the tap water and the barreled water are subjected to sterilization and disinfection treatment, bacteria can still grow if the early sterilization and disinfection are not thorough in the long-time transportation and filling processes, so that the health of a human body is harmed.

At present, the common drinking water sterilization and disinfection methods can be divided into physical methods and chemical methods. The physical method is mainly by ultraviolet irradiation, and the chemical method is classified into chlorine sterilization and ozone sterilization depending on the kind of sterilization. Among them, chlorine sterilization is the most important sterilization method for centralized water supply, and can be divided into free chlorine sterilization and combined chlorine sterilization according to different sterilization principles. The main chlorine-containing bactericides include liquid chlorine, monochloramine, dichloramine, chlorine dioxide, sodium hypochlorite and the like. Ozone sterilization is sterilization with strong oxidant ozone. However, the ultraviolet sterilization effect is general and not ideal enough, and sterilization can be performed only within a short time of opening, and long-term sterilization cannot be performed. Chlorine sterilization is the earliest adopted drinking water sterilization and disinfection mode, and has the advantages of mature and stable technology, strong sterilization capability, long duration, low cost and the like. At present, certain water supply plants in urban and rural areas in China all adopt a chlorine sterilization process to sterilize drinking water, but a large amount of residual chlorine in water usually exists by a chlorine sterilization method, so that secondary pollution is caused, and the water supply plants have bad smell. Many reports prove that organic halides such as chlorinated disinfection by-product chloroform and the like have different harmful effects, such as 767 organic pollutants measured in tap water by American health research institute, wherein 20 carcinogens, 26 suspicious carcinogens, 18 carcinogens or carcinogens and 48 Ames test mutagenic substances are confirmed, most of the substances are organic halides, and the research of many scholars in China also proves that the substances are toxic and harmful. The cost is high for the ozone sterilization and disinfection method. Therefore, research and development of a drinking water sterilizing material which can sterilize efficiently and does not cause secondary pollution are urgently needed.

Disclosure of Invention

Aiming at the defects and shortcomings of the prior art, the invention mainly aims to provide a preparation method of a slow-release antibacterial molecular cluster resin.

The invention also aims to provide the slow-release antibacterial molecular cluster resin prepared by the method.

The invention further aims to provide the application of the slow-release antibacterial molecular cluster resin in the drinking water antibiosis.

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

A preparation method of a slow-release antibacterial molecular cluster resin comprises the following steps:

(1) Adding amino polystyrene microspheres and polyacrylic acid into an ethanol solution, stirring and refluxing the mixture under an inert atmosphere for reaction, and washing and drying a product to obtain PS-PAA (polystyrene-polyacrylic acid) molecular cluster resin;

(2) Mixing the PS-PAA molecular cluster resin obtained in the step (1) with a silver nitrate solution, adding a reducing agent for reaction, and reducing the silver grafted on the PS-PAA molecular cluster resin to obtain nano silver, thereby obtaining the slow-release antibacterial molecular cluster resin.

Preferably, the mass ratio of the amino polystyrene microspheres to the polyacrylic acid in the step (1) is 1 (1-4).

preferably, the reducing agent in step (2) is sodium borohydride.

further, the amino polystyrene microsphere is prepared by the following method:

Adding the dried polystyrene microspheres into a mixed solution consisting of concentrated nitric acid and concentrated sulfuric acid, stirring for reaction to obtain nitro polystyrene microspheres, adding the dried product into a NaOH aqueous solution containing Na ₂ S ₂ O ₄, and reacting to obtain the amino polystyrene microspheres.

Preferably, in the mixed solution of the concentrated nitric acid and the concentrated sulfuric acid, the concentrated nitric acid and the concentrated sulfuric acid are mixed according to a volume ratio of 2: 3.

Preferably, the stirring reaction is carried out at 40 ℃ and a speed of 400r/min for 2-3 h.

Preferably, the temperature of the reaction in the NaOH aqueous solution is 75 ℃, and the reaction time is 4 h.

Further, the polystyrene microsphere is prepared by the following method:

Adding monomer styrene, a dispersing agent and an initiator into an ethanol water solution, and stirring and reacting at the temperature of 65-70 ℃ to obtain the polystyrene microsphere.

Preferably, the particle size of the polystyrene microsphere is 2-5 μm.

The slow-release antibacterial molecular cluster resin is prepared by the method.

The application of the slow-release antibacterial molecular cluster resin in drinking water antibiosis.

The preparation method and the obtained product have the following advantages and beneficial effects:

(1) The invention prevents the agglomeration phenomenon of the nano silver by the directional and tight combination of the dendritic active group in the molecular cluster resin and the nano silver.

(2) The invention fixes the nano silver on the surface in the form of ionic bond, so that the controllable slow release performance of the nano silver is stronger.

(3) the slow-release antibacterial molecular cluster resin can kill pathogenic microorganisms such as fungi, escherichia coli, staphylococcus aureus, mould and the like in water, has strong bactericidal performance, and the antibacterial effect does not decline along with the service life cycle of the material.

(4) The slow-release antibacterial molecular cluster resin obtained by the invention has good slow release performance, the concentration of Ag in water is lower than 4.5 mug/L, the maximum allowable concentration of Ag in drinking water according to the regulation of the national ministry of health is 5.0 mug/L, the use safety is good, the service life is long, the resin is harmless to human bodies, and the resin is suitable for industries such as household water purifiers, foods and medical treatment.

(5) the invention can control the slow release property and the antibacterial property of the slow release type antibacterial molecular cluster resin by adjusting the particle size of the nano silver.

(6) The slow-release antibacterial molecular cluster resin obtained by the invention has strong applicability, is suitable for filtering and purifying the tail end of a small household or group water purifier, solves the problems of excessive total bacterial count, odor, peculiar smell and the like of drinking water, and can be applied to slow-release antibacterial materials in the industries of food, pharmacy and the like to inhibit bacterial reproduction.

Detailed Description

The present invention will be described in further detail with reference to examples, but the embodiments of the present invention are not limited thereto.