阅读说明：本技术 一种铜离子掺杂海藻酸盐水凝胶抗菌过滤膜的制备方法 (Preparation method of copper ion-doped alginate hydrogel antibacterial filtering membrane ) 是由 赵孔银 白甜 谢文宾 苗君萍 赵磊 朱敦皖 张琳华 胡云霞 王晓磊 于 2019-11-26 设计创作，主要内容包括：本发明公开了一种铜离子掺杂海藻酸盐水凝胶抗菌过滤膜的制备方法。将海藻酸钠和高分子增强剂一起溶解于水中,静置脱泡得到铸膜液,将该铸膜液刮成膜并浸泡于戊二醛水溶液中,戊二醛同时交联高分子增强剂上的羟基和海藻酸盐上的羟基,起到增强海藻酸盐水凝胶的作用。用水充分洗涤去除残余的戊二醛,将戊二醛交联后的海藻酸盐水凝胶膜浸泡到过量的可溶性钙盐水溶液中交联,得到一种含高分子增强剂的海藻酸钙水凝胶过滤膜。为使膜具有抗菌功能,将膜浸泡在可溶性铜盐水溶液中交联,得到铜离子掺杂海藻酸盐水凝胶抗菌过滤膜,该膜机械强度大、溶胀率低,可应用在染料脱盐、乳化油过滤、废水处理等领域。(The invention discloses a preparation method of a copper ion-doped alginate hydrogel antibacterial filtering membrane. Dissolving sodium alginate and a high-molecular reinforcing agent in water, standing and defoaming to obtain a membrane casting solution, scraping the membrane casting solution into a membrane, and soaking the membrane casting solution into a glutaraldehyde aqueous solution, wherein glutaraldehyde simultaneously crosslinks hydroxyl on the high-molecular reinforcing agent and hydroxyl on alginate, so that the alginate hydrogel is reinforced. And fully washing with water to remove residual glutaraldehyde, and soaking the glutaraldehyde-crosslinked alginate hydrogel membrane into excessive soluble calcium salt aqueous solution for crosslinking to obtain the calcium alginate hydrogel filtering membrane containing the macromolecular reinforcing agent. In order to enable the membrane to have an antibacterial function, the membrane is soaked in a soluble copper salt aqueous solution for crosslinking to obtain the copper ion doped alginate hydrogel antibacterial filtering membrane, the membrane is high in mechanical strength and low in swelling rate, and can be applied to the fields of dye desalination, emulsified oil filtration, wastewater treatment and the like.)

1. A preparation method of a copper ion-doped alginate hydrogel antibacterial filtering membrane is characterized by comprising the following steps:

a) dissolving sodium alginate and a high-molecular reinforcing agent in water, standing and defoaming to obtain a membrane casting solution;

b) pouring the casting solution obtained in the step a) on a dry and clean glass plate, scraping the glass plate by using a glass rod with two ends wound with copper wires with the diameter of 20-1500 mu m, immediately soaking the glass plate and the scraped film into a glutaraldehyde aqueous solution with the mass percentage concentration of 0.1-10% for crosslinking for 5-600min, wherein the glutaraldehyde simultaneously crosslinks hydroxyl on a high molecular reinforcing agent and hydroxyl on alginate, so that the alginate hydrogel is enhanced, and the swelling performance of the alginate hydrogel is reduced; then, fully washing the membrane with deionized water to remove residual glutaraldehyde, and storing in the deionized water;

c) preparing a soluble calcium salt water solution with the mass percentage concentration of 0.2-10% as a first coagulating bath; preparing a soluble copper salt water solution with the mass percentage concentration of 0.2-5% as a second coagulating bath;

d) soaking the glutaraldehyde-crosslinked alginate membrane obtained in the step b) into the first coagulating bath obtained in the step c) for crosslinking for 10-600min to obtain a glutaraldehyde and calcium ion double-crosslinked alginate hydrogel membrane; in order to enable the membrane to have antibacterial performance and improve the flux of the membrane, soaking the glutaraldehyde and calcium ion double-crosslinked alginate hydrogel membrane into the second coagulation bath obtained in the step c) for crosslinking for 10-600min to obtain the copper ion doped alginate hydrogel antibacterial filtering membrane.

2. The method for preparing the copper ion-doped alginate hydrogel antibacterial filtering membrane as claimed in claim 1, wherein the polymer reinforcing agent is any one or a mixture of two or more of carboxymethyl cellulose, carboxymethyl chitosan, hydroxypropyl methyl cellulose and hydroxyethyl cellulose.

3. The method for preparing the copper ion-doped alginate hydrogel antibacterial filtering membrane as claimed in claim 1, wherein the soluble calcium salt is any one or a mixture of two or more of calcium chloride, calcium nitrate, calcium dihydrogen phosphate and calcium gluconate.

4. The method for preparing the copper ion-doped alginate hydrogel antibacterial filtering membrane as claimed in claim 1, characterized in that the soluble copper salt is any one or a mixture of two or more of copper chloride, copper sulfate and copper nitrate.

5. The method for preparing the copper ion-doped alginate hydrogel antibacterial filtering membrane as claimed in claim 1, wherein the copper ions endow the alginate hydrogel filtering membrane with good antibacterial performance, thereby preventing the alginate hydrogel filtering membrane from being degraded by bacteria in the using process.

6. A preparation method of a copper ion-doped alginate hydrogel antibacterial filtering membrane is characterized in that the structure of the calcium alginate hydrogel filtering membrane is changed by copper ion-doped crosslinking, and the pure water flux of the copper ion-doped alginate hydrogel antibacterial filtering membrane is 1.5-4 times of that of the calcium alginate hydrogel antibacterial filtering membrane.

7. The preparation method is characterized by being simple, and the obtained copper ion-doped alginate hydrogel antibacterial filtering membrane has good antibacterial and anti-pollution performances, high mechanical strength and low swelling rate, and has good application prospects in the fields of dye desalination, emulsified oil filtration, wastewater treatment and the like.

Technical Field

The invention relates to a preparation method of a copper ion-doped alginate hydrogel antibacterial filtering membrane, belonging to the field of functional materials and membrane separation.

The invention relates to the technical fields of antibiosis, filtering membranes, hydrogel and the like. In particular to a preparation method of a copper ion doped alginate hydrogel antibacterial filtering membrane.

Background

The membrane separation technology is an environment-friendly new technology, and compared with the traditional wastewater treatment method, the membrane separation technology does not produce secondary pollution, has low energy consumption and simple operation, and is one of the most promising water treatment technologies [ j.hazard.mater, 2016, 308: 75-83 deg. When the traditional polymer filter membrane is prepared, a polymer is firstly dissolved in an organic solvent, then phase transition is carried out in a water-phase coagulating bath to form a membrane, and a membrane structure with a compact surface and a large number of finger-shaped holes in the interior is usually formed.

The traditional membrane is usually made of inorganic materials (ceramics), organic high molecular materials or inorganic-organic composite materials, and the structure of the traditional membrane is divided into a plurality of types; different materials and structures determine the direction of application and the degree of separation of the membrane, and thus correspond to different applications. Compared with an inorganic membrane, the polymer membrane has the advantages of small size, low energy consumption, simple preparation, low price and the like, but has certain defects, such as acid and alkali resistance, organic solvent resistance of the separation membrane, easy bacterial breeding of the membrane in the application process, poor mechanical strength, poor thermal stability and the like.

The polymer gel is a multi-element system consisting of a polymer three-dimensional network and a solvent, and the hydrogel has good hydrophilicity because the hydrogel contains more than 80% of water. Sodium alginate is a natural high molecular substance which can be extracted from kelp or brown algae, has wide sources and low price, and is widely applied to the fields of food, biological medicine, wastewater treatment and the like at present. Sodium alginate and calcium ions can form hydrogel through ionic crosslinking. In the previous researches, a series of calcium alginate-based hydrogel filtering membranes are prepared [ patent No. ZL201310424398.7, ZL201310424399.1, ZL201310424397.2 ], and the calcium alginate-based hydrogel filtering membranes have good anti-pollution performance, but have the defects of poor mechanical property, low mechanical strength and easy bacterial degradation, thereby causing a plurality of problems in the membrane separation process.

Copper has good antibacterial activity, and compared with silver and zinc, copper has strong antibacterial activity, low price and higher environmental safety. Malagurski I, et al prepared two bimetallic (Zn/Cu) sodium alginate-based nanocomposites with copper using a simple process, the copper-containing sodium alginate-based nanocomposites had higher removal efficiency for microorganisms than non-mineralized samples. The copper mineralized alginate can be used as an antibacterial material with low price and easy production [ Materials Letters ]. 2018, 212, 32-36 ]. The existing method for preparing the antibacterial agent by taking hydroxyapatite as a carrier is mainly an ion exchange method, and the method has the defect that the combination of copper ions and the carrier is weak, so that the copper ions are rapidly dissociated and the long-term antibacterial property of the product cannot be maintained. However, the SalehihRobati M. et al showed that the removal effect of calcium alginate on copper in water was studied by using calcium alginate as a carrier and immobilized seaweed as a carrier.

The invention discloses a preparation method of a copper ion-doped alginate hydrogel antibacterial filtering membrane. Dissolving sodium alginate and a high-molecular reinforcing agent in water, standing and defoaming to obtain a membrane casting solution, scraping the membrane casting solution into a membrane, and soaking the membrane casting solution into a glutaraldehyde aqueous solution, wherein glutaraldehyde simultaneously crosslinks hydroxyl on the high-molecular reinforcing agent and hydroxyl on alginate, so that the alginate hydrogel is reinforced. And fully washing with water to remove residual glutaraldehyde, and soaking the glutaraldehyde-crosslinked alginate hydrogel membrane into excessive soluble calcium salt aqueous solution for crosslinking to obtain the calcium alginate hydrogel filtering membrane containing the macromolecular reinforcing agent. In order to enable the membrane to have an antibacterial function, the membrane is soaked in a soluble copper salt aqueous solution for crosslinking to obtain the copper ion-doped alginate hydrogel antibacterial filtering membrane which is high in mechanical strength and low in swelling rate and can be applied to the fields of dye desalination, emulsified oil filtration, wastewater treatment and the like

Disclosure of Invention

Aiming at the defects of the prior art, the invention aims to solve the technical problems that the traditional membrane is not pollution-resistant, has poor hydrophilicity, and the calcium alginate hydrogel filtering membrane has low strength and is easy to degrade by bacteria.

The invention provides a preparation method of a copper ion-doped alginate hydrogel antibacterial filtering membrane, which solves the problems that the traditional membrane is not pollution-resistant, has poor hydrophilicity, is low in strength of a calcium alginate hydrogel filtering membrane, is easy to degrade by bacteria and the like.

The invention provides a preparation method of a copper ion-doped alginate hydrogel antibacterial filtering membrane, which is characterized by comprising the following steps of:

a) dissolving sodium alginate and a high-molecular reinforcing agent in water, standing and defoaming to obtain a membrane casting solution;

b) pouring the casting solution obtained in the step a) on a dry and clean glass plate, scraping the glass plate by using a glass rod with two ends wound with copper wires with the diameter of 20-1500 mu m, immediately soaking the glass plate and the scraped film into a glutaraldehyde aqueous solution with the mass percentage concentration of 0.1-10% for crosslinking for 5-600min, wherein the glutaraldehyde simultaneously crosslinks hydroxyl on a high molecular reinforcing agent and hydroxyl on alginate, so that the alginate hydrogel is enhanced, and the swelling performance of the alginate hydrogel is reduced; then, fully washing the membrane with deionized water to remove residual glutaraldehyde, and storing in the deionized water;

c) preparing a soluble calcium salt water solution with the mass percentage concentration of 0.2-10% as a first coagulating bath; preparing a soluble copper salt water solution with the mass percentage concentration of 0.2-5% as a second coagulating bath;

d) soaking the glutaraldehyde-crosslinked alginate membrane obtained in the step b) into the first coagulating bath obtained in the step c) for crosslinking for 10-600min to obtain a glutaraldehyde and calcium ion double-crosslinked alginate hydrogel membrane; in order to enable the membrane to have antibacterial performance and improve the flux of the membrane, soaking the glutaraldehyde and calcium ion double-crosslinked alginate hydrogel membrane into the second coagulation bath obtained in the step c) for crosslinking for 10-600min to obtain the copper ion doped alginate hydrogel antibacterial filtering membrane.

The macromolecular reinforcing agent is any one or a mixture of two or more of carboxymethyl cellulose, carboxymethyl chitosan, hydroxypropyl methyl cellulose and hydroxyethyl cellulose; the soluble calcium salt is any one or mixture of two or more of calcium chloride, calcium nitrate, calcium dihydrogen phosphate and calcium gluconate; the soluble copper salt is any one or a mixture of two or more of copper chloride, copper sulfate and copper nitrate.

In the invention, copper ions endow the alginate hydrogel filtering membrane with good antibacterial performance, and the alginate hydrogel filtering membrane is prevented from being degraded by bacteria in the using process. The structure of the calcium alginate hydrogel filtering membrane is changed by copper ion doping and crosslinking, and the pure water flux of the copper ion doping alginate hydrogel antibacterial filtering membrane is 1.5-4 times that of the calcium alginate hydrogel antibacterial filtering membrane.

The preparation method is simple, and the obtained copper ion-doped alginate hydrogel antibacterial filtering membrane has good antibacterial and anti-pollution performances, high mechanical strength and low swelling rate, and has good application prospects in the fields of dye desalination, emulsified oil filtration, wastewater treatment and the like.

Detailed Description

Specific examples of the present invention will be described below, but the present invention is not limited to the examples.