阅读说明：本技术 一种高透明度高韧性抗菌型聚乙烯醇水凝胶及其制备方法 (High-transparency high-toughness antibacterial polyvinyl alcohol hydrogel and preparation method thereof ) 是由 杨明成 郭文慧 刘树博 刘文涛 张本尚 田青亮 王允 樊红丽 赵惠东 王宏正 于 2020-06-28 设计创作，主要内容包括：本发明公开了一种高透明度高韧性抗菌型聚乙烯醇水凝胶,由聚乙烯醇与植物多酚制备而成,属于功能化新材料领域。其通过以下步骤制备而成：(1)将定量聚乙烯醇加入水中,搅拌升温得到聚乙烯醇水溶液；(2)将聚乙烯醇水溶液转移至模具中,<Sup>60</Sup>Coγ射线或电子束辐照成型；(3)将植物多酚加入水中,得到植物多酚水溶液；(4)将成型的聚乙烯醇水凝胶在植物多酚水溶液中浸泡一定时间。所制备的水凝胶最大拉伸强度和最大断裂伸长率分别是未浸泡植物多酚水溶液聚乙烯醇水凝胶的14.8倍和4.7倍,并表现出良好的抗菌性和透明度。(The invention discloses a high-transparency high-toughness antibacterial polyvinyl alcohol hydrogel which is prepared from polyvinyl alcohol and plant polyphenol, and belongs to the field of novel functional materials. The preparation method comprises the following steps: (1) adding a certain amount of polyvinyl alcohol into water, stirring and heating to obtain a polyvinyl alcohol aqueous solution; (2) the aqueous polyvinyl alcohol solution is transferred to a mold, 60 irradiating and forming Co gamma rays or electron beams; (3) adding plant polyphenol into water to obtain plant polyphenol water solution; (4) soaking the formed polyvinyl alcohol hydrogel in a plant polyphenol water solution for a certain time. The maximum tensile strength and the maximum elongation at break of the prepared hydrogel are respectively the plant polyphenol water which is not soaked14.8 times and 4.7 times of the solution polyvinyl alcohol hydrogel, and shows good antibacterial property and transparency.)

1. An antibacterial polyvinyl alcohol hydrogel is characterized by being prepared by the following method: (1) adding polyvinyl alcohol into water, stirring and heating to obtain a polyvinyl alcohol aqueous solution;

(2) the aqueous polyvinyl alcohol solution is transferred to a mold,⁶⁰irradiating and forming Co gamma rays or electron beams;

(3) adding plant polyphenol into water to obtain plant polyphenol water solution;

(4) soaking the polyvinyl alcohol hydrogel formed in the step (2) in a plant polyphenol aqueous solution;

the plant polyphenol is Tannic Acid (TA), epigallocatechin gallate (EGCG), catechin, and gallic acid.

2. The antibacterial polyvinyl alcohol hydrogel according to claim 1, wherein,

in the step (1), the mass fraction of the polyvinyl alcohol aqueous solution is 10-15%; in the step (3), the mass fraction of the plant polyphenol water solution is 0.1-1%.

3. The antibacterial polyvinyl alcohol hydrogel according to claim 1 or 2,

in the step (2),⁶⁰the irradiation dose of Co gamma rays or electron beams is 10-30 kGy;

in the step (4), the formed polyvinyl alcohol hydrogel is soaked in the plant polyphenol water solution for 2-48 h.

4. A method for preparing the antibacterial polyvinyl alcohol hydrogel according to claim 1, which is achieved by the steps of:

(1) adding polyvinyl alcohol into water, stirring and heating to obtain a polyvinyl alcohol aqueous solution;

(2) the aqueous polyvinyl alcohol solution is transferred to a mold,⁶⁰irradiating and forming Co gamma rays or electron beams;

(3) adding plant polyphenol into water to obtain plant polyphenol water solution;

(4) soaking the polyvinyl alcohol hydrogel formed in the step (2) in a plant polyphenol aqueous solution;

the plant polyphenol is Tannic Acid (TA), epigallocatechin gallate (EGCG), catechin, and gallic acid.

5. The method for preparing an antibacterial polyvinyl alcohol hydrogel according to claim 4, wherein in the step (1), the mass fraction of the polyvinyl alcohol aqueous solution is 10-15%; in the step (3), the mass fraction of the plant polyphenol water solution is 0.1-1%.

6. The method for preparing an antibacterial polyvinyl alcohol hydrogel according to claim 4, wherein the polyvinyl alcohol hydrogel is a polyvinyl alcohol hydrogel,

in the step (2),⁶⁰the irradiation dose of Co gamma rays or electron beams is 10-30 kGy;

in the step (4), the formed polyvinyl alcohol hydrogel is soaked in the plant polyphenol water solution for 2-48 h.

Technical Field

The invention belongs to the field of novel functionalized materials, and particularly relates to an antibacterial polyvinyl alcohol hydrogel with high transparency and high toughness and a preparation method thereof.

Background

The hydrogel is a high molecular material containing a large amount of water and having a three-dimensional network structure, and has important application prospects in the fields of joint lubrication, biological tissue engineering, drug controlled release carriers and the like. The polyvinyl alcohol is a water-soluble polymer, has excellent biocompatibility and no toxicity, meets the requirement of current environmental protection in production and use, and is a green chemical material, so that the polyvinyl alcohol hydrogel is widely applied to the fields of agriculture and forestry, industry, medicine and health and the like.

The polyvinyl alcohol hydrogel is usually prepared by a chemical method, a physical method, a radiation method and the like. The chemical method uses toxic reagents such as glyoxal, glutaraldehyde, genipin or boric acid (CN201610026855.0) and the like as cross-linking agents, the toxic cross-linking agents are difficult to eliminate, and the hydrogel loses no toxicity due to trace residues; the freeze-thaw method (CN201710928649.3) is the most common physical method for preparing polyvinyl alcohol hydrogel, and the hydrogel prepared by the method has the advantage of good elasticity, but the hydrogel is a physical gel, and can be dissolved into a solution at a higher temperature, and multiple times of freeze-thaw methods are required for preparation, so that energy consumption and time consumption are required, and the prepared hydrogel has low swelling degree and is opaque; the radiation method is a green method for synthesizing polyvinyl alcohol hydrogel, has high synthesis efficiency and good gel transparency, but has the problems of poor mechanical property, low strength, poor toughness and easy breakage. Improvements are also needed.

Disclosure of Invention

Aiming at the problems of the current synthetic route and existence of polyvinyl alcohol hydrogel, the invention aims to provide a simple and efficient antibacterial polyvinyl alcohol hydrogel with high transparency and high toughness and a preparation method thereof.

In order to achieve the purpose, the invention firstly utilizes the polyvinyl alcohol aqueous solution⁶⁰Co gamma ray or electron beam irradiation forming, and soaking the PVA hydrogel in plant polyphenol water solution.

The following technical scheme is adopted specifically:

the preparation method of the high-transparency high-toughness antibacterial polyvinyl alcohol hydrogel comprises the following steps:

(1) adding polyvinyl alcohol into water, stirring and heating to obtain a polyvinyl alcohol aqueous solution;

(2) the aqueous polyvinyl alcohol solution is transferred to a mold,⁶⁰irradiating and forming Co gamma rays or electron beams;

(3) adding plant polyphenol into water to obtain plant polyphenol water solution;

(4) soaking the formed polyvinyl alcohol hydrogel in a plant polyphenol aqueous solution.

Further, in the step (1), the mass fraction of the polyvinyl alcohol aqueous solution is 10-15%.

Further, in the step (2),⁶⁰the irradiation dose of Co gamma rays or electron beams is 10-30 kGy, crosslinking and degradation exist simultaneously in the process of synthesizing the polyvinyl alcohol hydrogel by irradiation, the polyvinyl alcohol gel cannot be formed at an excessively low dose, and energy consumption is wasted at an excessively high dose.

Further, in the step (3), the mass fraction of the plant polyphenol water solution is 0.1-1%.

Further, in the step (4), the formed polyvinyl alcohol hydrogel is soaked in the plant polyphenol water solution for 2-48 hours.

Further, the plant polyphenol is Tannic Acid (TA), epigallocatechin gallate (EGCG), catechin, gallic acid, etc.

Tannic Acid (TA), epigallocatechin gallate (EGCG), Catechin (Catechin), gallic acid (Ellagic acid) and the like are extracted natural polyphenol compounds, and the chemical structures of the compounds are rich in phenolic hydroxyl groups, so that the compounds have excellent antibacterial, antiviral, antioxidant and hemostatic functions. The composite hydrogel prepared from the polyphenol and the polyvinyl alcohol has good antibacterial performance.

The invention has the innovation points and advantages that: by adopting the method of irradiating and then soaking in the plant polyphenol solution, the high transparency of the polyvinyl alcohol hydrogel can be maintained, the hydrogel is endowed with good antibacterial property and excellent toughness, and the mechanical property of the prepared hydrogel can be controlled by changing the soaking time and the concentration of the polyphenol solution. The maximum tensile strength and the maximum elongation at break of the hydrogel prepared by the invention are respectively 14.8 times and 4.7 times of those of the polyvinyl alcohol hydrogel without soaking the plant polyphenol aqueous solution, and the hydrogel shows good antibacterial property and transparency (see the comparison in figure 3).

By adopting the method, the irradiation hydrogel can be produced in large scale in the early stage, and can be directly soaked in plant polyphenol solutions of different types according to actual requirements in the later stage, so that the procedure of early preparation is reduced, and the rapid preparation is facilitated.

Drawings

FIG. 1 is a graph showing tensile strength and elongation at break of hydrogels prepared in examples 1 to 3 of the present invention and comparative example 1 as a function of immersion concentration.

FIG. 2 is a graph showing the antibacterial effect of hydrogels prepared by soaking with tannic acid of different concentrations on Escherichia coli (a) and Staphylococcus aureus (b) samples according to the present invention.

FIG. 3 is a graph showing the transparency of the hydrogel (a) of example 2 of the present invention before soaking, the hydrogel (b) prepared in example 2, and the hydrogel (c) of comparative example 2.

Detailed Description

The present invention will be described in detail with reference to examples.