A modified polyvinyl alcohol gel and a method for preparing and using the same

Abstract

This invention discloses a modified polyvinyl alcohol gel, its preparation method, and its application. The preparation method includes the following steps: S1. Reaction of 5,5-dimethylhydantoin, a strong base, and epichlorohydrin to obtain 3-glycidyl-5,5-dimethylhydantoin; S2. Reaction of polyvinyl alcohol, 3,4-epoxycyclohexylmethyl 3,4-epoxycyclohexylcarbamate, glycidyl ether, and 3-glycidyl-5,5-dimethylhydantoin to obtain the modified polyvinyl alcohol gel; wherein the mass ratio of 5,5-dimethylhydantoin, polyvinyl alcohol, 3,4-epoxycyclohexylmethyl 3,4-epoxycyclohexylcarbamate, and glycidyl ether is 1:(0.5-2.5):(1-3):(0.2-1). The modified polyvinyl alcohol gel prepared by this invention has good antibacterial effect.

Description

Technical Field

[0001] This invention relates to the field of gel technology, and more specifically, to a modified polyvinyl alcohol gel, its preparation method, and its application. Background Technology

[0002] Bacteria are one of the major groups of organisms, with the vast majority ranging in diameter from 0.5 to 5 μm. They are widely distributed in soil and water, or live in symbiosis with other organisms. For example, the human body is a habitat for a large number of bacteria, which are distributed on the skin surface, intestines, mouth, nose, and other parts of the body. Although the human body itself contains a large number of bacteria, they can coexist mutually beneficially as long as the dynamic balance between the bacterial colonies and the human body is not disrupted. When this dynamic balance is disrupted, the bacteria present in the human body can cause various inflammations. In addition, many foreign bacteria are pathogens that can cause various diseases in the human body, seriously affecting human health. Therefore, to protect human health, numerous antibacterial drugs or preparations have been developed, and antibacterial gels are one such example.

[0003] Antibacterial gels are gel-like preparations with antibacterial properties, composed of an antibacterial agent and a gel matrix. Polyvinyl alcohol gel is an antibacterial gel with polyvinyl alcohol as the gel matrix, and it has been widely used in the medical and health fields. However, the antibacterial effect of polyvinyl alcohol gel is currently unsatisfactory and needs further improvement.

[0004] Therefore, it is of great significance to develop a method for preparing modified polyvinyl alcohol gel with high antibacterial effect. Summary of the Invention

[0005] The purpose of this invention is to solve the problem of poor antibacterial effect of polyvinyl alcohol gel in the prior art, and to provide a modified polyvinyl alcohol gel, its preparation method and application.

[0006] To achieve the above objectives, the technical solution adopted by the present invention is as follows:

[0007] In a first aspect, the present invention provides a method for preparing modified polyvinyl alcohol gel, the method comprising the following steps:

[0008] S1,5,5-dimethylhydantoin, a strong base, and epichlorohydrin are reacted to give 3-glycidyl-5,5-dimethylhydantoin.

[0009] S2. Polyvinyl alcohol, 3,4-epoxycyclohexylmethyl 3,4-epoxycyclohexyl carboxylate, glycidyl ether, and 3-glycidyl-5,5-dimethylhydantoin are reacted to obtain modified polyvinyl alcohol gel.

[0010] The mass ratio of 5,5-dimethylhydantoin, polyvinyl alcohol, 3,4-epoxycyclohexylmethyl 3,4-epoxycyclohexylcarbamate and glycidyl ether is 1:(0.5-2.5):(1-3):(0.2-1).

[0011] In this invention, by controlling the mass ratio of 5,5-dimethylhydantoin, polyvinyl alcohol, 3,4-epoxycyclohexylmethyl 3,4-epoxycyclohexylcarbamate, and glycidyl ether, a stable three-dimensional network structure can be formed. This allows the antibacterial 5,5-dimethylhydantoin to be stably and uniformly bonded to the three-dimensional network structure through chemical bonds. Simultaneously, the formed three-dimensional network structure can also delay the loss of 5,5-dimethylhydantoin, which is beneficial for improving the stability of the modified polyvinyl alcohol gel, thereby achieving the goal of improving the antibacterial effect of the modified polyvinyl alcohol gel.

[0012] In this invention, the structural formula of the 3-glycidyl-5,5-dimethylhydantoin is shown in formula (I):

[0013]

[0014] Preferably, the mass ratio of 5,5-dimethylhydantoin, polyvinyl alcohol, 3,4-epoxycyclohexylmethyl 3,4-epoxycyclohexylcarbamate and glycidyl ether is 1:(1-2):(1.5-2.5):(0.4-0.8).

[0015] More preferably, the mass ratio of 5,5-dimethylhydantoin, polyvinyl alcohol, 3,4-epoxycyclohexylmethyl 3,4-epoxycyclohexylcarbamate and glycidyl ether is 1:1.5:2:0.6.

[0016] Preferably, in step S1, the molar ratio of 5,5-dimethylhydantoin, the strong base, and epichlorohydrin is 1:(0.8-2):1.

[0017] Preferably, in step S1, the strong alkali is at least one of sodium hydroxide and potassium hydroxide.

[0018] Preferably, in step S1, the reaction temperature is 35-60°C.

[0019] Preferably, in step S1, the reaction time is 6-15 hours.

[0020] Preferably, in step S1, the catalyst used in the reaction is benzyltrimethylammonium chloride.

[0021] More preferably, the mass ratio of 5,5-dimethylhydantoin to benzyltrimethylammonium chloride is 1:(0.05-0.5).

[0022] Preferably, in step S1, the solvent used in the reaction is water and ethanol.

[0023] More preferably, the mass ratio of water to ethanol is 1:(0.5-3).

[0024] More preferably, the solid-liquid ratio of the 5,5-dimethylhydantoin to the solvent is 1 g:(5-80) mL.

[0025] Preferably, in step S2, the weight-average molecular weight Mw of the polyvinyl alcohol is 9000-186000.

[0026] In this invention, the weight-average molecular weight Mw of the polyvinyl alcohol is one of 9000-10000, 13000-23000, 31000-50000, 85000-124000, and 146000-186000.

[0027] More preferably, the weight-average molecular weight (Mw) of the polyvinyl alcohol is 13,000-124,000.

[0028] More preferably, the weight-average molecular weight (Mw) of the polyvinyl alcohol is 31,000-50,000.

[0029] Preferably, in step S2, the reaction temperature is 20-60°C.

[0030] Preferably, in step S2, the reaction time is 2-15 hours.

[0031] Preferably, in step S2, after the reaction, the process further includes filtration and washing.

[0032] More preferably, the solvent used for washing is at least one of water, ethanol, methanol, and isopropanol.

[0033] Secondly, the present invention provides a modified polyvinyl alcohol gel, which is prepared by the preparation method described in the first aspect.

[0034] Thirdly, the present invention provides an application of modified polyvinyl alcohol gel in antibacterial applications.

[0035] Compared with the prior art, the beneficial effects of the present invention are as follows:

[0036] In this invention, by controlling the mass ratio of 5,5-dimethylhydantoin, polyvinyl alcohol, 3,4-epoxycyclohexylmethyl 3,4-epoxycyclohexylcarbamate, and glycidyl ether, a stable three-dimensional network structure can be formed. This allows the antibacterial 5,5-dimethylhydantoin to be stably and uniformly bonded to the three-dimensional network structure through chemical bonds. Simultaneously, the formed three-dimensional network structure can also delay the loss of 5,5-dimethylhydantoin, which is beneficial for improving the stability of the modified polyvinyl alcohol gel, thereby achieving the goal of improving the antibacterial effect of the modified polyvinyl alcohol gel. Attached Figure Description

[0037] Figure 1 This is a photograph of the modified polyvinyl alcohol gel from Example 1. Detailed Implementation

[0038] To better illustrate the purpose, technical solution, and advantages of the present invention, the present invention will be further described below in conjunction with specific embodiments.

[0039] The experimental methods in the following examples, unless otherwise specified, are generally performed under conventional conditions in the art or as recommended by the manufacturer; the raw materials and reagents used, unless otherwise specified, are all commercially available from the conventional market.

[0040] The reagents used in the various embodiments and comparative examples of this invention are as follows:

[0041] Polyvinyl alcohol-1, P434376, weight-average molecular weight Mw = 31000-50000, Shanghai Aladdin;

[0042] Polyvinyl alcohol-2, P434367, weight-average molecular weight Mw = 13000-23000, Shanghai Aladdin;

[0043] Polyvinyl alcohol-3, P434370, weight-average molecular weight Mw = 85,000-124,000, Shanghai Aladdin;

[0044] Polyvinyl alcohol-4, P434372, weight-average molecular weight Mw = 9000-10000, Shanghai Aladdin;

[0045] Polyvinyl alcohol-5, P434375, weight-average molecular weight Mw = 146,000-186,000, Shanghai Aladdin.

[0046] Example 1

[0047] This embodiment provides a modified polyvinyl alcohol gel, the preparation method of which includes the following steps:

[0048] S1. In 500 mL of solvent (water and ethanol in a 1:1 mass ratio), 10 g of 5,5-dimethylhydantoin (0.078 mol), 3.12 g of sodium hydroxide (0.078 mol), 7.22 g of epichlorohydrin (0.078 mol), and 1 g of benzyltrimethylammonium chloride catalyst were added and mixed. The mixture was reacted at 50 °C for 10 h to obtain 3-glycidyl-5,5-dimethylhydantoin. The reaction process is shown below.

[0049]

[0050] S2. To the 3-glycidyl-5,5-dimethylhydantoin prepared in step S1, add 15g of polyvinyl alcohol-1 (weight average molecular weight Mw = 31000-50000), 20g of 3,4-epoxycyclohexylmethyl 3,4-epoxycyclohexylcarbamate, and 6g of glycidyl ether. Heat to 60℃ and react for 4 hours. Filter and wash with ultrapure water to obtain modified polyvinyl alcohol gel. Figure 1 Here is a photograph of the modified polyvinyl alcohol gel.

[0051] The mass ratio of 5,5-dimethylhydantoin, polyvinyl alcohol-1, 3,4-epoxycyclohexylmethyl 3,4-epoxycyclohexylcarbamate, and glycidyl ether is 1:1.5:2:0.6.

[0052] In step S1, the molar ratio of 5,5-dimethylhydantoin, strong base and epichlorohydrin is 1:1:1, the mass ratio of 5,5-dimethylhydantoin and benzyltrimethylammonium chloride is 1:0.1, and the solid-liquid ratio of 5,5-dimethylhydantoin and solvent is 1g:50mL.

[0053] Example 2

[0054] This embodiment provides a modified polyvinyl alcohol gel, the preparation method of which includes the following steps:

[0055] S1. In 500 mL of solvent (water and ethanol in a 1:1 mass ratio), 10 g of 5,5-dimethylhydantoin (0.078 mol), 3.12 g of sodium hydroxide (0.078 mol), 7.22 g of epichlorohydrin (0.078 mol), and 1 g of benzyltrimethylammonium chloride catalyst were added and mixed. The mixture was reacted at 50 °C for 10 h to obtain 3-glycidyl-5,5-dimethylhydantoin.

[0056] S2. To the 3-glycidyl-5,5-dimethylhydantoin prepared in step S1, add 10g of polyvinyl alcohol-1 (weight average molecular weight Mw = 31000-50000), 20g of 3,4-epoxycyclohexylmethyl 3,4-epoxycyclohexylcarbamate and 6g of glycidyl ether, heat to 60℃ and react for 4h, filter, wash with ultrapure water to obtain modified polyvinyl alcohol gel;

[0057] The mass ratio of 5,5-dimethylhydantoin, polyvinyl alcohol-1, 3,4-epoxycyclohexylmethyl 3,4-epoxycyclohexylcarbamate and glycidyl ether is 1:1:2:0.6.

[0058] In step S1, the molar ratio of 5,5-dimethylhydantoin, strong base and epichlorohydrin is 1:1:1, the mass ratio of 5,5-dimethylhydantoin and benzyltrimethylammonium chloride is 1:0.1, and the solid-liquid ratio of 5,5-dimethylhydantoin and solvent is 1g:50mL.

[0059] Example 3

[0060] This embodiment provides a modified polyvinyl alcohol gel, the preparation method of which includes the following steps:

[0061] S1. In 500 mL of solvent (water and ethanol in a 1:1 mass ratio), 10 g of 5,5-dimethylhydantoin (0.078 mol), 3.12 g of sodium hydroxide (0.078 mol), 7.22 g of epichlorohydrin (0.078 mol), and 1 g of benzyltrimethylammonium chloride catalyst were added and mixed. The mixture was reacted at 50 °C for 10 h to obtain 3-glycidyl-5,5-dimethylhydantoin.

[0062] S2. To the 3-glycidyl-5,5-dimethylhydantoin prepared in step S1, add 20g of polyvinyl alcohol-1 (weight average molecular weight Mw = 31000-50000), 20g of 3,4-epoxycyclohexylmethyl 3,4-epoxycyclohexylcarbamate and 6g of glycidyl ether, heat to 60℃ and react for 4h, filter, wash with ultrapure water to obtain modified polyvinyl alcohol gel;

[0063] The mass ratio of 5,5-dimethylhydantoin, polyvinyl alcohol-1, 3,4-epoxycyclohexylmethyl 3,4-epoxycyclohexylcarbamate and glycidyl ether is 1:2:2:0.6.

[0064] In step S1, the molar ratio of 5,5-dimethylhydantoin, strong base and epichlorohydrin is 1:1:1, the mass ratio of 5,5-dimethylhydantoin and benzyltrimethylammonium chloride is 1:0.1, and the solid-liquid ratio of 5,5-dimethylhydantoin and solvent is 1g:50mL.

[0065] Example 4

[0066] This embodiment provides a modified polyvinyl alcohol gel, the preparation method of which includes the following steps:

[0067] S1. In 500 mL of solvent (water and ethanol in a 1:1 mass ratio), 10 g of 5,5-dimethylhydantoin (0.078 mol), 3.12 g of sodium hydroxide (0.078 mol), 7.22 g of epichlorohydrin (0.078 mol), and 1 g of benzyltrimethylammonium chloride catalyst were added and mixed. The mixture was reacted at 50 °C for 10 h to obtain 3-glycidyl-5,5-dimethylhydantoin.

[0068] S2. In the 3-glycidyl-5,5-dimethylhydantoin prepared in step S1, add 5g of polyvinyl alcohol-1 (weight average molecular weight Mw = 31000-50000), 20g of 3,4-epoxycyclohexylmethyl 3,4-epoxycyclohexylcarbamate and 6g of glycidyl ether, heat to 60℃ and react for 4h, filter, wash with ultrapure water to obtain modified polyvinyl alcohol gel;

[0069] The mass ratio of 5,5-dimethylhydantoin, polyvinyl alcohol-1, 3,4-epoxycyclohexylmethyl 3,4-epoxycyclohexylcarbamate, and glycidyl ether is 1:0.5:2:0.6.

[0070] In step S1, the molar ratio of 5,5-dimethylhydantoin, strong base and epichlorohydrin is 1:1:1, the mass ratio of 5,5-dimethylhydantoin and benzyltrimethylammonium chloride is 1:0.1, and the solid-liquid ratio of 5,5-dimethylhydantoin and solvent is 1g:50mL.

[0071] Example 5

[0072] This embodiment provides a modified polyvinyl alcohol gel, the preparation method of which includes the following steps:

[0073] S1. In 500 mL of solvent (water and ethanol in a 1:1 mass ratio), 10 g of 5,5-dimethylhydantoin (0.078 mol), 3.12 g of sodium hydroxide (0.078 mol), 7.22 g of epichlorohydrin (0.078 mol), and 1 g of benzyltrimethylammonium chloride catalyst were added and mixed. The mixture was reacted at 50 °C for 10 h to obtain 3-glycidyl-5,5-dimethylhydantoin.

[0074] S2. To the 3-glycidyl-5,5-dimethylhydantoin prepared in step S1, add 25g of polyvinyl alcohol-1 (weight average molecular weight Mw = 31000-50000), 20g of 3,4-epoxycyclohexylmethyl 3,4-epoxycyclohexylcarbamate and 6g of glycidyl ether, heat to 60℃ and react for 4h, filter, wash with ultrapure water to obtain modified polyvinyl alcohol gel;

[0075] The mass ratio of 5,5-dimethylhydantoin, polyvinyl alcohol-1, 3,4-epoxycyclohexylmethyl 3,4-epoxycyclohexylcarbamate, and glycidyl ether is 1:2.5:2:0.6.

[0076] In step S1, the molar ratio of 5,5-dimethylhydantoin, strong base and epichlorohydrin is 1:1:1, the mass ratio of 5,5-dimethylhydantoin and benzyltrimethylammonium chloride is 1:0.1, and the solid-liquid ratio of 5,5-dimethylhydantoin and solvent is 1g:50mL.

[0077] Example 6

[0078] This embodiment provides a modified polyvinyl alcohol gel, the preparation method of which includes the following steps:

[0079] S1. In 500 mL of solvent (water and ethanol in a 1:1 mass ratio), 10 g of 5,5-dimethylhydantoin (0.078 mol), 3.12 g of sodium hydroxide (0.078 mol), 7.22 g of epichlorohydrin (0.078 mol), and 1 g of benzyltrimethylammonium chloride catalyst were added and mixed. The mixture was reacted at 50 °C for 10 h to obtain 3-glycidyl-5,5-dimethylhydantoin.

[0080] S2. To the 3-glycidyl-5,5-dimethylhydantoin prepared in step S1, add 15g of polyvinyl alcohol-1 (weight average molecular weight Mw = 31000-50000), 15g of 3,4-epoxycyclohexylmethyl 3,4-epoxycyclohexylcarbamate and 6g of glycidyl ether, heat to 60℃ and react for 4h, filter, wash with ultrapure water to obtain modified polyvinyl alcohol gel;

[0081] The mass ratio of 5,5-dimethylhydantoin, polyvinyl alcohol-1, 3,4-epoxycyclohexylmethyl 3,4-epoxycyclohexylcarbamate, and glycidyl ether is 1:1.5:1.5:0.6.

[0082] In step S1, the molar ratio of 5,5-dimethylhydantoin, strong base and epichlorohydrin is 1:1:1, the mass ratio of 5,5-dimethylhydantoin and benzyltrimethylammonium chloride is 1:0.1, and the solid-liquid ratio of 5,5-dimethylhydantoin and solvent is 1g:50mL.

[0083] Example 7

[0084] This embodiment provides a modified polyvinyl alcohol gel, the preparation method of which includes the following steps:

[0085] S1. In 500 mL of solvent (water and ethanol in a 1:1 mass ratio), 10 g of 5,5-dimethylhydantoin (0.078 mol), 3.12 g of sodium hydroxide (0.078 mol), 7.22 g of epichlorohydrin (0.078 mol), and 1 g of benzyltrimethylammonium chloride catalyst were added and mixed. The mixture was reacted at 50 °C for 10 h to obtain 3-glycidyl-5,5-dimethylhydantoin.

[0086] S2. To the 3-glycidyl-5,5-dimethylhydantoin prepared in step S1, add 15g of polyvinyl alcohol-1 (weight average molecular weight Mw = 31000-50000), 25g of 3,4-epoxycyclohexylmethyl 3,4-epoxycyclohexylcarbamate and 6g of glycidyl ether, heat to 60℃ and react for 4h, filter, wash with ultrapure water to obtain modified polyvinyl alcohol gel;

[0087] The mass ratio of 5,5-dimethylhydantoin, polyvinyl alcohol-1, 3,4-epoxycyclohexylmethyl 3,4-epoxycyclohexylcarbamate, and glycidyl ether is 1:1.5:2.5:0.6.

[0088] In step S1, the molar ratio of 5,5-dimethylhydantoin, strong base and epichlorohydrin is 1:1:1, the mass ratio of 5,5-dimethylhydantoin and benzyltrimethylammonium chloride is 1:0.1, and the solid-liquid ratio of 5,5-dimethylhydantoin and solvent is 1g:50mL.

[0089] Example 8

[0090] This embodiment provides a modified polyvinyl alcohol gel, the preparation method of which includes the following steps:

[0091] S1. In 500 mL of solvent (water and ethanol in a 1:1 mass ratio), 10 g of 5,5-dimethylhydantoin (0.078 mol), 3.12 g of sodium hydroxide (0.078 mol), 7.22 g of epichlorohydrin (0.078 mol), and 1 g of benzyltrimethylammonium chloride catalyst were added and mixed. The mixture was reacted at 50 °C for 10 h to obtain 3-glycidyl-5,5-dimethylhydantoin.

[0092] S2. To the 3-glycidyl-5,5-dimethylhydantoin prepared in step S1, add 15g of polyvinyl alcohol-1 (weight average molecular weight Mw = 31000-50000), 10g of 3,4-epoxycyclohexylmethyl 3,4-epoxycyclohexylcarbamate and 6g of glycidyl ether, heat to 60℃ and react for 4h, filter, wash with ultrapure water to obtain modified polyvinyl alcohol gel;

[0093] The mass ratio of 5,5-dimethylhydantoin, polyvinyl alcohol-1, 3,4-epoxycyclohexylmethyl 3,4-epoxycyclohexylcarbamate, and glycidyl ether is 1:1.5:1:0.6.

[0094] In step S1, the molar ratio of 5,5-dimethylhydantoin, strong base and epichlorohydrin is 1:1:1, the mass ratio of 5,5-dimethylhydantoin and benzyltrimethylammonium chloride is 1:0.1, and the solid-liquid ratio of 5,5-dimethylhydantoin and solvent is 1g:50mL.

[0095] Example 9

[0096] This embodiment provides a modified polyvinyl alcohol gel, the preparation method of which includes the following steps:

[0097] S1. In 500 mL of solvent (water and ethanol in a 1:1 mass ratio), 10 g of 5,5-dimethylhydantoin (0.078 mol), 3.12 g of sodium hydroxide (0.078 mol), 7.22 g of epichlorohydrin (0.078 mol), and 1 g of benzyltrimethylammonium chloride catalyst were added and mixed. The mixture was reacted at 50 °C for 10 h to obtain 3-glycidyl-5,5-dimethylhydantoin.

[0098] S2. To the 3-glycidyl-5,5-dimethylhydantoin prepared in step S1, add 15g of polyvinyl alcohol-1 (weight average molecular weight Mw = 31000-50000), 30g of 3,4-epoxycyclohexylmethyl 3,4-epoxycyclohexylcarbamate and 6g of glycidyl ether, heat to 60℃ and react for 4h, filter, wash with ultrapure water to obtain modified polyvinyl alcohol gel;

[0099] The mass ratio of 5,5-dimethylhydantoin, polyvinyl alcohol-1, 3,4-epoxycyclohexylmethyl 3,4-epoxycyclohexylcarbamate, and glycidyl ether is 1:1.5:3:0.6.

[0100] In step S1, the molar ratio of 5,5-dimethylhydantoin, strong base and epichlorohydrin is 1:1:1, the mass ratio of 5,5-dimethylhydantoin and benzyltrimethylammonium chloride is 1:0.1, and the solid-liquid ratio of 5,5-dimethylhydantoin and solvent is 1g:50mL.

[0101] Example 10

[0102] This embodiment provides a modified polyvinyl alcohol gel, the preparation method of which includes the following steps:

[0103] S1. In 500 mL of solvent (water and ethanol in a 1:1 mass ratio), 10 g of 5,5-dimethylhydantoin (0.078 mol), 3.12 g of sodium hydroxide (0.078 mol), 7.22 g of epichlorohydrin (0.078 mol), and 1 g of benzyltrimethylammonium chloride catalyst were added and mixed. The mixture was reacted at 50 °C for 10 h to obtain 3-glycidyl-5,5-dimethylhydantoin.

[0104] S2. To the 3-glycidyl-5,5-dimethylhydantoin prepared in step S1, add 15g of polyvinyl alcohol-1 (weight average molecular weight Mw = 31000-50000), 20g of 3,4-epoxycyclohexylmethyl 3,4-epoxycyclohexylcarbamate and 4g of glycidyl ether, heat to 60℃ and react for 4h, filter, wash with ultrapure water to obtain modified polyvinyl alcohol gel;

[0105] The mass ratio of 5,5-dimethylhydantoin, polyvinyl alcohol-1, 3,4-epoxycyclohexylmethyl 3,4-epoxycyclohexylcarbamate, and glycidyl ether is 1:1.5:2:0.4.

[0106] In step S1, the molar ratio of 5,5-dimethylhydantoin, strong base and epichlorohydrin is 1:1:1, the mass ratio of 5,5-dimethylhydantoin and benzyltrimethylammonium chloride is 1:0.1, and the solid-liquid ratio of 5,5-dimethylhydantoin and solvent is 1g:50mL.

[0107] Example 11

[0108] This embodiment provides a modified polyvinyl alcohol gel, the preparation method of which includes the following steps:

[0109] S1. In 500 mL of solvent (water and ethanol in a 1:1 mass ratio), 10 g of 5,5-dimethylhydantoin (0.078 mol), 3.12 g of sodium hydroxide (0.078 mol), 7.22 g of epichlorohydrin (0.078 mol), and 1 g of benzyltrimethylammonium chloride catalyst were added and mixed. The mixture was reacted at 50 °C for 10 h to obtain 3-glycidyl-5,5-dimethylhydantoin.

[0110] S2. To the 3-glycidyl-5,5-dimethylhydantoin prepared in step S1, add 15g of polyvinyl alcohol-1 (weight average molecular weight Mw = 31000-50000), 20g of 3,4-epoxycyclohexylmethyl 3,4-epoxycyclohexylcarbamate and 8g of glycidyl ether, heat to 60℃ and react for 4h, filter, wash with ultrapure water to obtain modified polyvinyl alcohol gel;

[0111] The mass ratio of 5,5-dimethylhydantoin, polyvinyl alcohol-1, 3,4-epoxycyclohexylmethyl 3,4-epoxycyclohexylcarbamate, and glycidyl ether is 1:1.5:2:0.8.

[0112] In step S1, the molar ratio of 5,5-dimethylhydantoin, strong base and epichlorohydrin is 1:1:1, the mass ratio of 5,5-dimethylhydantoin and benzyltrimethylammonium chloride is 1:0.1, and the solid-liquid ratio of 5,5-dimethylhydantoin and solvent is 1g:50mL.

[0113] Example 12

[0114] This embodiment provides a modified polyvinyl alcohol gel, the preparation method of which includes the following steps:

[0115] S1. In 500 mL of solvent (water and ethanol in a 1:1 mass ratio), 10 g of 5,5-dimethylhydantoin (0.078 mol), 3.12 g of sodium hydroxide (0.078 mol), 7.22 g of epichlorohydrin (0.078 mol), and 1 g of benzyltrimethylammonium chloride catalyst were added and mixed. The mixture was reacted at 50 °C for 10 h to obtain 3-glycidyl-5,5-dimethylhydantoin.

[0116] S2. To the 3-glycidyl-5,5-dimethylhydantoin prepared in step S1, add 15g of polyvinyl alcohol-1 (weight average molecular weight Mw = 31000-50000), 20g of 3,4-epoxycyclohexylmethyl 3,4-epoxycyclohexylcarbamate and 2g of glycidyl ether, heat to 60℃ and react for 4h, filter, wash with ultrapure water to obtain modified polyvinyl alcohol gel;

[0117] The mass ratio of 5,5-dimethylhydantoin, polyvinyl alcohol-1, 3,4-epoxycyclohexylmethyl 3,4-epoxycyclohexylcarbamate, and glycidyl ether is 1:1.5:2:0.2.

[0118] In step S1, the molar ratio of 5,5-dimethylhydantoin, strong base and epichlorohydrin is 1:1:1, the mass ratio of 5,5-dimethylhydantoin and benzyltrimethylammonium chloride is 1:0.1, and the solid-liquid ratio of 5,5-dimethylhydantoin and solvent is 1g:50mL.

[0119] Example 13

[0120] This embodiment provides a modified polyvinyl alcohol gel, the preparation method of which includes the following steps:

[0121] S1. In 500 mL of solvent (water and ethanol in a 1:1 mass ratio), 10 g of 5,5-dimethylhydantoin (0.078 mol), 3.12 g of sodium hydroxide (0.078 mol), 7.22 g of epichlorohydrin (0.078 mol), and 1 g of benzyltrimethylammonium chloride catalyst were added and mixed. The mixture was reacted at 50 °C for 10 h to obtain 3-glycidyl-5,5-dimethylhydantoin.

[0122] S2. To the 3-glycidyl-5,5-dimethylhydantoin prepared in step S1, add 15g of polyvinyl alcohol-1 (weight average molecular weight Mw = 31000-50000), 20g of 3,4-epoxycyclohexylmethyl 3,4-epoxycyclohexylcarbamate and 10g of glycidyl ether, heat to 60℃ and react for 4h, filter, wash with ultrapure water to obtain modified polyvinyl alcohol gel;

[0123] The mass ratio of 5,5-dimethylhydantoin, polyvinyl alcohol-1, 3,4-epoxycyclohexylmethyl 3,4-epoxycyclohexylcarbamate and glycidyl ether is 1:1.5:2:1.

[0124] In step S1, the molar ratio of 5,5-dimethylhydantoin, strong base and epichlorohydrin is 1:1:1, the mass ratio of 5,5-dimethylhydantoin and benzyltrimethylammonium chloride is 1:0.1, and the solid-liquid ratio of 5,5-dimethylhydantoin and solvent is 1g:50mL.

[0125] Example 14

[0126] This embodiment provides a modified polyvinyl alcohol gel, the preparation method of which includes the following steps:

[0127] S1. In 500 mL of solvent (water and ethanol in a 1:1 mass ratio), 10 g of 5,5-dimethylhydantoin (0.078 mol), 3.12 g of sodium hydroxide (0.078 mol), 7.22 g of epichlorohydrin (0.078 mol), and 1 g of benzyltrimethylammonium chloride catalyst were added and mixed. The mixture was reacted at 50 °C for 10 h to obtain 3-glycidyl-5,5-dimethylhydantoin.

[0128] S2. To the 3-glycidyl-5,5-dimethylhydantoin prepared in step S1, add 15g of polyvinyl alcohol-2 (weight average molecular weight Mw = 13000-23000), 20g of 3,4-epoxycyclohexylmethyl 3,4-epoxycyclohexylcarbamate, and 6g of glycidyl ether. Heat to 60℃ and react for 4 hours. Filter and wash with ultrapure water to obtain the modified polyvinyl alcohol gel. Figure 1 Here is a photograph of the modified polyvinyl alcohol gel.

[0129] The mass ratio of 5,5-dimethylhydantoin, polyvinyl alcohol-1, 3,4-epoxycyclohexylmethyl 3,4-epoxycyclohexylcarbamate, and glycidyl ether is 1:1.5:2:0.6.

[0130] In step S1, the molar ratio of 5,5-dimethylhydantoin, strong base and epichlorohydrin is 1:1:1, the mass ratio of 5,5-dimethylhydantoin and benzyltrimethylammonium chloride is 1:0.1, and the solid-liquid ratio of 5,5-dimethylhydantoin and solvent is 1g:50mL.

[0131] Example 15

[0132] This embodiment provides a modified polyvinyl alcohol gel, the preparation method of which includes the following steps:

[0133] S1. In 500 mL of solvent (water and ethanol in a 1:1 mass ratio), 10 g of 5,5-dimethylhydantoin (0.078 mol), 3.12 g of sodium hydroxide (0.078 mol), 7.22 g of epichlorohydrin (0.078 mol), and 1 g of benzyltrimethylammonium chloride catalyst were added and mixed. The mixture was reacted at 50 °C for 10 h to obtain 3-glycidyl-5,5-dimethylhydantoin.

[0134] S2. To the 3-glycidyl-5,5-dimethylhydantoin prepared in step S1, add 15g of polyvinyl alcohol-3 (weight average molecular weight Mw = 85000-124000), 20g of 3,4-epoxycyclohexylmethyl 3,4-epoxycyclohexylcarbamate, and 6g of glycidyl ether. Heat to 60℃ and react for 4 hours. Filter and wash with ultrapure water to obtain modified polyvinyl alcohol gel. Figure 1 Here is a photograph of the modified polyvinyl alcohol gel.

[0135] The mass ratio of 5,5-dimethylhydantoin, polyvinyl alcohol-1, 3,4-epoxycyclohexylmethyl 3,4-epoxycyclohexylcarbamate, and glycidyl ether is 1:1.5:2:0.6.

[0136] In step S1, the molar ratio of 5,5-dimethylhydantoin, strong base and epichlorohydrin is 1:1:1, the mass ratio of 5,5-dimethylhydantoin and benzyltrimethylammonium chloride is 1:0.1, and the solid-liquid ratio of 5,5-dimethylhydantoin and solvent is 1g:50mL.

[0137] Example 16

[0138] This embodiment provides a modified polyvinyl alcohol gel, the preparation method of which includes the following steps:

[0139] S1. In 500 mL of solvent (water and ethanol in a 1:1 mass ratio), 10 g of 5,5-dimethylhydantoin (0.078 mol), 3.12 g of sodium hydroxide (0.078 mol), 7.22 g of epichlorohydrin (0.078 mol), and 1 g of benzyltrimethylammonium chloride catalyst were added and mixed. The mixture was reacted at 50 °C for 10 h to obtain 3-glycidyl-5,5-dimethylhydantoin.

[0140] S2. To the 3-glycidyl-5,5-dimethylhydantoin prepared in step S1, add 15g of polyvinyl alcohol-4 (weight average molecular weight Mw = 9000-10000), 20g of 3,4-epoxycyclohexylmethyl 3,4-epoxycyclohexylcarbamate, and 6g of glycidyl ether. Heat to 60℃ and react for 4 hours. Filter and wash with ultrapure water to obtain the modified polyvinyl alcohol gel. Figure 1 Here is a photograph of the modified polyvinyl alcohol gel.

[0141] The mass ratio of 5,5-dimethylhydantoin, polyvinyl alcohol-1, 3,4-epoxycyclohexylmethyl 3,4-epoxycyclohexylcarbamate, and glycidyl ether is 1:1.5:2:0.6.

[0142] In step S1, the molar ratio of 5,5-dimethylhydantoin, strong base and epichlorohydrin is 1:1:1, the mass ratio of 5,5-dimethylhydantoin and benzyltrimethylammonium chloride is 1:0.1, and the solid-liquid ratio of 5,5-dimethylhydantoin and solvent is 1g:50mL.

[0143] Example 17

[0144] This embodiment provides a modified polyvinyl alcohol gel, the preparation method of which includes the following steps:

[0145] S1. In 500 mL of solvent (water and ethanol in a 1:1 mass ratio), 10 g of 5,5-dimethylhydantoin (0.078 mol), 3.12 g of sodium hydroxide (0.078 mol), 7.22 g of epichlorohydrin (0.078 mol), and 1 g of benzyltrimethylammonium chloride catalyst were added and mixed. The mixture was reacted at 50 °C for 10 h to obtain 3-glycidyl-5,5-dimethylhydantoin.

[0146] S2. To the 3-glycidyl-5,5-dimethylhydantoin prepared in step S1, add 15g of polyvinyl alcohol-5 (weight average molecular weight Mw = 146000-186000), 20g of 3,4-epoxycyclohexylmethyl 3,4-epoxycyclohexylcarbamate, and 6g of glycidyl ether. Heat to 60℃ and react for 4 hours. Filter and wash with ultrapure water to obtain the modified polyvinyl alcohol gel. Figure 1 Here is a photograph of the modified polyvinyl alcohol gel.

[0147] The mass ratio of 5,5-dimethylhydantoin, polyvinyl alcohol-1, 3,4-epoxycyclohexylmethyl 3,4-epoxycyclohexylcarbamate, and glycidyl ether is 1:1.5:2:0.6.

[0148] In step S1, the molar ratio of 5,5-dimethylhydantoin, strong base and epichlorohydrin is 1:1:1, the mass ratio of 5,5-dimethylhydantoin and benzyltrimethylammonium chloride is 1:0.1, and the solid-liquid ratio of 5,5-dimethylhydantoin and solvent is 1g:50mL.

[0149] Comparative Example 1

[0150] This comparative example provides a modified polyvinyl alcohol gel, the preparation method of which includes the following steps:

[0151] S1. In 500 mL of solvent (water and ethanol in a 1:1 mass ratio), 10 g of 5,5-dimethylhydantoin (0.078 mol), 3.12 g of sodium hydroxide (0.078 mol), 7.22 g of epichlorohydrin (0.078 mol), and 1 g of benzyltrimethylammonium chloride catalyst were added and mixed. The mixture was reacted at 50 °C for 10 h to obtain 3-glycidyl-5,5-dimethylhydantoin.

[0152] S2. To the 3-glycidyl-5,5-dimethylhydantoin prepared in step S1, add 30g of polyvinyl alcohol-1 (weight average molecular weight Mw = 31000-50000), 20g of 3,4-epoxycyclohexylmethyl 3,4-epoxycyclohexylcarbamate and 6g of glycidyl ether, heat to 60℃ and react for 4h, filter, wash with ultrapure water to obtain modified polyvinyl alcohol gel;

[0153] The mass ratio of 5,5-dimethylhydantoin, polyvinyl alcohol-1, 3,4-epoxycyclohexylmethyl 3,4-epoxycyclohexylcarbamate and glycidyl ether is 1:3:2:0.6.

[0154] In step S1, the molar ratio of 5,5-dimethylhydantoin, strong base and epichlorohydrin is 1:1:1, the mass ratio of 5,5-dimethylhydantoin and benzyltrimethylammonium chloride is 1:0.1, and the solid-liquid ratio of 5,5-dimethylhydantoin and solvent is 1g:50mL.

[0155] Comparative Example 2

[0156] This comparative example provides a modified polyvinyl alcohol gel, the preparation method of which includes the following steps:

[0157] S1. In 500 mL of solvent (water and ethanol in a 1:1 mass ratio), 10 g of 5,5-dimethylhydantoin (0.078 mol), 3.12 g of sodium hydroxide (0.078 mol), 7.22 g of epichlorohydrin (0.078 mol), and 1 g of benzyltrimethylammonium chloride catalyst were added and mixed. The mixture was reacted at 50 °C for 10 h to obtain 3-glycidyl-5,5-dimethylhydantoin.

[0158] S2. To the 3-glycidyl-5,5-dimethylhydantoin prepared in step S1, add 15g of polyvinyl alcohol-1 (weight average molecular weight Mw = 31000-50000), 35g of 3,4-epoxycyclohexylmethyl 3,4-epoxycyclohexylcarbamate and 6g of glycidyl ether, heat to 60℃ and react for 4h, filter, wash with ultrapure water to obtain modified polyvinyl alcohol gel;

[0159] The mass ratio of 5,5-dimethylhydantoin, polyvinyl alcohol-1, 3,4-epoxycyclohexylmethyl 3,4-epoxycyclohexylcarbamate, and glycidyl ether is 1:1.5:3.5:0.6.

[0160] In step S1, the molar ratio of 5,5-dimethylhydantoin, strong base and epichlorohydrin is 1:1:1, the mass ratio of 5,5-dimethylhydantoin and benzyltrimethylammonium chloride is 1:0.1, and the solid-liquid ratio of 5,5-dimethylhydantoin and solvent is 1g:50mL.

[0161] Comparative Example 3

[0162] This comparative example provides a modified polyvinyl alcohol gel, the preparation method of which includes the following steps:

[0163] S1. In 500 mL of solvent (water and ethanol in a 1:1 mass ratio), 10 g of 5,5-dimethylhydantoin (0.078 mol), 3.12 g of sodium hydroxide (0.078 mol), 7.22 g of epichlorohydrin (0.078 mol), and 1 g of benzyltrimethylammonium chloride catalyst were added and mixed. The mixture was reacted at 50 °C for 10 h to obtain 3-glycidyl-5,5-dimethylhydantoin.

[0164] S2. To the 3-glycidyl-5,5-dimethylhydantoin prepared in step S1, add 15g of polyvinyl alcohol-1 (weight average molecular weight Mw = 31000-50000), 20g of 3,4-epoxycyclohexylmethyl 3,4-epoxycyclohexylcarbamate and 15g of glycidyl ether, heat to 60℃ and react for 4h, filter, wash with ultrapure water to obtain modified polyvinyl alcohol gel;

[0165] The mass ratio of 5,5-dimethylhydantoin, polyvinyl alcohol-1, 3,4-epoxycyclohexylmethyl 3,4-epoxycyclohexylcarbamate, and glycidyl ether is 1:1.5:2:1.5.

[0166] In step S1, the molar ratio of 5,5-dimethylhydantoin, strong base and epichlorohydrin is 1:1:1, the mass ratio of 5,5-dimethylhydantoin and benzyltrimethylammonium chloride is 1:0.1, and the solid-liquid ratio of 5,5-dimethylhydantoin and solvent is 1g:50mL.

[0167] Comparative Example 4

[0168] This comparative example provides a modified polyvinyl alcohol gel, the preparation method of which includes the following steps:

[0169] S1. In 500 mL of solvent (water and ethanol in a 1:1 mass ratio), 10 g of 5,5-dimethylhydantoin (0.078 mol), 3.12 g of sodium hydroxide (0.078 mol), 7.22 g of epichlorohydrin (0.078 mol), and 1 g of benzyltrimethylammonium chloride catalyst were added and mixed. The mixture was reacted at 50 °C for 10 h to obtain 3-glycidyl-5,5-dimethylhydantoin.

[0170] S2. To the 3-glycidyl-5,5-dimethylhydantoin prepared in step S1, add 0g of polyvinyl alcohol-1 (weight average molecular weight Mw = 31000-50000), 20g of 3,4-epoxycyclohexylmethyl 3,4-epoxycyclohexylcarbamate and 6g of glycidyl ether, heat to 60℃ and react for 4h, filter, wash with ultrapure water to obtain modified polyvinyl alcohol gel;

[0171] The mass ratio of 5,5-dimethylhydantoin, polyvinyl alcohol-1, 3,4-epoxycyclohexylmethyl 3,4-epoxycyclohexylcarbamate and glycidyl ether is 1:0:2:0.6.

[0172] In step S1, the molar ratio of 5,5-dimethylhydantoin, strong base and epichlorohydrin is 1:1:1, the mass ratio of 5,5-dimethylhydantoin and benzyltrimethylammonium chloride is 1:0.1, and the solid-liquid ratio of 5,5-dimethylhydantoin and solvent is 1g:50mL.

[0173] Comparative Example 5

[0174] This comparative example provides a modified polyvinyl alcohol gel, the preparation method of which includes the following steps:

[0175] S1. In 500 mL of solvent (water and ethanol in a 1:1 mass ratio), 10 g of 5,5-dimethylhydantoin (0.078 mol), 3.12 g of sodium hydroxide (0.078 mol), 7.22 g of epichlorohydrin (0.078 mol), and 1 g of benzyltrimethylammonium chloride catalyst were added and mixed. The mixture was reacted at 50 °C for 10 h to obtain 3-glycidyl-5,5-dimethylhydantoin.

[0176] S2. To the 3-glycidyl-5,5-dimethylhydantoin prepared in step S1, add 15g of polyvinyl alcohol-1 (weight average molecular weight Mw = 31000-50000), 0g of 3,4-epoxycyclohexylmethyl 3,4-epoxycyclohexylcarbamate and 6g of glycidyl ether, heat to 60℃ and react for 4h, filter, wash with ultrapure water to obtain modified polyvinyl alcohol gel;

[0177] The mass ratio of 5,5-dimethylhydantoin, polyvinyl alcohol-1, 3,4-epoxycyclohexylmethyl 3,4-epoxycyclohexylcarbamate, and glycidyl ether is 1:1.5:0:0.6.

[0178] In step S1, the molar ratio of 5,5-dimethylhydantoin, strong base and epichlorohydrin is 1:1:1, the mass ratio of 5,5-dimethylhydantoin and benzyltrimethylammonium chloride is 1:0.1, and the solid-liquid ratio of 5,5-dimethylhydantoin and solvent is 1g:50mL.

[0179] Comparative Example 6

[0180] This comparative example provides a modified polyvinyl alcohol gel, the preparation method of which includes the following steps:

[0181] S1. In 500 mL of solvent (water and ethanol in a 1:1 mass ratio), 10 g of 5,5-dimethylhydantoin (0.078 mol), 3.12 g of sodium hydroxide (0.078 mol), 7.22 g of epichlorohydrin (0.078 mol), and 1 g of benzyltrimethylammonium chloride catalyst were added and mixed. The mixture was reacted at 50 °C for 10 h to obtain 3-glycidyl-5,5-dimethylhydantoin.

[0182] S2. To the 3-glycidyl-5,5-dimethylhydantoin prepared in step S1, add 15g of polyvinyl alcohol-1 (weight average molecular weight Mw = 31000-50000), 20g of 3,4-epoxycyclohexylmethyl 3,4-epoxycyclohexylcarbamate and 0g of glycidyl ether, heat to 60℃ and react for 4h, filter, wash with ultrapure water to obtain modified polyvinyl alcohol gel;

[0183] The mass ratio of 5,5-dimethylhydantoin, polyvinyl alcohol-1, 3,4-epoxycyclohexylmethyl 3,4-epoxycyclohexylcarbamate and glycidyl ether is 1:1.5:2:0.

[0184] In step S1, the molar ratio of 5,5-dimethylhydantoin, strong base and epichlorohydrin is 1:1:1, the mass ratio of 5,5-dimethylhydantoin and benzyltrimethylammonium chloride is 1:0.1, and the solid-liquid ratio of 5,5-dimethylhydantoin and solvent is 1g:50mL.

[0185] Comparative Example 7

[0186] This comparative example provides a modified polyvinyl alcohol gel, the preparation method of which includes the following steps:

[0187] S1. In 500 mL of solvent (water and ethanol in a 1:1 mass ratio), 10 g of 5,5-dimethylhydantoin (0.078 mol), 3.12 g of sodium hydroxide (0.078 mol), 7.22 g of epichlorohydrin (0.078 mol), and 1 g of benzyltrimethylammonium chloride catalyst were added and mixed. The mixture was reacted at 50 °C for 10 h to obtain 3-glycidyl-5,5-dimethylhydantoin.

[0188] S2. To the 3-glycidyl-5,5-dimethylhydantoin prepared in step S1, add 15g of polyvinyl alcohol-1 (weight average molecular weight Mw = 31000-50000), 20g of 3,4-epoxycyclohexylmethyl 3,4-epoxycyclohexylcarboxylate and 6g of epichlorohydrin, heat to 60℃ and react for 4h, filter, wash with ultrapure water to obtain modified polyvinyl alcohol gel;

[0189] The mass ratio of 5,5-dimethylhydantoin, polyvinyl alcohol-1, 3,4-epoxycyclohexylmethyl 3,4-epoxycyclohexylcarbamate and epichlorohydrin is 1:1.5:2:0.6.

[0190] In step S1, the molar ratio of 5,5-dimethylhydantoin, strong base and epichlorohydrin is 1:1:1, the mass ratio of 5,5-dimethylhydantoin and benzyltrimethylammonium chloride is 1:0.1, and the solid-liquid ratio of 5,5-dimethylhydantoin and solvent is 1g:50mL.

[0191] Performance testing

[0192] Antibacterial tests were performed on the modified polyvinyl alcohol gels of each embodiment and comparative example:

[0193] 1. Antibacterial effect of modified polyvinyl alcohol gel against Staphylococcus aureus

[0194] (1) Dry the modified polyvinyl alcohol gel prepared in each example or comparative example at 60°C. Use the dilution coating plate method to take 0.3g of modified polyvinyl alcohol gel in a 6-well plate as the experimental group, and use the experiment without adding modified polyvinyl alcohol gel as the blank control group.

[0195] (2) Add 2.3 mL of LB liquid culture medium to each well of the 6-well plate treated in step (1), and then add 450 μL of 10% LB liquid culture medium. 6 A suspension of Staphylococcus aureus at CFU / mL was incubated at 37°C for 5 hours, and then the colony count was calculated according to GB 4789.2-2010 standard.

[0196] (3) The antibacterial rate of the modified polyvinyl alcohol gel in each embodiment and comparative example was calculated using the following formula. The higher the antibacterial rate, the better the antibacterial effect of the modified polyvinyl alcohol gel against Staphylococcus aureus:

[0197] The inhibition rate (%) of modified polyvinyl alcohol gel against Staphylococcus aureus = (number of colonies in the blank control group - number of colonies in the experimental group) / number of colonies in the blank control group × 100%;

[0198] 2. Antibacterial effect of modified polyvinyl alcohol gel against Escherichia coli

[0199] (1) Dry the modified polyvinyl alcohol gel prepared in each example or comparative example at 60°C. Use the dilution coating plate method to take 0.3g of modified polyvinyl alcohol gel in a 6-well plate as the experimental group, and use the experiment without adding modified polyvinyl alcohol gel as the blank control group.

[0200] (2) Add 2.3 mL of LB liquid culture medium to each well of the 6-well plate treated in step (1), and then add 450 μL of 10% LB liquid culture medium. 6 The CFU / mL Escherichia coli suspension was incubated at 37°C for 5 hours, and then the colony count was calculated according to GB 4789.2-2010 standard.

[0201] (3) The antibacterial rate of the modified polyvinyl alcohol gel in each embodiment and comparative example was calculated using the following formula. The higher the antibacterial rate, the better the antibacterial effect of the modified polyvinyl alcohol gel against Escherichia coli:

[0202] The inhibition rate (%) of modified polyvinyl alcohol gel against Escherichia coli = (number of colonies in the blank control group - number of colonies in the experimental group) / number of colonies in the blank control group × 100%;

[0203] The experimental results are shown in the table below:

[0204] Table 1. Antibacterial effects of modified polyvinyl alcohol gels in each example and comparative example.

[0205]

[0206]

[0207] As shown in Table 1, in this invention, by controlling the mass ratio of 5,5-dimethylhydantoin, polyvinyl alcohol, 3,4-epoxycyclohexylmethyl 3,4-epoxycyclohexylcarbamate, and glycidyl ether, a stable three-dimensional network structure can be formed. This allows the antibacterial 5,5-dimethylhydantoin to be stably and uniformly bonded to the three-dimensional network structure through chemical bonds. At the same time, the formed three-dimensional network structure can also delay the loss of 5,5-dimethylhydantoin, which is beneficial to improving the stability of the modified polyvinyl alcohol gel, thereby achieving the purpose of improving the antibacterial effect of the modified polyvinyl alcohol gel.

[0208] Finally, it should be noted that the above embodiments are only used to illustrate the technical solutions of the present invention and are not intended to limit the scope of protection of the present invention. Although the present invention has been described in detail with reference to preferred embodiments, those skilled in the art should understand that modifications or equivalent substitutions can be made to the technical solutions of the present invention without departing from the essence and scope of the technical solutions of the present invention.

Claims

1. A method for preparing a modified polyvinyl alcohol gel, characterized in that, The preparation method includes the following steps: S1,5,5-dimethylhydantoin, a strong base, and epichlorohydrin are reacted to give 3-glycidyl-5,5-dimethylhydantoin. S2. Polyvinyl alcohol, 3,4-epoxycyclohexylmethyl 3,4-epoxycyclohexyl carboxylate, glycidyl ether, and 3-glycidyl-5,5-dimethylhydantoin are reacted to obtain modified polyvinyl alcohol gel. The mass ratio of 5,5-dimethylhydantoin, polyvinyl alcohol, 3,4-epoxycyclohexylmethyl 3,4-epoxycyclohexylcarbamate and glycidyl ether is 1:(0.5-2.5):(1-3):(0.2-1).

2. The method for preparing the modified polyvinyl alcohol gel as described in claim 1, characterized in that, The mass ratio of 5,5-dimethylhydantoin, polyvinyl alcohol, 3,4-epoxycyclohexylmethyl 3,4-epoxycyclohexylcarbamate and glycidyl ether is 1:(1-2):(1.5-2.5):(0.4-0.8).

3. The method for preparing the modified polyvinyl alcohol gel as described in claim 1, characterized in that, In step S2, the weight-average molecular weight Mw of the polyvinyl alcohol is 9000-186000.

4. The method for preparing the modified polyvinyl alcohol gel as described in claim 3, characterized in that, The weight-average molecular weight (Mw) of the polyvinyl alcohol is 13,000-124,000.

5. The method for preparing the modified polyvinyl alcohol gel as described in claim 4, characterized in that, The weight-average molecular weight (Mw) of the polyvinyl alcohol is 31,000-50,000.

6. The method for preparing the modified polyvinyl alcohol gel as described in claim 1, characterized in that, Includes at least one of the following (1)-(6): (1) In step S1, the molar ratio of 5,5-dimethylhydantoin, strong base and epichlorohydrin is 1:(0.8-2):1; (2) In step S1, the strong base is at least one of sodium hydroxide and potassium hydroxide; (3) In step S1, the reaction temperature is 35-60℃; (4) In step S1, the reaction time is 6-15 hours; (5) In step S1, the catalyst used in the reaction is benzyltrimethylammonium chloride; (6) In step S1, the solvents used in the reaction are water and ethanol.

7. The method for preparing the modified polyvinyl alcohol gel as described in claim 6, characterized in that, Includes at least one of the following (1)-(3): (1) The mass ratio of 5,5-dimethylhydantoin to benzyltrimethylammonium chloride is 1:(0.05-0.5); (2) The mass ratio of water to ethanol is 1:(0.5-3); (3) The solid-liquid ratio of the 5,5-dimethylhydantoin and the solvent is 1 g: (5-80) mL.

8. The method for preparing the modified polyvinyl alcohol gel as described in claim 1, characterized in that, Includes at least one of the following (1)-(3): (1) In step S2, the reaction temperature is 20-60℃; (2) In step S2, the reaction time is 2-15 hours; (3) In step S2, after the reaction, filtration and washing are also included.

9. A modified polyvinyl alcohol gel, characterized in that, It is prepared by any one of the preparation methods described in claims 1-8.

10. The application of the modified polyvinyl alcohol gel of claim 9 in antibacterial applications.

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