Haloamine polyethyleneimine gel as well as preparation method and application thereof

Abstract

The invention discloses halamine polyethyleneimine gel as well as a preparation method and application thereof, the preparation method comprises the following steps: S1, heating 3-(2 '-chloroethyl)-5, 5-dimethyl hydantoin and polyethyleneimine for reaction to obtain halamine quaternized polyethyleneimine; s2, carrying out a dehydration reaction on the halamine quaternized polyethyleneimine and lysine, and then carrying out a reaction with glutaraldehyde to obtain halamine polyethyleneimine gel; the mass ratio of the 3-(2 '-chloroethyl)-5, 5-dimethyl hydantoin to the polyethyleneimine is 1: (1-10), the mass ratio of the polyethyleneimine to the lysine is 1: (0.002-0.020), and the mass ratio of the polyethyleneimine to the glutaraldehyde is 1: (1-3). The halamine polyethyleneimine gel has a good antibacterial effect on staphylococcus aureus.

Description

Technical Field

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

[0002] Bacteria are ubiquitous in the human environment, present even in the air we breathe and inside the human body. When a person's immune system weakens, bacteria can breach the body's three lines of defense, leading to various bacterial infections and other diseases. To combat bacteria and prevent their invasion, scientists and researchers have developed numerous antibacterial drugs and materials, among which antibacterial gels are one such example.

[0003] Antimicrobial gels consist of an antimicrobial agent and a gel matrix. The antimicrobial agent is the core substance that enables the antimicrobial action of the gel, while the gel matrix provides stability and viscosity. Because antimicrobial gels can inhibit bacterial growth or kill bacteria, they can be used to treat diseases caused by bacterial infections and reduce the risk of bacterial transmission. They are now widely used in the medical and health field and have achieved effective therapeutic results; however, their antimicrobial efficacy still needs improvement.

[0004] Staphylococcus aureus is a Gram-positive bacterium that can cause localized purulent infections, pericarditis, pseudomembranous colitis, pneumonia, and in severe cases, even systemic infectious diseases such as sepsis and septicemia after infecting humans.

[0005] Therefore, developing a halogenated amine polyethyleneimine gel with high antibacterial effect against Staphylococcus aureus is of great significance. Summary of the Invention

[0006] The purpose of this invention is to solve the problem of insufficient antibacterial effect of antibacterial gels in the prior art, and to provide a halogenated amine polyethyleneimine gel, its preparation method and application.

[0007] To achieve the above objectives, the technical solution adopted by the present invention is as follows:

[0008] In a first aspect, the present invention provides a method for preparing a haloamine polyethyleneimine gel, the method comprising the following steps:

[0009] S1. Reaction of 3-(2'-chloroethyl)-5,5-dimethylhydantoin and polyethyleneimine by heating yields quaternized halogenated polyethyleneimine;

[0010] S2. Haloamine quaternized polyethyleneimine first undergoes a dehydration reaction with lysine, and then reacts with glutaraldehyde to obtain haloamine polyethyleneimine gel;

[0011] The mass ratio of 3-(2'-chloroethyl)-5,5-dimethylhydantoin to polyethyleneimine is 1:(1-10).

[0012] The mass ratio of polyethyleneimine to lysine is 1:(0.002-0.020);

[0013] The mass ratio of polyethyleneimine to glutaraldehyde is 1:(1-3).

[0014] This invention uses 3-(2'-chloroethyl)-5,5-dimethylhydantoin as an antibacterial agent, and modifies polyethyleneimine with lysine, which has antibacterial effects. Then, a gel is synthesized by Schiff base reaction between polyethyleneimine and glutaraldehyde, thereby obtaining a haloamine polyethyleneimine gel.

[0015] In the haloamine polyethyleneimine gel of the present invention, 3-(2'-chloroethyl)-5,5-dimethylhydantoin is used as the main antibacterial agent, and lysine and polyethyleneimine are used as auxiliary antibacterial agents. Modifying polyethyleneimine with 3-(2'-chloroethyl)-5,5-dimethylhydantoin and lysine can improve the antibacterial effect of the haloamine polyethyleneimine gel against Staphylococcus aureus. Furthermore, by controlling the mass ratio of 3-(2'-chloroethyl)-5,5-dimethylhydantoin to polyethyleneimine, the mass ratio of polyethyleneimine to lysine, and the mass ratio of polyethyleneimine to glutaraldehyde, the antibacterial effects of 3-(2'-chloroethyl)-5,5-dimethylhydantoin, lysine, and polyethyleneimine can be promoted, thereby significantly improving the antibacterial effect of the haloamine polyethyleneimine gel against Staphylococcus aureus.

[0016] It is worth noting that by controlling the mass ratio of polyethyleneimine and lysine, this invention can cause the carboxyl group of lysine to react with the amino group of polyethyleneimine, creating steric hindrance on the long chain of polyethyleneimine. This allows for the regulation of the number of amino groups in polyethyleneimine that react with glutaraldehyde, thus controlling the degree of reaction between polyethyleneimine and glutaraldehyde. This enables polyethyleneimine to react with glutaraldehyde to form a gel while retaining its strong antibacterial properties, which is beneficial for improving the antibacterial effect of haloamine polyethyleneimine gel against Staphylococcus aureus.

[0017] Preferably, the mass ratio of 3-(2'-chloroethyl)-5,5-dimethylhydantoin to polyethyleneimine is 1:(3-8).

[0018] Preferably, the mass ratio of polyethyleneimine to lysine is 1:(0.005-0.015).

[0019] Preferably, the mass ratio of polyethyleneimine to glutaraldehyde is 1:(1.5-2.5).

[0020] Preferably, in step S1, the weight-average molecular weight Mw of the polyethyleneimine is 600-250000.

[0021] In this invention, by regulating the weight-average molecular weight Mw of polyethyleneimine, the antibacterial effects of 3-(2'-chloroethyl)-5,5-dimethylhydantoin and polyethyleneimine can be further enhanced, thereby improving the antibacterial effect of haloamine polyethyleneimine gel against Staphylococcus aureus.

[0022] More preferably, the weight-average molecular weight Mw of the polyethyleneimine is one or any two of the following: 600, 1200, 1800, 2500, 10000, 100000, 250000.

[0023] More preferably, in step S1, the weight-average molecular weight Mw of the polyethyleneimine is 1800-250000.

[0024] More preferably, in step S1, the weight-average molecular weight Mw of the polyethyleneimine is 2500-100000.

[0025] Preferably, in step S1, the heating temperature is 75-80°C.

[0026] Preferably, in step S1, the reaction time is 18-24 hours.

[0027] Preferably, in step S1, the liquid environment of the reaction is water, and the solid-liquid ratio of the polyethyleneimine to water is 1g:(5-15)mL.

[0028] Preferably, in step S1, the preparation method of 3-(2'-chloroethyl)-5,5-dimethylhydantoin includes the following steps:

[0029] (1) 5,5-Dimethylhydantoin, a strong base and 1-bromo-2-chloroethane were reacted at 75-90℃, and the mixture was distilled under reduced pressure. Ethyl acetate and water were used as the extraction solution to extract the organic phase 1 of the supernatant.

[0030] (2) Mix the organic phase 1 of the supernatant liquid with the sodium bicarbonate aqueous solution, shake, and retain the organic phase 2 of the supernatant liquid.

[0031] (3) Add anhydrous sodium sulfate to the organic phase 2 of the upper clear liquid, filter, and collect the filtrate;

[0032] (4) The filtrate was concentrated and distilled under reduced pressure to obtain crystals, which were then ground, pulverized, and dried to obtain 3-(2'-chloroethyl)-5,5-dimethylhydantoin.

[0033] More preferably, in step (1), the molar ratio of 5,5-dimethylhydantoin, the strong base and 1-bromo-2-chloroethane is 1:1:(1-2).

[0034] More preferably, in step (1), the strong alkali is at least one of sodium hydroxide and potassium hydroxide.

[0035] More preferably, in step (1), the reaction time is 8-10 hours.

[0036] More preferably, in step (1), the liquid environment of the reaction is anhydrous ethanol, and the solid-liquid ratio of 5,5-dimethylhydantoin to anhydrous ethanol is 1g:(3-8)mL.

[0037] More preferably, in step (1), the endpoint of the vacuum distillation is the appearance of a white or pale yellow viscous solid-liquid mixture.

[0038] More preferably, in step (1), the volume ratio of ethyl acetate to water is (1-2):1.

[0039] More preferably, in step (2), the mass fraction of the sodium bicarbonate aqueous solution is 4-8%.

[0040] More preferably, in step (4), the drying temperature is 35-45°C.

[0041] Preferably, in step S2, the temperature of the dehydration reaction is 15-55℃ and the time is 0.5-48h.

[0042] Preferably, in step S2, the catalyst for the dehydration reaction is 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide hydrochloride (EDC) and N-hydroxysuccinimide (NHS).

[0043] More preferably, the molar ratio of 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide hydrochloride (EDC) to N-hydroxysuccinimide (NHS) is 1:(0.1-10).

[0044] More preferably, the molar ratio of 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide hydrochloride (EDC) to the mass ratio of polyethyleneimine is (0.2-2) mmol:1g.

[0045] Preferably, step S2 specifically involves: first adding lysine to quaternized polyethyleneimine with haloamine for dehydration reaction, then adding glutaraldehyde, stirring to carry out the reaction, pouring into a mold for gelation, and thus obtaining haloamine polyethyleneimine gel.

[0046] More preferably, the stirring time is 2-30 minutes.

[0047] In a second aspect, the present invention provides a haloamine polyethyleneimine gel, which is prepared by the preparation method described in the first aspect.

[0048] Thirdly, the present invention provides an application of haloamine polyethyleneimine gel in antibacterial applications.

[0049] Compared with the prior art, the beneficial effects of the present invention are as follows:

[0050] This invention uses 3-(2'-chloroethyl)-5,5-dimethylhydantoin as an antibacterial agent, and modifies polyethyleneimine with lysine, which has antibacterial effects. Then, a gel is synthesized by Schiff base reaction between polyethyleneimine and glutaraldehyde, thereby obtaining a haloamine polyethyleneimine gel.

[0051] In the haloamine polyethyleneimine gel of the present invention, 3-(2'-chloroethyl)-5,5-dimethylhydantoin is used as the main antibacterial agent, and lysine and polyethyleneimine are used as auxiliary antibacterial agents. Modifying polyethyleneimine with 3-(2'-chloroethyl)-5,5-dimethylhydantoin and lysine can improve the antibacterial effect of the haloamine polyethyleneimine gel against Staphylococcus aureus. Furthermore, by controlling the mass ratio of 3-(2'-chloroethyl)-5,5-dimethylhydantoin to polyethyleneimine, the mass ratio of polyethyleneimine to lysine, and the mass ratio of polyethyleneimine to glutaraldehyde, the antibacterial effects of 3-(2'-chloroethyl)-5,5-dimethylhydantoin, lysine, and polyethyleneimine can be promoted, thereby significantly improving the antibacterial effect of the haloamine polyethyleneimine gel against Staphylococcus aureus.

[0052] It is worth noting that by controlling the mass ratio of polyethyleneimine and lysine, this invention can cause the carboxyl group of lysine to react with the amino group of polyethyleneimine, creating steric hindrance on the long chain of polyethyleneimine. This allows for the regulation of the number of amino groups in polyethyleneimine that react with glutaraldehyde, thus controlling the degree of reaction between polyethyleneimine and glutaraldehyde. This enables polyethyleneimine to react with glutaraldehyde to form a gel while retaining its strong antibacterial properties, which is beneficial for improving the antibacterial effect of haloamine polyethyleneimine gel against Staphylococcus aureus. Attached Figure Description

[0053] Figure 1 The reaction flow diagram is for 3-(2'-chloroethyl)-5,5-dimethylhydantoin.

[0054] Figure 2 This is a flow chart of the reaction of quaternizing polyethyleneimine with haloamines, where n represents the degree of polymerization of polyethyleneimine.

[0055] Figure 3 This is a photograph of the haloamine polyethyleneimine gel from Example 1. Figure 3 A and Figure 3B are actual images of the haloamine polyethyleneimine gel from Example 1. Detailed Implementation

[0056] 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.

[0057] 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.

[0058] The reagents used in the various embodiments and comparative examples of this invention are as follows:

[0059] Polyethyleneimine 1, weight average molecular weight Mw = 10000, E808880, Maclean;

[0060] Polyethyleneimine 2, weight-average molecular weight Mw = 100,000, 767,276, Maclean;

[0061] Polyethyleneimine 3, weight-average molecular weight Mw = 2500, 767275, Maclean;

[0062] Polyethyleneimine 4, weight-average molecular weight Mw = 250,000, 767,274, Maclean;

[0063] Polyethyleneimine 5, weight-average molecular weight Mw = 1800, E808879, Maclean;

[0064] Polyethyleneimine 6, weight-average molecular weight Mw = 600, E808878, McLean.

[0065] The reaction flow chart of 3-(2'-chloroethyl)-5,5-dimethylhydantoin is as follows: Figure 1 As shown, its preparation method specifically includes the following steps:

[0066] (1) Add 5,5-dimethylhydantoin, sodium hydroxide and 1-bromo-2-chloroethane to anhydrous ethanol, heat to 80°C and reflux for 8 hours, distill under reduced pressure until a white or pale yellow viscous solid-liquid mixture appears. Use ethyl acetate and water in a volume ratio of 1:1 as the extraction solution for extraction, and retain the organic phase 1 of the supernatant liquid.

[0067] (2) Mix the organic phase 1 of the supernatant with a 5% sodium bicarbonate aqueous solution, shake for 5 min, and retain the organic phase 2 of the supernatant.

[0068] (3) Add anhydrous sodium sulfate to the organic phase 2 of the upper clear liquid, shake for 5 min, filter, and collect the filtrate;

[0069] (4) The filtrate was concentrated and distilled under reduced pressure to obtain crystals, which were then ground and dried at 40°C to obtain 3-(2'-chloroethyl)-5,5-dimethylhydantoin.

[0070] In step (1), the molar ratio of 5,5-dimethylhydantoin, strong base and 1-bromo-2-chloroethane is 1:1:1.5, the solid-liquid ratio of 5,5-dimethylhydantoin to anhydrous ethanol is 1g:5mL, and the volume ratio of the extract to anhydrous ethanol is 1:1.

[0071] The volume ratio of the sodium bicarbonate aqueous solution to anhydrous ethanol is 1:1.

[0072] Example 1

[0073] This embodiment provides a haloamine polyethyleneimine gel, the preparation method of which includes the following steps:

[0074] S1. Add 5.0 g of 3-(2'-chloroethyl)-5,5-dimethylhydantoin and 25.0 g of polyethyleneimine 1 (weight average molecular weight Mw = 10000) to 225 mL of water, heat to 75 °C and react for 24 h to obtain quaternized halogenated polyethyleneimine. The reaction flow chart is shown below. Figure 2 As shown;

[0075] S2. In step S1, 12.5 mmol of 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide hydrochloride (EDC), 12.5 mmol of N-hydroxysuccinimide (NHS), and 0.25 g of lysine were added to the quaternized polyethyleneimine of the haloamine. The mixture was subjected to a dehydration reaction at 25 °C for 2 h. Then, 50.0 g of glacial glutaraldehyde was added. The mixture was first stirred vigorously for 1 minute, then slowly stirred for 15 minutes until the viscosity of the solution increased significantly. The solution was poured into a mold for gelation to obtain the haloamine polyethyleneimine gel. A sample image is shown below. Figure 3 As shown;

[0076] The mass ratio of 3-(2'-chloroethyl)-5,5-dimethylhydantoin to polyethyleneimine is 1:5.

[0077] The mass ratio of polyethyleneimine to lysine is 1:0.010;

[0078] The mass ratio of polyethyleneimine to glutaraldehyde is 1:2.

[0079] Example 2

[0080] This embodiment provides a haloamine polyethyleneimine gel, the preparation method of which includes the following steps:

[0081] S1. Add 8.33 g of 3-(2'-chloroethyl)-5,5-dimethylhydantoin and 25.0 g of polyethyleneimine 1 (weight average molecular weight Mw = 10000) to 225 mL of water, heat to 75 °C and react for 24 h to obtain quaternized halogenated polyethyleneimine;

[0082] S2. In step S1, 12.5 mmol of 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide hydrochloride (EDC), 12.5 mmol of N-hydroxysuccinimide (NHS) and 0.25 g of lysine are added to the quaternized polyethyleneimine of haloamines. The mixture is dehydrated at 25 °C for 2 h. Then, 50.0 g of glacial glutaraldehyde is added. The mixture is first stirred vigorously for 1 minute, and then slowly stirred for 15 min until the viscosity of the solution increases significantly. The mixture is then poured into a mold for gelation to obtain haloamine polyethyleneimine gel.

[0083] The mass ratio of 3-(2'-chloroethyl)-5,5-dimethylhydantoin to polyethyleneimine is 1:3.

[0084] The mass ratio of polyethyleneimine to lysine is 1:0.010;

[0085] The mass ratio of polyethyleneimine to glutaraldehyde is 1:2.

[0086] Example 3

[0087] This embodiment provides a haloamine polyethyleneimine gel, the preparation method of which includes the following steps:

[0088] S1. Add 3.125 g of 3-(2'-chloroethyl)-5,5-dimethylhydantoin and 25.0 g of polyethyleneimine 1 (weight average molecular weight Mw = 10000) to 225 mL of water, heat to 75 °C and react for 24 h to obtain quaternized polyethyleneimine with haloamine;

[0089] S2. In step S1, 12.5 mmol of 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide hydrochloride (EDC), 12.5 mmol of N-hydroxysuccinimide (NHS) and 0.25 g of lysine are added to the quaternized polyethyleneimine of haloamines. The mixture is dehydrated at 25 °C for 2 h. Then, 50.0 g of glacial glutaraldehyde is added. The mixture is first stirred vigorously for 1 minute, and then slowly stirred for 15 min until the viscosity of the solution increases significantly. The mixture is then poured into a mold for gelation to obtain haloamine polyethyleneimine gel.

[0090] The mass ratio of 3-(2'-chloroethyl)-5,5-dimethylhydantoin to polyethyleneimine is 1:8.

[0091] The mass ratio of polyethyleneimine to lysine is 1:0.010;

[0092] The mass ratio of polyethyleneimine to glutaraldehyde is 1:2.

[0093] Example 4

[0094] This embodiment provides a haloamine polyethyleneimine gel, the preparation method of which includes the following steps:

[0095] S1. Add 25.0 g of 3-(2'-chloroethyl)-5,5-dimethylhydantoin and 25.0 g of polyethyleneimine 1 (weight average molecular weight Mw = 10000) to 225 mL of water, heat to 75 °C and react for 24 h to obtain quaternized polyethyleneimine with haloamine;

[0096] S2. In step S1, 12.5 mmol of 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide hydrochloride (EDC), 12.5 mmol of N-hydroxysuccinimide (NHS) and 0.25 g of lysine are added to the quaternized polyethyleneimine of haloamines. The mixture is dehydrated at 25 °C for 2 h. Then, 50.0 g of glacial glutaraldehyde is added. The mixture is first stirred vigorously for 1 minute, and then slowly stirred for 15 min until the viscosity of the solution increases significantly. The mixture is then poured into a mold for gelation to obtain haloamine polyethyleneimine gel.

[0097] The mass ratio of 3-(2'-chloroethyl)-5,5-dimethylhydantoin to polyethyleneimine is 1:1.

[0098] The mass ratio of polyethyleneimine to lysine is 1:0.010;

[0099] The mass ratio of polyethyleneimine to glutaraldehyde is 1:2.

[0100] Example 5

[0101] This embodiment provides a haloamine polyethyleneimine gel, the preparation method of which includes the following steps:

[0102] S1. Add 2.5 g of 3-(2'-chloroethyl)-5,5-dimethylhydantoin and 25.0 g of polyethyleneimine 1 (weight average molecular weight Mw = 10000) to 225 mL of water, heat to 75 °C and react for 24 h to obtain quaternized polyethyleneimine with haloamine;

[0103] S2. In step S1, 12.5 mmol of 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide hydrochloride (EDC), 12.5 mmol of N-hydroxysuccinimide (NHS) and 0.25 g of lysine are added to the quaternized polyethyleneimine of haloamines. The mixture is dehydrated at 25 °C for 2 h. Then, 50.0 g of glacial glutaraldehyde is added. The mixture is first stirred vigorously for 1 minute, and then slowly stirred for 15 min until the viscosity of the solution increases significantly. The mixture is then poured into a mold for gelation to obtain haloamine polyethyleneimine gel.

[0104] The mass ratio of 3-(2'-chloroethyl)-5,5-dimethylhydantoin to polyethyleneimine is 1:10.

[0105] The mass ratio of polyethyleneimine to lysine is 1:0.010;

[0106] The mass ratio of polyethyleneimine to glutaraldehyde is 1:2.

[0107] Example 6

[0108] This embodiment provides a haloamine polyethyleneimine gel, the preparation method of which includes the following steps:

[0109] S1. Add 5.0 g of 3-(2'-chloroethyl)-5,5-dimethylhydantoin and 25.0 g of polyethyleneimine 2 (weight average molecular weight Mw = 100,000) to 225 mL of water, heat to 75 °C and react for 24 h to obtain quaternized polyethyleneimine with haloamine;

[0110] S2. In step S1, 12.5 mmol of 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide hydrochloride (EDC), 12.5 mmol of N-hydroxysuccinimide (NHS) and 0.25 g of lysine are added to the quaternized polyethyleneimine of haloamines. The mixture is dehydrated at 25 °C for 2 h. Then, 50.0 g of glacial glutaraldehyde is added. The mixture is first stirred vigorously for 1 minute, and then slowly stirred for 15 min until the viscosity of the solution increases significantly. The mixture is then poured into a mold for gelation to obtain haloamine polyethyleneimine gel.

[0111] The mass ratio of 3-(2'-chloroethyl)-5,5-dimethylhydantoin to polyethyleneimine is 1:5.

[0112] The mass ratio of polyethyleneimine to lysine is 1:0.010;

[0113] The mass ratio of polyethyleneimine to glutaraldehyde is 1:2.

[0114] Example 7

[0115] This embodiment provides a haloamine polyethyleneimine gel, the preparation method of which includes the following steps:

[0116] S1. Add 5.0 g of 3-(2'-chloroethyl)-5,5-dimethylhydantoin and 25.0 g of polyethyleneimine 3 (weight average molecular weight Mw = 2500) to 225 mL of water, heat to 75 °C and react for 24 h to obtain quaternized polyethyleneimine with haloamine;

[0117] S2. In step S1, 12.5 mmol of 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide hydrochloride (EDC), 12.5 mmol of N-hydroxysuccinimide (NHS) and 0.25 g of lysine are added to the quaternized polyethyleneimine of haloamines. The mixture is dehydrated at 25 °C for 2 h. Then, 50.0 g of glacial glutaraldehyde is added. The mixture is first stirred vigorously for 1 minute, and then slowly stirred for 15 min until the viscosity of the solution increases significantly. The mixture is then poured into a mold for gelation to obtain haloamine polyethyleneimine gel.

[0118] The mass ratio of 3-(2'-chloroethyl)-5,5-dimethylhydantoin to polyethyleneimine is 1:5.

[0119] The mass ratio of polyethyleneimine to lysine is 1:0.010;

[0120] The mass ratio of polyethyleneimine to glutaraldehyde is 1:2.

[0121] Example 8

[0122] This embodiment provides a haloamine polyethyleneimine gel, the preparation method of which includes the following steps:

[0123] S1. Add 5.0 g of 3-(2'-chloroethyl)-5,5-dimethylhydantoin and 25.0 g of polyethyleneimine 4 (weight average molecular weight Mw = 250000) to 225 mL of water, heat to 75 °C and react for 24 h to obtain quaternized polyethyleneimine with haloamine;

[0124] S2. In step S1, 12.5 mmol of 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide hydrochloride (EDC), 12.5 mmol of N-hydroxysuccinimide (NHS) and 0.25 g of lysine are added to the quaternized polyethyleneimine of haloamines. The mixture is dehydrated at 25 °C for 2 h. Then, 50.0 g of glacial glutaraldehyde is added. The mixture is first stirred vigorously for 1 minute, and then slowly stirred for 15 min until the viscosity of the solution increases significantly. The mixture is then poured into a mold for gelation to obtain haloamine polyethyleneimine gel.

[0125] The mass ratio of 3-(2'-chloroethyl)-5,5-dimethylhydantoin to polyethyleneimine is 1:5.

[0126] The mass ratio of polyethyleneimine to lysine is 1:0.010;

[0127] The mass ratio of polyethyleneimine to glutaraldehyde is 1:2.

[0128] Example 9

[0129] This embodiment provides a haloamine polyethyleneimine gel, the preparation method of which includes the following steps:

[0130] S1. Add 5.0 g of 3-(2'-chloroethyl)-5,5-dimethylhydantoin and 25.0 g of polyethyleneimine 5 (weight average molecular weight Mw = 1800) to 225 mL of water, heat to 75 °C and react for 24 h to obtain quaternized polyethyleneimine with haloamine;

[0131] S2. In step S1, 12.5 mmol of 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide hydrochloride (EDC), 12.5 mmol of N-hydroxysuccinimide (NHS) and 0.25 g of lysine are added to the quaternized polyethyleneimine of haloamines. The mixture is dehydrated at 25 °C for 2 h. Then, 50.0 g of glacial glutaraldehyde is added. The mixture is first stirred vigorously for 1 minute, and then slowly stirred for 15 min until the viscosity of the solution increases significantly. The mixture is then poured into a mold for gelation to obtain haloamine polyethyleneimine gel.

[0132] The mass ratio of 3-(2'-chloroethyl)-5,5-dimethylhydantoin to polyethyleneimine is 1:5.

[0133] The mass ratio of polyethyleneimine to lysine is 1:0.010;

[0134] The mass ratio of polyethyleneimine to glutaraldehyde is 1:2.

[0135] Example 10

[0136] This embodiment provides a haloamine polyethyleneimine gel, the preparation method of which includes the following steps:

[0137] S1. Add 5.0 g of 3-(2'-chloroethyl)-5,5-dimethylhydantoin and 25.0 g of polyethyleneimine 6 (weight average molecular weight Mw = 600) to 225 mL of water, heat to 75 °C and react for 24 h to obtain quaternized polyethyleneimine with haloamine;

[0138] S2. In step S1, 12.5 mmol of 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide hydrochloride (EDC), 12.5 mmol of N-hydroxysuccinimide (NHS) and 0.25 g of lysine are added to the quaternized polyethyleneimine of haloamines. The mixture is dehydrated at 25 °C for 2 h. Then, 50.0 g of glacial glutaraldehyde is added. The mixture is first stirred vigorously for 1 minute, and then slowly stirred for 15 min until the viscosity of the solution increases significantly. The mixture is then poured into a mold for gelation to obtain haloamine polyethyleneimine gel.

[0139] The mass ratio of 3-(2'-chloroethyl)-5,5-dimethylhydantoin to polyethyleneimine is 1:5.

[0140] The mass ratio of polyethyleneimine to lysine is 1:0.010;

[0141] The mass ratio of polyethyleneimine to glutaraldehyde is 1:2.

[0142] Example 11

[0143] This embodiment provides a haloamine polyethyleneimine gel, the preparation method of which includes the following steps:

[0144] S1. Add 5.0 g of 3-(2'-chloroethyl)-5,5-dimethylhydantoin and 25.0 g of polyethyleneimine 1 (weight average molecular weight Mw = 10000) to 225 mL of water, heat to 75 °C and react for 24 h to obtain quaternized polyethyleneimine with haloamine;

[0145] S2. In step S1, 12.5 mmol of 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide hydrochloride (EDC), 12.5 mmol of N-hydroxysuccinimide (NHS) and 0.125 g of lysine are added to the quaternized polyethyleneimine of the haloamine. The mixture is dehydrated at 25 °C for 2 h. Then, 50.0 g of glacial glutaraldehyde is added. The mixture is first stirred vigorously for 1 minute, and then slowly stirred for 15 min until the viscosity of the solution increases significantly. The mixture is then poured into a mold for gelation to obtain the haloamine polyethyleneimine gel.

[0146] The mass ratio of 3-(2'-chloroethyl)-5,5-dimethylhydantoin to polyethyleneimine is 1:5.

[0147] The mass ratio of polyethyleneimine to lysine is 1:0.005;

[0148] The mass ratio of polyethyleneimine to glutaraldehyde is 1:2.

[0149] Example 12

[0150] This embodiment provides a haloamine polyethyleneimine gel, the preparation method of which includes the following steps:

[0151] S1. Add 5.0 g of 3-(2'-chloroethyl)-5,5-dimethylhydantoin and 25.0 g of polyethyleneimine 1 (weight average molecular weight Mw = 10000) to 225 mL of water, heat to 75 °C and react for 24 h to obtain quaternized polyethyleneimine with haloamine;

[0152] S2. In step S1, 12.5 mmol of 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide hydrochloride (EDC), 12.5 mmol of N-hydroxysuccinimide (NHS) and 0.375 g of lysine were added to the quaternized polyethyleneimine of haloamines. The mixture was dehydrated at 25 °C for 2 h. Then, 50.0 g of glacial glutaraldehyde was added. The mixture was first stirred vigorously for 1 minute, and then slowly stirred for 15 min until the viscosity of the solution increased significantly. The mixture was then poured into a mold for gelation to obtain haloamine polyethyleneimine gel.

[0153] The mass ratio of 3-(2'-chloroethyl)-5,5-dimethylhydantoin to polyethyleneimine is 1:5.

[0154] The mass ratio of polyethyleneimine to lysine is 1:0.015;

[0155] The mass ratio of polyethyleneimine to glutaraldehyde is 1:2.

[0156] Example 13

[0157] This embodiment provides a haloamine polyethyleneimine gel, the preparation method of which includes the following steps:

[0158] S1. Add 5.0 g of 3-(2'-chloroethyl)-5,5-dimethylhydantoin and 25.0 g of polyethyleneimine 1 (weight average molecular weight Mw = 10000) to 225 mL of water, heat to 75 °C and react for 24 h to obtain quaternized polyethyleneimine with haloamine;

[0159] S2. In step S1, 12.5 mmol of 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide hydrochloride (EDC), 12.5 mmol of N-hydroxysuccinimide (NHS) and 0.05 g of lysine are added to the quaternized polyethyleneimine of haloamines. The mixture is dehydrated at 25 °C for 2 h. Then, 50.0 g of glacial glutaraldehyde is added. The mixture is first stirred vigorously for 1 minute, and then slowly stirred for 15 min until the viscosity of the solution increases significantly. The mixture is then poured into a mold for gelation to obtain haloamine polyethyleneimine gel.

[0160] The mass ratio of 3-(2'-chloroethyl)-5,5-dimethylhydantoin to polyethyleneimine is 1:5.

[0161] The mass ratio of polyethyleneimine to lysine is 1:0.002;

[0162] The mass ratio of polyethyleneimine to glutaraldehyde is 1:2.

[0163] Example 14

[0164] This embodiment provides a haloamine polyethyleneimine gel, the preparation method of which includes the following steps:

[0165] S1. Add 5.0 g of 3-(2'-chloroethyl)-5,5-dimethylhydantoin and 25.0 g of polyethyleneimine 1 (weight average molecular weight Mw = 10000) to 225 mL of water, heat to 75 °C and react for 24 h to obtain quaternized polyethyleneimine with haloamine;

[0166] S2. In step S1, 12.5 mmol of 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide hydrochloride (EDC), 12.5 mmol of N-hydroxysuccinimide (NHS) and 0.50 g of lysine are added to the quaternized polyethyleneimine of haloamines. The mixture is dehydrated at 25 °C for 2 h. Then, 50.0 g of glacial glutaraldehyde is added. The mixture is first stirred vigorously for 1 minute, and then slowly stirred for 15 min until the viscosity of the solution increases significantly. The mixture is then poured into a mold for gelation to obtain haloamine polyethyleneimine gel.

[0167] The mass ratio of 3-(2'-chloroethyl)-5,5-dimethylhydantoin to polyethyleneimine is 1:5.

[0168] The mass ratio of polyethyleneimine to lysine is 1:0.020;

[0169] The mass ratio of polyethyleneimine to glutaraldehyde is 1:2.

[0170] Example 15

[0171] This embodiment provides a haloamine polyethyleneimine gel, the preparation method of which includes the following steps:

[0172] S1. Add 5.0 g of 3-(2'-chloroethyl)-5,5-dimethylhydantoin and 25.0 g of polyethyleneimine 1 (weight average molecular weight Mw = 10000) to 225 mL of water, heat to 75 °C and react for 24 h to obtain quaternized polyethyleneimine with haloamine;

[0173] S2. In step S1, 12.5 mmol of 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide hydrochloride (EDC), 12.5 mmol of N-hydroxysuccinimide (NHS) and 0.25 g of lysine are added to the quaternized polyethyleneimine of haloamines. The mixture is dehydrated at 25 °C for 2 h. Then, 50.0 g of glacial glutaraldehyde is added. The mixture is first stirred vigorously for 1 minute, and then slowly stirred for 15 min until the viscosity of the solution increases significantly. The mixture is then poured into a mold for gelation to obtain haloamine polyethyleneimine gel.

[0174] The mass ratio of 3-(2'-chloroethyl)-5,5-dimethylhydantoin to polyethyleneimine is 1:5.

[0175] The mass ratio of polyethyleneimine to lysine is 1:0.010;

[0176] The mass ratio of polyethyleneimine to glutaraldehyde is 1:1.5.

[0177] Example 16

[0178] This embodiment provides a haloamine polyethyleneimine gel, the preparation method of which includes the following steps:

[0179] S1. Add 5.0 g of 3-(2'-chloroethyl)-5,5-dimethylhydantoin and 25.0 g of polyethyleneimine 1 (weight average molecular weight Mw = 10000) to 225 mL of water, heat to 75 °C and react for 24 h to obtain quaternized polyethyleneimine with haloamine;

[0180] S2. In step S1, 12.5 mmol of 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide hydrochloride (EDC), 12.5 mmol of N-hydroxysuccinimide (NHS) and 0.25 g of lysine are added to the quaternized polyethyleneimine of haloamines. The mixture is dehydrated at 25 °C for 2 h. Then, 50.0 g of glacial glutaraldehyde is added. The mixture is first stirred vigorously for 1 minute, and then slowly stirred for 15 min until the viscosity of the solution increases significantly. The mixture is then poured into a mold for gelation to obtain haloamine polyethyleneimine gel.

[0181] The mass ratio of 3-(2'-chloroethyl)-5,5-dimethylhydantoin to polyethyleneimine is 1:5.

[0182] The mass ratio of polyethyleneimine to lysine is 1:0.010;

[0183] The mass ratio of polyethyleneimine to glutaraldehyde is 1:2.5.

[0184] Example 17

[0185] This embodiment provides a haloamine polyethyleneimine gel, the preparation method of which includes the following steps:

[0186] S1. Add 5.0 g of 3-(2'-chloroethyl)-5,5-dimethylhydantoin and 25.0 g of polyethyleneimine 1 (weight average molecular weight Mw = 10000) to 225 mL of water, heat to 75 °C and react for 24 h to obtain quaternized polyethyleneimine with haloamine;

[0187] S2. In step S1, 12.5 mmol of 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide hydrochloride (EDC), 12.5 mmol of N-hydroxysuccinimide (NHS) and 0.25 g of lysine are added to the quaternized polyethyleneimine of haloamines. The mixture is dehydrated at 25 °C for 2 h. Then, 50.0 g of glacial glutaraldehyde is added. The mixture is first stirred vigorously for 1 minute, and then slowly stirred for 15 min until the viscosity of the solution increases significantly. The mixture is then poured into a mold for gelation to obtain haloamine polyethyleneimine gel.

[0188] The mass ratio of 3-(2'-chloroethyl)-5,5-dimethylhydantoin to polyethyleneimine is 1:5.

[0189] The mass ratio of polyethyleneimine to lysine is 1:0.010;

[0190] The mass ratio of polyethyleneimine to glutaraldehyde is 1:1.

[0191] Example 18

[0192] This embodiment provides a haloamine polyethyleneimine gel, the preparation method of which includes the following steps:

[0193] S1. Add 5.0 g of 3-(2'-chloroethyl)-5,5-dimethylhydantoin and 25.0 g of polyethyleneimine 1 (weight average molecular weight Mw = 10000) to 225 mL of water, heat to 75 °C and react for 24 h to obtain quaternized polyethyleneimine with haloamine;

[0194] S2. In step S1, 12.5 mmol of 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide hydrochloride (EDC), 12.5 mmol of N-hydroxysuccinimide (NHS) and 0.25 g of lysine are added to the quaternized polyethyleneimine of haloamines. The mixture is dehydrated at 25 °C for 2 h. Then, 50.0 g of glacial glutaraldehyde is added. The mixture is first stirred vigorously for 1 minute, and then slowly stirred for 15 min until the viscosity of the solution increases significantly. The mixture is then poured into a mold for gelation to obtain haloamine polyethyleneimine gel.

[0195] The mass ratio of 3-(2'-chloroethyl)-5,5-dimethylhydantoin to polyethyleneimine is 1:5.

[0196] The mass ratio of polyethyleneimine to lysine is 1:0.010;

[0197] The mass ratio of polyethyleneimine to glutaraldehyde is 1:3.

[0198] Comparative Example 1

[0199] This comparative example provides a haloamine polyethyleneimine gel, the preparation method of which includes the following steps:

[0200] S1. Add 31.25 g of 3-(2'-chloroethyl)-5,5-dimethylhydantoin and 25.0 g of polyethyleneimine 1 (weight average molecular weight Mw = 10000) to 225 mL of water, heat to 75 °C and react for 24 h to obtain quaternized polyethyleneimine with haloamine;

[0201] S2. In step S1, 12.5 mmol of 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide hydrochloride (EDC), 12.5 mmol of N-hydroxysuccinimide (NHS) and 0.25 g of lysine are added to the quaternized polyethyleneimine of haloamines. The mixture is dehydrated at 25 °C for 2 h. Then, 50.0 g of glacial glutaraldehyde is added. The mixture is first stirred vigorously for 1 minute, and then slowly stirred for 15 min until the viscosity of the solution increases significantly. The mixture is then poured into a mold for gelation to obtain haloamine polyethyleneimine gel.

[0202] The mass ratio of 3-(2'-chloroethyl)-5,5-dimethylhydantoin to polyethyleneimine is 1:0.8.

[0203] The mass ratio of polyethyleneimine to lysine is 1:0.010;

[0204] The mass ratio of polyethyleneimine to glutaraldehyde is 1:2.

[0205] Comparative Example 2

[0206] This comparative example provides a haloamine polyethyleneimine gel, the preparation method of which includes the following steps:

[0207] S1. Add 1.67 g of 3-(2'-chloroethyl)-5,5-dimethylhydantoin and 25.0 g of polyethyleneimine 1 (weight average molecular weight Mw = 10000) to 225 mL of water, heat to 75 °C and react for 24 h to obtain quaternized polyethyleneimine with haloamine;

[0208] S2. In step S1, 12.5 mmol of 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide hydrochloride (EDC), 12.5 mmol of N-hydroxysuccinimide (NHS) and 0.25 g of lysine are added to the quaternized polyethyleneimine of haloamines. The mixture is dehydrated at 25 °C for 2 h. Then, 50.0 g of glacial glutaraldehyde is added. The mixture is first stirred vigorously for 1 minute, and then slowly stirred for 15 min until the viscosity of the solution increases significantly. The mixture is then poured into a mold for gelation to obtain haloamine polyethyleneimine gel.

[0209] The mass ratio of 3-(2'-chloroethyl)-5,5-dimethylhydantoin to polyethyleneimine is 1:15.

[0210] The mass ratio of polyethyleneimine to lysine is 1:0.010;

[0211] The mass ratio of polyethyleneimine to glutaraldehyde is 1:2.

[0212] Comparative Example 3

[0213] This comparative example provides a haloamine polyethyleneimine gel, the preparation method of which includes the following steps:

[0214] S1. Add 5.0 g of 3-(2'-chloroethyl)-5,5-dimethylhydantoin and 25.0 g of polyethyleneimine 1 (weight average molecular weight Mw = 10000) to 225 mL of water, heat to 75 °C and react for 24 h to obtain quaternized polyethyleneimine with haloamine;

[0215] S2. Add 50.0g of glacial glutaraldehyde to the quaternized polyethyleneimine of haloamine in step S1, stir vigorously for 1 minute, then stir slowly for 15 minutes until the viscosity of the solution increases significantly, pour into a mold for gelation, and obtain haloamine polyethyleneimine gel.

[0216] The mass ratio of 3-(2'-chloroethyl)-5,5-dimethylhydantoin to polyethyleneimine is 1:5.

[0217] The mass ratio of polyethyleneimine to glutaraldehyde is 1:2.

[0218] Comparative Example 4

[0219] This comparative example provides a haloamine polyethyleneimine gel, the preparation method of which includes the following steps:

[0220] S1. Add 5.0 g of 3-(2'-chloroethyl)-5,5-dimethylhydantoin and 25.0 g of polyethyleneimine 1 (weight average molecular weight Mw = 10000) to 225 mL of water, heat to 75 °C and react for 24 h to obtain quaternized polyethyleneimine with haloamine;

[0221] S2. In step S1, 12.5 mmol of 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide hydrochloride (EDC), 12.5 mmol of N-hydroxysuccinimide (NHS) and 2.5 g of lysine were added to the quaternized polyethyleneimine of haloamines. The mixture was dehydrated at 25 °C for 2 h. Then, 50.0 g of glacial glutaraldehyde was added. The mixture was stirred vigorously for 1 minute and then slowly stirred for 15 min until the viscosity of the solution increased significantly. The mixture was then poured into a mold for gelation to obtain haloamine polyethyleneimine gel.

[0222] The mass ratio of 3-(2'-chloroethyl)-5,5-dimethylhydantoin to polyethyleneimine is 1:5.

[0223] The mass ratio of polyethyleneimine to lysine is 1:0.10;

[0224] The mass ratio of polyethyleneimine to glutaraldehyde is 1:2.

[0225] Comparative Example 5

[0226] This comparative example provides a haloamine polyethyleneimine gel, the preparation method of which includes the following steps:

[0227] S1. Add 5.0 g of 3-(2'-chloroethyl)-5,5-dimethylhydantoin and 25.0 g of polyethyleneimine 1 (weight average molecular weight Mw = 10000) to 225 mL of water, heat to 75 °C and react for 24 h to obtain quaternized polyethyleneimine with haloamine;

[0228] S2. In step S1, 12.5 mmol of 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide hydrochloride (EDC), 12.5 mmol of N-hydroxysuccinimide (NHS) and 0.25 g of lysine are added to the quaternized polyethyleneimine of haloamines. The mixture is dehydrated at 25 °C for 2 h. Then, 50.0 g of glacial glutaraldehyde is added. The mixture is first stirred vigorously for 1 minute, and then slowly stirred for 15 min until the viscosity of the solution increases significantly. The mixture is then poured into a mold for gelation to obtain haloamine polyethyleneimine gel.

[0229] The mass ratio of 3-(2'-chloroethyl)-5,5-dimethylhydantoin to polyethyleneimine is 1:5.

[0230] The mass ratio of polyethyleneimine to lysine is 1:0.010;

[0231] The mass ratio of polyethyleneimine to glutaraldehyde is 1:0.5.

[0232] Comparative Example 6

[0233] This comparative example provides a haloamine polyethyleneimine gel, the preparation method of which includes the following steps:

[0234] S1. Add 5.0 g of 3-(2'-chloroethyl)-5,5-dimethylhydantoin and 25.0 g of polyethyleneimine 1 (weight average molecular weight Mw = 10000) to 225 mL of water, heat to 75 °C and react for 24 h to obtain quaternized polyethyleneimine with haloamine;

[0235] S2. In step S1, 12.5 mmol of 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide hydrochloride (EDC), 12.5 mmol of N-hydroxysuccinimide (NHS) and 0.25 g of lysine are added to the quaternized polyethyleneimine of haloamines. The mixture is dehydrated at 25 °C for 2 h. Then, 50.0 g of glacial glutaraldehyde is added. The mixture is first stirred vigorously for 1 minute, and then slowly stirred for 15 min until the viscosity of the solution increases significantly. The mixture is then poured into a mold for gelation to obtain haloamine polyethyleneimine gel.

[0236] The mass ratio of 3-(2'-chloroethyl)-5,5-dimethylhydantoin to polyethyleneimine is 1:5.

[0237] The mass ratio of polyethyleneimine to lysine is 1:0.010;

[0238] The mass ratio of polyethyleneimine to glutaraldehyde is 1:4.

[0239] Comparative Example 7

[0240] This comparative example provides a haloamine polyethyleneimine gel, the preparation method of which includes the following steps:

[0241] Add 5.0 g of 3-(2'-chloroethyl)-5,5-dimethylhydantoin, 25.0 g of polyethyleneimine 1 (weight average molecular weight Mw = 10000), 12.5 mmol of 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide hydrochloride (EDC), 12.5 mmol of N-hydroxysuccinimide (NHS) and 0.25 g of lysine to 225 mL of water. Perform a dehydration reaction at 25 °C for 2 h. Then add 50.0 g of glacial glutaraldehyde. Stir vigorously for 1 minute, then stir slowly until the viscosity of the solution increases significantly. Pour the solution into a mold for gelation to obtain haloamine polyethyleneimine gel.

[0242] The mass ratio of 3-(2'-chloroethyl)-5,5-dimethylhydantoin to polyethyleneimine is 1:5.

[0243] The mass ratio of polyethyleneimine to lysine is 1:0.010;

[0244] The mass ratio of polyethyleneimine to glutaraldehyde is 1:2.

[0245] Performance testing

[0246] Antibacterial tests were performed on the haloamine polyethyleneimine gels of each embodiment and comparative example:

[0247] 1. Antibacterial test against Staphylococcus aureus:

[0248] (1) Using the dilution coating plate method, 0.4g of each example or comparative example of haloamine polyethyleneimine gel was placed in a 6-well plate as the experimental group, and the experiment without haloamine polyethyleneimine gel was used as the blank control group.

[0249] (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 CFU / mL Staphylococcus aureus suspension was incubated at 37°C for 6 hours. Then, 100 μL of the suspension was diluted 1000 times with LB liquid medium, and 100 μL of the suspension was spread on Luria-Bertani (LB) agar medium. After incubation at 37°C for 24 hours, the colony count was calculated.

[0250] (3) The antibacterial rate of the haloamine polyethyleneimine gels in each example and comparative example was calculated using the following formula:

[0251] The inhibition rate (%) of halogenated amine polyethyleneimine 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%;

[0252] 2. Antibacterial test against Escherichia coli:

[0253] (1) Using the dilution coating plate method, 0.4g of each example or comparative example of haloamine polyethyleneimine gel was placed in a 6-well plate as the experimental group, and the experiment without haloamine polyethyleneimine gel was used as the blank control group.

[0254] (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 6 hours. Then, 100 μL was diluted 1000 times with LB liquid medium, and 100 μL was spread on Luria-Bertani (LB) agar medium. After incubation at 37°C for 24 hours, the colony count was calculated.

[0255] (3) The antibacterial rate of the haloamine polyethyleneimine gels in each example and comparative example was calculated using the following formula:

[0256] The inhibition rate (%) of halogenated amine polyethyleneimine 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%;

[0257] The experimental results are shown in the table below:

[0258] Table 4. Antibacterial effects of haloamine polyethyleneimine gels in various examples and comparative examples.

[0259]

[0260]

[0261] As shown in Table 4, in the haloamine polyethyleneimine gel of the present invention, 3-(2'-chloroethyl)-5,5-dimethylhydantoin is used as the main antibacterial agent, and lysine and polyethyleneimine are used as auxiliary antibacterial agents. Modifying polyethyleneimine with 3-(2'-chloroethyl)-5,5-dimethylhydantoin and lysine can improve the antibacterial effect of the haloamine polyethyleneimine gel against Staphylococcus aureus. Furthermore, by controlling the mass ratio of 3-(2'-chloroethyl)-5,5-dimethylhydantoin to polyethyleneimine, the mass ratio of polyethyleneimine to lysine, and the mass ratio of polyethyleneimine to glutaraldehyde, the antibacterial effects of 3-(2'-chloroethyl)-5,5-dimethylhydantoin, lysine, and polyethyleneimine can be promoted, thereby significantly improving the antibacterial effect of the haloamine polyethyleneimine gel against Staphylococcus aureus.

[0262] It is worth noting that, as can be seen from Examples 1 and 6-10, in this invention, by controlling the weight-average molecular weight Mw of polyethyleneimine, the antibacterial effects of 3-(2'-chloroethyl)-5,5-dimethylhydantoin and polyethyleneimine can be further enhanced, thereby improving the antibacterial effect of haloamine polyethyleneimine gel against Staphylococcus aureus.

[0263] 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 haloamine polyethyleneimine gel, characterized in that, The preparation method includes the following steps: S1. Reaction of 3-(2'-chloroethyl)-5,5-dimethylhydantoin and polyethyleneimine by heating yields quaternized halogenated polyethyleneimine; S2. Haloamine quaternized polyethyleneimine first undergoes a dehydration reaction with lysine, and then reacts with glutaraldehyde to obtain haloamine polyethyleneimine gel; The mass ratio of 3-(2'-chloroethyl)-5,5-dimethylhydantoin to polyethyleneimine is 1:(1-10). The mass ratio of polyethyleneimine to lysine is 1:(0.002-0.020); The mass ratio of polyethyleneimine to glutaraldehyde is 1:(1-3).

2. The method for preparing the haloamine polyethyleneimine gel as described in claim 1, characterized in that, The mass ratio of 3-(2'-chloroethyl)-5,5-dimethylhydantoin to polyethyleneimine is 1:(3-8).

3. The method for preparing the haloamine polyethyleneimine gel as described in claim 1, characterized in that, The mass ratio of the polyethyleneimine to lysine is 1:(0.005-0.015).

4. The method for preparing the haloamine polyethyleneimine gel as described in claim 1, characterized in that, The mass ratio of polyethyleneimine to glutaraldehyde is 1:(1.5-2.5).

5. The method for preparing the haloamine polyethyleneimine gel as described in claim 1, characterized in that, In step S1, the weight-average molecular weight Mw of the polyethyleneimine is 600-250000.

6. The method for preparing the haloamine polyethyleneimine gel as described in claim 5, characterized in that, In step S1, the weight-average molecular weight Mw of the polyethyleneimine is 1800-250000.

7. The method for preparing the haloamine polyethyleneimine gel as described in claim 1, characterized in that, In step S1, the preparation method of 3-(2'-chloroethyl)-5,5-dimethylhydantoin includes the following steps: (1) 5,5-Dimethylhydantoin, a strong base and 1-bromo-2-chloroethane were reacted at 75-90℃, and the mixture was distilled under reduced pressure. Ethyl acetate and water were used as the extraction solution to extract the organic phase 1 of the supernatant. (2) Mix the organic phase 1 of the supernatant liquid with the sodium bicarbonate aqueous solution, shake, and retain the organic phase 2 of the supernatant liquid. (3) Add anhydrous sodium sulfate to the organic phase 2 of the upper clear liquid, filter, and collect the filtrate; (4) The filtrate was concentrated and distilled under reduced pressure to obtain crystals, which were then ground, pulverized, and dried to obtain 3-(2'-chloroethyl)-5,5-dimethylhydantoin.

8. The method for preparing the haloamine polyethyleneimine gel as described in claim 7, characterized in that, In step (1), the molar ratio of 5,5-dimethylhydantoin, strong base and 1-bromo-2-chloroethane is 1:1:(1-2).

9. A haloamine polyethyleneimine gel, characterized in that, It is prepared by any of the preparation methods described in claims 1-8.

10. The use of the haloamine polyethyleneimine gel of claim 9 in antibacterial applications.

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