Polymer antibacterial agent, antibacterial nylon material and preparation method and application thereof

Abstract

The invention discloses a macromolecular antibacterial agent, an antibacterial nylon material as well as a preparation method and application thereof, and relates to the technical field of antibacterial macromolecular materials. According to the invention, lysine is used as a raw material, the polymer antibacterial agent is prepared through reactions such as dehydration ring formation and re-ring opening polymerization, the polymer antibacterial agent has the characteristics of high safety, biodegradability and good biocompatibility, and has the same polyamide main chain structure as nylon, the polymer antibacterial agent and nylon have good compatibility, and the polymer antibacterial agent and nylon 6 are fused and blended to form a nylon 6 sample. Through amide exchange reaction and hydrogen bond interaction between the macromolecular antibacterial agent and nylon 6 molecular chains, the antibacterial nylon material with excellent mechanical property and lasting and stable antibacterial effect is prepared, and the requirements of people for safety and environmental friendliness are met. The prepared antibacterial nylon material can be applied to antibacterial products such as textiles, daily necessities and packaging materials. Meanwhile, the macromolecular antibacterial agent and the antibacterial nylon material are simple in preparation process, low in raw material cost and suitable for industrial production.

Description

Technical Field

[0001] The present invention relates to the technical field of antibacterial polymer materials, and in particular to a polymer antibacterial agent, an antibacterial nylon material, and a preparation method and application thereof. Background Art

[0002] In recent years, nylon materials have been widely used in many industries and fields due to their excellent mechanical properties, heat resistance, corrosion resistance and good processability, becoming an indispensable key material in modern society. However, the amide groups in the nylon molecular chain make it highly hygroscopic and easy to absorb moisture in the environment. Although this property can improve the toughness of nylon materials during application, it also provides an ideal breeding ground for the growth of bacteria and fungi, becoming a potential health hazard. Therefore, the development of nylon materials with antibacterial properties is of great significance to improving the human living environment and reducing the spread of diseases.

[0003] Currently, commercial antibacterial nylon materials are mainly prepared by blending nylon with small molecule antibacterial agents (such as silver ions, copper ions, etc.). However, this type of antibacterial nylon material still has defects in terms of safety, environmental friendliness, and high efficiency and durability of antibacterial properties. Unlike small molecule antibacterial agents, polymer antibacterial agents have the characteristics of long-lasting antibacterial effects, low residual toxicity, and high safety, which have attracted widespread attention. However, the application of polymer antibacterial agents in antibacterial nylon is still in its infancy and needs further development.

[0004] On the other hand, lysine is a natural renewable resource with abundant output and low price. Chinese patent document ZL202010008867.7 uses lysine as raw material, and prepares poly(ε-lysine) mimics with antibacterial properties by first cyclization and then ring-opening polymerization and functionalization after polymerization. The poly(ε-lysine) mimic has excellent antibacterial properties and low cytotoxicity and hemolysis, and is highly safe, but its types are limited, which to a certain extent limits its promotion and application in antibacterial nylon materials; at the same time, in the process of preparing the intermediate product aminocaprolactam from lysine cyclization, two-step reactions of esterification and dehydration cyclization are required, and a large amount of strong acid and strong base are required, and a large amount of inorganic salt by-products are produced. The preparation process is complicated and industrial amplification is difficult. Therefore, it is of great significance to develop an ideal polymer antibacterial agent to be added to nylon materials to prepare environmentally friendly, safe, and durable and efficient antibacterial nylon materials, which is of great significance to improving the application performance of nylon materials and broadening the application fields of nylon materials. Summary of the invention

[0005] In order to overcome the problem of complex preparation process of existing lysine-based polymer antibacterial agents; at the same time, to improve the deficiencies of existing antibacterial nylon materials added with small molecule antibacterial agents in terms of antibacterial effect, safety and environmental friendliness. The present invention proposes a polymer antibacterial agent, an antibacterial nylon material and a preparation method and application thereof. The technical scheme of the present invention is as follows:

[0006] A polymer antibacterial agent, the structural formula of which is shown in formula (I):

[0007]

[0008] In the formula (I), the R1 group and the R2 group are respectively substituted or unsubstituted straight chain or branched C 1-20 Aliphatic, substituted or unsubstituted C 3-12 Any of alicyclic hydrocarbon groups, substituted or unsubstituted aryl groups, substituted or unsubstituted aralkyl groups, or R1 and R2 groups on the same nitrogen atom together with the connected nitrogen atom form a 5-7 membered saturated or unsaturated heterocyclic ring;

[0009] In the formula (I), the R3 group is -H, a substituted or unsubstituted straight or branched chain C 1-20 Aliphatic, substituted or unsubstituted C 3-12 Any one of an alicyclic hydrocarbon group, a substituted or unsubstituted aryl group, and a substituted or unsubstituted aralkyl group;

[0010] In the formula (I), X is chlorine, bromine, iodine, sulfonate, substituted or unsubstituted benzoate, C 1-5 Any one of monobasic organic acid radicals, trifluoroacetate radicals, trifluoromethanesulfonate radicals, and oxygen-containing acid radicals of sulfur, nitrogen or phosphorus;

[0011] In the formula (I), the value range of n is 10≤n≤1000;

[0012] Furthermore, in the formula (I), the R1 group and the R2 group are respectively substituted or unsubstituted, linear or branched C 1-15 Aliphatic, substituted or unsubstituted C 3-6 Any of alicyclic hydrocarbon groups, substituted or unsubstituted aryl groups, substituted or unsubstituted aralkyl groups, or R1 and R2 groups on the same nitrogen atom together with the connected nitrogen atom form a 5-7 membered saturated or unsaturated heterocyclic ring;

[0013] Furthermore, the R3 group in the formula (I) is selected from -H, substituted or unsubstituted, linear or branched C 1-10 Aliphatic, substituted or unsubstituted C 3-6 Any one of an alicyclic hydrocarbon group, a substituted or unsubstituted aryl group, and a substituted or unsubstituted aralkyl group;

[0014] Furthermore, X is one of chlorine, bromine, iodine, sulfonate, benzoate, acetate, trifluoroacetate, and trifluoromethanesulfonate.

[0015] A method for preparing the above-mentioned polymer antibacterial agent comprises the following steps:

[0016] S1: adding a raw material containing lysine and methanol to a reaction kettle, stirring under a nitrogen atmosphere to dehydrate the mixture into a ring; cooling to room temperature after the reaction, filtering to remove insoluble impurities, then evaporating and concentrating to remove the solvent, recovering methanol, and extracting with ethyl acetate to obtain an intermediate product α-amino-ε-caprolactam;

[0017] S2: adding a solvent to the α-amino-ε-caprolactam prepared in S1, and continuing to react with the corresponding aldehyde and / or halogenated hydrocarbon compound containing the R1 and / or R2 groups in the formula (I), and performing post-treatment after the reaction to obtain a seven-membered cyclic lysine monomer;

[0018] S3: adding the seven-membered cyclic lysine monomer prepared in S2 into a reaction kettle for ring-opening polymerization, and continuing to react with a halogenated hydrocarbon containing the R3 group in the formula (I) or a corresponding acid, and after the reaction is completed, precipitating the product in an ethyl acetate-ether mixed solution, and then filtering and drying to obtain a polymer antibacterial agent;

[0019] Furthermore, the raw material containing lysine in S1 is one or a combination of at least two of lysine, lysine hydrochloride, lysine sulfate, and an aqueous solution containing lysine; when the raw material containing lysine is lysine hydrochloride or lysine sulfate, an equimolar equivalent of sodium hydroxide needs to be added before the reaction;

[0020] Furthermore, the stirring temperature in S1 is 120-200° C., and the stirring time is 1-6 hours;

[0021] Further, the solvent in S2 is one or a combination of at least two of methanol, ethanol, dichloromethane, chloroform, acetonitrile, acetone, tetrahydrofuran, toluene, xylene, mesitylene, dioxane, N,N-dimethylformamide, N,N-dimethylacetamide, and dimethyl sulfoxide;

[0022] Further, the aldehyde and / or halogenated hydrocarbon compound in S2 includes any one or two of paraformaldehyde, acetaldehyde, isobutylaldehyde, isovaleraldehyde, benzaldehyde, ethyl bromide, propyl bromide, butyl bromide, octane bromide, hexadecane bromide, 1,4-dibromobutane, 1,5-dibromopentane, 1,6-dibromohexane, 3-propylene bromide, benzyl bromide, p-methoxybenzyl chloride, di(2-chloroethyl) ether, and di(2-chloroethyl)amine hydrochloride;

[0023] Furthermore, the reaction temperature in S2 is -40 to 200°C, and the reaction time is 1 to 24h;

[0024] Furthermore, the post-treatment method in S2 is one or a combination of at least two of filtration, washing, solvent extraction, recrystallization, vacuum distillation, vacuum sublimation, and column chromatography;

[0025] Furthermore, the ring-opening polymerization reaction in S3 adopts a hydrolysis polymerization method or an anion polymerization method;

[0026] The hydrolysis polymerization method is to add water and an optional molecular weight regulator to the reactants; the molecular weight regulator is any one of acetic acid, adipic acid, and benzoic acid; the molar ratio of the seven-membered cyclic lysine monomer, water, and molecular weight regulator is 100:0.1-5:0-5;

[0027] The anionic polymerization method comprises adding an activator and a catalyst to the reactants; the catalyst is one or a combination of at least two of alkali metals, alkali metal oxides, alkali metal hydroxides, alkali metal hydrides, alkali metal alkoxides, alkaline earth metals, alkaline earth metal oxides, alkaline earth metal hydroxides, alkaline earth metal hydrides, alkaline earth metal alkoxides, carbene reagents, guanidine reagents, amidine reagents, and phosphazene reagents; the structural formula of the activator is as shown in formula (II), wherein R4 in formula (II) is a substituted or unsubstituted straight chain or branched C 1-5 Aliphatic hydrocarbon group, substituted or unsubstituted aromatic group; the molar ratio of the seven-membered cyclic lysine monomer, the activator and the catalyst is 100: 0.1-5: 0.1-5;

[0028]

[0029] Furthermore, the hydrolysis polymerization method includes three stages: pressure reaction, normal pressure reaction and reduced pressure reaction; the reaction temperature of the pressure reaction stage is 140°C to 230°C, the reaction time is 2h to 24h, and the reaction pressure is 0.3MPa to 5MPa; the reaction temperature of the normal pressure reaction stage is 180°C to 280°C, the reaction time is 0.5h to 10h, and the reaction pressure is -0.05MPa to 0.1MPa; the reaction temperature of the reduced pressure reaction stage is 200°C to 320°C, the reaction time is 2h to 36h, and the reaction pressure is -0.1MPa to 0MPa;

[0030] Furthermore, the polymerization temperature of the anionic polymerization method is 140-230° C., and the polymerization time is 1-6 hours; the catalyst includes any one of sodium hydride, potassium hydride, phosphazene base, potassium tert-butoxide, sodium methoxide, potassium methoxide, sodium, and potassium.

[0031] A method for preparing an antibacterial nylon material comprises the following steps: mixing a polymer antibacterial agent and a nylon 6 sample, then adding the mixture into a micro twin-screw extruder for melt blending, and obtaining the antibacterial nylon material after extrusion;

[0032] Furthermore, the mass ratio of the polymer antibacterial agent to nylon 6 is 0.5-30:100;

[0033] Furthermore, the melt blending temperature is 200-300° C., and the melt blending time is 2-60 min.

[0034] An application of the antibacterial nylon material is specifically used in the preparation of antibacterial products such as textiles, daily necessities, and packaging materials.

[0035] Compared with the prior art, the polymer antibacterial agent prepared by the present invention solves the problem of complex preparation process of lysine-based polymer antibacterial agent; at the same time, the antibacterial nylon material prepared by the present invention improves the deficiencies of antibacterial nylon material added with small molecule antibacterial agent in terms of antibacterial effect, safety and environmental friendliness. The specific beneficial effects are:

[0036] 1. Development of highly safe and environmentally friendly polymer antibacterial agents: The present invention uses biomass resource lysine as raw material, and prepares a polymer antibacterial agent with excellent antibacterial effect, biodegradability, good biocompatibility and low cytotoxicity through one-step dehydration cyclization, re-ring-opening polymerization and other reactions. It effectively optimizes the defects of existing small molecule antibacterial agents in terms of safety, biocompatibility and environmental friendliness, and meets the requirements of green environmental protection. At the same time, the present invention uses different lysine raw materials to prepare different types of polymer antibacterial agents, and the preparation process is simple, the raw material cost is low, and in the preparation process, it avoids the use of a large amount of strong acid, strong alkali and the production of a large amount of inorganic salts, which is suitable for large-scale industrial production, and effectively overcomes the defects of existing lysine-based polymer antibacterial agents such as complex preparation process, single raw material selection and great difficulty in industrial scale-up.

[0037] 2. Development of antibacterial nylon materials with excellent antibacterial effects: The antibacterial nylon materials prepared by the present invention have excellent antibacterial properties and mechanical properties. The polymer antibacterial agent prepared by the present invention has the same polyamide main chain structure as the nylon material, and is melt-blended with the nylon material. The polymer antibacterial agent can be firmly fixed on the nylon main chain through the amide exchange reaction and hydrogen bond interaction between the molecular chains. This molecular-level bonding enhances the structural stability of the material and avoids the situation where the polymer antibacterial agent is easily detached due to the influence of the external environment, so that the prepared antibacterial nylon material exhibits excellent mechanical properties and lasting and stable antibacterial effects, meeting people's needs for antibacterial nylon materials in terms of antibacterial effects, safety and environmental friendliness, and effectively solving the deficiencies in antibacterial effects, safety and environmental friendliness of the current antibacterial nylon materials prepared by adding small molecule antibacterial agents. BRIEF DESCRIPTION OF THE DRAWINGS

[0038] Figure 1 The figure is a process flow chart for the preparation of polymer antibacterial agents;

[0039] Figure 2 This is a comparison chart of the antibacterial effects of conventional nylon materials and antibacterial nylon materials on Staphylococcus aureus;

[0040] Figure 3 This is a comparison chart of the antibacterial effects of conventional nylon materials and antibacterial nylon materials on Escherichia coli. DETAILED DESCRIPTION

[0041] In order to make the technical solution of the present invention clearer, the technical solution in the embodiments of the present invention will be clearly and completely described below in conjunction with the drawings in the specification of the present invention. It should be noted that the following embodiments are only used to better understand the technical solution of the present invention and should not be understood as a limitation to the present invention.

[0042] Example 1.

[0043] S1: Add 50 mol of lysine hydrochloride, 50 mol of sodium hydroxide and 50 L of methanol into a 100 L reactor, and stir the reaction for 3 h under a nitrogen atmosphere at a reaction temperature of 190°C; after the reaction is completed, cool to room temperature, filter to remove insoluble impurities, then evaporate and concentrate to remove the solvent, recover methanol, and extract with ethyl acetate to obtain the intermediate product α-amino-ε-caprolactam with a yield of 94%. According to H-NMR analysis, its purity is 99%. 1 H NMR (300MHz, D2O) δ3.69-3.72 (dd, 1H), 3.22-3.26 (m, 2H), 1.26-1.99 (m, 6H).

[0044] S2: Add 5 mol of α-amino-ε-caprolactam prepared in S1 into a 20 L reactor, and continue to add 10 mol of polyformaldehyde, 30 g of palladium carbon (5%) and 10 L of methanol. After replacing with nitrogen and hydrogen in turn, fill with hydrogen (pressure 3.0 MPa), stir and react at 100°C for 3 hours. After the reaction is completed, filter and recover the palladium carbon. After the filtrate is spin-dried, recrystallize with ethyl acetate to obtain dimethyl seven-membered cyclic lysine monomer with a yield of 95%. According to nuclear magnetic hydrogen spectrum analysis, its purity is 98%. 1 H NMR(300MHz CDC13)δ6.98(s,1H),3.46-3.53(m,1H),2.91-2.98(m,1H),2.83-2.86(t, 1H), 2.23(s, 6H), 1.79-1.91(m, 1H), 1.66-1.69(m, 2H), 1.42-1.58(m, 3H).

[0045] S3: Add 100mmol of the dimethyl seven-membered cyclic lysine monomer prepared in S2 to the reactor, continue to add 0.1mmol of water, replace with nitrogen and maintain the nitrogen atmosphere, react under pressure at 180℃ and 0.8MPa for 4h, then heat to 210℃, react under normal pressure for 4h, finally heat to 230℃, and react under reduced pressure at -0.1MPa for 8h; after the reaction, cool to room temperature, add the product to methanol to dissolve, add 100mmol of trifluoroacetic acid, stir at room temperature for 5h, and further precipitate the product in ethyl acetate-ether mixed solution, wherein the volume ratio of ethyl acetate to ether is 1:1; then filter and dry to obtain a polymer antibacterial agent (in Formula I, R1 and R2 are methyl, R3 is -H, and X is trifluoroacetate), with a yield of 90%. Figure 1 This is a process flow chart for the preparation of polymer antibacterial agents.

[0046] S4: 10 g of the polymer antibacterial agent prepared in S3 and 100 g of nylon 6 sample were mixed, and then added into a micro twin-screw extruder for melt blending. The screw temperature of the micro twin-screw extruder was 230° C., the rotation speed was 80 r / min, the blending time was 5 min, and the antibacterial nylon material was obtained after extrusion.

[0047] Example 2.

[0048] S1: The preparation method of α-amino-ε-caprolactam is the same as the preparation method and steps described in S1 in Example 1.

[0049] S2: The preparation method of the dimethyl seven-membered cyclic lysine monomer is the same as the preparation method and steps described in S2 in Example 1.

[0050] S3: Add 100mmol of the dimethyl seven-membered cyclic lysine monomer prepared in S2 into the reactor, continue to add 0.1mmol of water, replace with nitrogen and maintain the nitrogen atmosphere, react under pressure at 180℃ and 0.8MPa for 4h, then heat to 210℃, react under normal pressure for 4h, finally heat to 230℃, and react under reduced pressure at -0.1MPa for 8h; after the reaction is completed, cool to room temperature, add the product to methanol to dissolve, add 100mmol of n-butyl bromide, reflux for 5h, cool to room temperature, and further precipitate the product in an ethyl acetate-ether mixed solution, wherein the volume ratio of ethyl acetate to ether is 1:1; then filter and dry to obtain a polymer antibacterial agent (in Formula I, R1 and R2 are methyl, R3 is n-butyl, and X is bromine) with a yield of 85%.

[0051] S4: 10 g of the polymer antibacterial agent prepared in S3 and 100 g of nylon 6 sample were mixed, and then added into a micro twin-screw extruder for melt blending. The screw temperature of the micro twin-screw extruder was 230° C., the rotation speed was 80 r / min, the blending time was 5 min, and the antibacterial nylon material was obtained after extrusion.

[0052] Example 3.

[0053] S1: The preparation method of α-amino-ε-caprolactam is the same as the preparation method and steps described in S1 in Example 1.

[0054] S2: The preparation method of the dimethyl seven-membered cyclic lysine monomer is the same as the preparation method and steps described in S2 in Example 1.

[0055] S3: 100 mmol of the dimethyl seven-membered cyclic lysine monomer prepared in S2 was added to the reactor, and 0.5 mmol of sodium hydride and 0.5 mmol of an activator (in Formula II, R4 is a phenyl group) were added continuously. The mixture was stirred at 180°C for 3 h under a nitrogen atmosphere. After the reaction, the product was dissolved in methanol, and 100 mmol of benzyl bromide was added. After reflux reaction for 5 h, the mixture was cooled to room temperature, and the product was further precipitated in an ethyl acetate-ether mixed solution, wherein the volume ratio of ethyl acetate to ether was 1:1. The mixture was then filtered and dried to obtain a polymer antibacterial agent (in Formula I, R1 and R2 are methyl groups, R3 is a benzyl group, and X is bromine) with a yield of 83%.

[0056] S4: 2 g of the polymer antibacterial agent prepared in S3 and 100 g of nylon 6 sample were mixed, and then added into a micro twin-screw extruder for melt blending. The screw temperature of the micro twin-screw extruder was 230° C., the rotation speed was 80 r / min, the blending time was 5 min, and the antibacterial nylon material was obtained after extrusion.

[0057] Example 4.

[0058] S1: The preparation method of α-amino-ε-caprolactam is the same as the preparation method and steps described in S1 in Example 1.

[0059] S2: Dissolve 2 mol of α-amino-ε-caprolactam prepared in S1 in 10 L of acetonitrile, continue to add 2.1 mol K2CO3 and 4 mol p-methoxybenzyl chloride, react at 80°C for 6 h, then filter and remove solid impurities, concentrate the filtrate, add water and extract with dichloromethane, spin dry the organic phase, and recrystallize with ethyl acetate to obtain a bis-p-methoxybenzyl seven-membered cyclic lysine monomer with a yield of 80%. According to H-NMR analysis, its purity is 96%. 1H NMR (300MHz CDCl3) δ 6.83-7.29 (m, 8H), 6.01 (s, 1H), 3.79-3.99 (m, 10H), 3.38-3.41 (d, 1H), 2.90-3.09 (m, 2H), 1.41-1.91 (m, 6H).

[0060] S3: 100 mmol of the di-p-methoxybenzyl seven-membered cyclic lysine monomer prepared in S2 was added to the reactor, and 0.1 mmol of water was added continuously. The mixture was replaced with nitrogen and the nitrogen atmosphere was maintained. The mixture was reacted under pressure at 180°C and 0.8 MPa for 4 h. The mixture was heated to 210°C and reacted under normal pressure for 4 h. The mixture was finally heated to 230°C and reacted under reduced pressure at -0.1 MPa for 8 h to obtain an intermediate product. After cooling to room temperature, the product was dissolved in methanol, and then an aqueous solution of hydrochloric acid containing 100 mmol of HCl was added. After stirring at room temperature for 8 h, the product was further precipitated in an ethyl acetate-ether mixed solution, wherein the volume ratio of ethyl acetate to ether was 1:1. The mixture was then filtered and dried to obtain a polymer antibacterial agent (in Formula I, R1 and R2 are p-methoxybenzyl, R3 is hydrogen, and X is chlorine) with a yield of 86%.

[0061] S4: 2 g of the polymer antibacterial agent prepared in S3 and 100 g of nylon 6 sample were mixed, and then added into a micro twin-screw extruder for melt blending. The screw temperature of the micro twin-screw extruder was 230° C., the rotation speed was 80 r / min, the blending time was 5 min, and the antibacterial nylon material was obtained after extrusion.

[0062] Example 5.

[0063] S1: The preparation method of α-amino-ε-caprolactam is the same as the preparation method and steps described in S1 in Example 1.

[0064] S2: The preparation method of the di-p-methoxybenzyl seven-membered cyclic lysine monomer is the same as the preparation method and steps described in S2 in Example 4.

[0065] S3: 100 mmol of the di-p-methoxybenzyl seven-membered cyclic lysine monomer prepared in S2 was added to the reactor, and 0.1 mmol of water was added, and the nitrogen atmosphere was replaced with nitrogen. The reaction was carried out under pressure at 180°C and 0.8 MPa for 4 h, and the temperature was further increased to 210°C, and the reaction was carried out under normal pressure for 4 h. Finally, the temperature was increased to 230°C, and the reaction was carried out under reduced pressure at -0.1 MPa for 8 h to obtain an intermediate product. After the reaction was completed, the product was cooled to room temperature, and dissolved in methanol. 100 mmol of iodomethane was added, and the product was further precipitated in an ethyl acetate-ether mixed solution, wherein the volume ratio of ethyl acetate to ether was 1:1. The product was then filtered and dried to obtain a polymer antibacterial agent (in Formula I, R1 and R2 are p-methoxybenzyl, R3 is methyl, and X is iodine) with a yield of 84%.

[0066] S4: 2 g of the polymer antibacterial agent prepared in S3 and 100 g of nylon 6 sample were mixed, and then added into a micro twin-screw extruder for melt blending. The screw temperature of the micro twin-screw extruder was 230° C., the rotation speed was 80 r / min, the blending time was 5 min, and the antibacterial nylon material was obtained after extrusion.

[0067] Example 6.

[0068] S1: The preparation method of α-amino-ε-caprolactam is the same as the preparation method and steps described in S1 in Example 1.

[0069] S2: The preparation method of the di-p-methoxybenzyl seven-membered cyclic lysine monomer is the same as the preparation method and steps described in S2 in Example 4.

[0070] S3: 100 mmol of the di-p-methoxybenzyl seven-membered cyclic lysine monomer prepared in S2 was added to the reactor, and 0.5 mmol of sodium hydride and 0.5 mmol of an activator (in Formula II, R4 is a phenyl group) were added, and the mixture was stirred for reaction for 3 h under a nitrogen atmosphere at a reaction temperature of 180°C. After the reaction, the product was dissolved in methanol, and 100 mmol of ethyl bromide was added. After reflux reaction for 5 h, the mixture was cooled to room temperature, and the product was further precipitated in an ethyl acetate-ether mixed solution, wherein the volume ratio of ethyl acetate to ether was 1:1. The mixture was then filtered and dried to obtain a polymer antibacterial agent (in Formula I, R1 and R2 are p-methoxybenzyl groups, R3 is an ethyl group, and X is bromine) with a yield of 90%.

[0071] S4: 2g of the polymer antibacterial agent prepared in S3 and 100g of nylon 6 sample were mixed, and then added into a micro twin-screw extruder for melt blending. The screw temperature of the micro twin-screw extruder was 230°C, the rotation speed was 80r / min, and the blending time was 5min. After extrusion, the antibacterial nylon material was obtained.

[0072] Example 7.

[0073] S1: The preparation method of α-amino-ε-caprolactam is the same as the preparation method and steps described in S1 in Example 1.

[0074] S2: Dissolve 2 mol of α-amino-ε-caprolactam prepared in S1 in 10 L of acetonitrile, continue to add 2.1 mol K2CO3 and 4 mol di(2-chloroethyl) ether, react at 80°C for 8 h, then filter to remove solid impurities, concentrate the filtrate, add water and extract with dichloromethane, spin dry the organic phase, and recrystallize with ethyl acetate to obtain morpholino seven-membered cyclic lysine monomer with a yield of 78%. According to H-NMR analysis, its purity is 96%. 1 H NMR(300MHz CDC13) δ6.01 (s, 1H), 3.57-3.61 (m, 4H), 3.43-3.51 (m, 1H), 3.25-3.34 (m, 1H), 3.16-3.20 (m, 1H), 2.65-2.69 (m, 4H), 1.41-1.91 (m, 6H).

[0075] S3: Weigh 100 mmol of the morpholino seven-membered cyclic lysine monomer prepared in S2 and add it to the reactor, continue to add 0.1 mmol of water, replace with nitrogen and maintain the nitrogen atmosphere, react under pressure at 180°C and 0.8 MPa for 4 hours, continue to heat up to 210°C, react under normal pressure for 4 hours, finally heat up to 230°C, and react under reduced pressure at -0.1 MPa for 8 hours; after the reaction is completed, cool to room temperature, add the product to methanol to dissolve, then add 100 mmol of iodomethane and stir for 8 hours at 40°C, further precipitate the product in an ethyl acetate-ether mixed solution, wherein the volume ratio of ethyl acetate to ether is 1:1; then filter and dry to obtain a polymer antibacterial agent (in Formula I, R1, R2 and N together form a morpholine ring, R3 is methyl, and X is iodine) with a yield of 82%.

[0076] S4: 2 g of the polymer antibacterial agent prepared in S3 and 100 g of nylon 6 sample were mixed, and then added into a micro twin-screw extruder for melt blending. The screw temperature of the micro twin-screw extruder was 230° C., the rotation speed was 80 r / min, the blending time was 5 min, and the antibacterial nylon material was obtained after extrusion.

[0077] Example 8.

[0078] S1: The preparation method of α-amino-ε-caprolactam is the same as the preparation method and steps described in S1 in Example 1.

[0079] S2: The preparation method of the morpholino seven-membered cyclic lysine monomer is the same as the preparation method and steps described in S2 in Example 7.

[0080] S3: 100mmol of the morpholino seven-membered cyclic lysine monomer prepared in S2 was added to a reaction kettle, and 0.5mmol of sodium hydride and 0.5mmol of an activator (in Formula II, R4 is a phenyl group) were added, and the mixture was stirred for 3h under a nitrogen atmosphere at a reaction temperature of 180°C. After the reaction, the product was dissolved in methanol, and then a hydrochloric acid aqueous solution containing 100mmol of HCl was added. After stirring at room temperature for 8h, the product was further precipitated in an ethyl acetate-ether mixed solution, wherein the volume ratio of ethyl acetate to ether was 1:1. The mixture was then filtered and dried to obtain a polymer antibacterial agent (in Formula I, R1, R2 and N together form a morpholine ring, R3 is hydrogen, and X is chlorine) with a yield of 90%.

[0081] S4: 2 g of the polymer antibacterial agent prepared in S3 and 100 g of nylon 6 sample were mixed, and then added into a micro twin-screw extruder for melt blending. The screw temperature of the micro twin-screw extruder was 230° C., the rotation speed was 80 r / min, the blending time was 5 min, and the antibacterial nylon material was obtained after extrusion.

[0082] Example 9.

[0083] S1: The preparation method of α-amino-ε-caprolactam is the same as the preparation method and steps described in S1 in Example 1.

[0084] S2: The preparation method of the morpholino seven-membered cyclic lysine monomer is the same as the preparation method and steps described in S2 in Example 7.

[0085] S3: 100 mmol of the morpholino seven-membered cyclic lysine monomer prepared in S2 was added to a reaction kettle, and 0.5 mmol of sodium hydride and 0.5 mmol of an activator (in Formula II, R4 is a phenyl group) were added, and the mixture was stirred for reaction for 3 h under a nitrogen atmosphere at a reaction temperature of 180°C. After the reaction, the product was dissolved in methanol, and 100 mmol of bromopropane was added, and the mixture was refluxed for 8 h. The mixture was cooled to room temperature, and the product was further precipitated in an ethyl acetate-ether mixed solution, wherein the volume ratio of ethyl acetate to ether was 1:1. The mixture was then filtered and dried to obtain a polymer antibacterial agent (in Formula I, R1, R2 and N together form a morpholine ring, R3 is a propyl group, and X is bromine) with a yield of 90%.

[0086] S4: 2 g of the polymer antibacterial agent prepared in S3 and 100 g of nylon 6 sample were mixed, and then added into a micro twin-screw extruder for melt blending. The screw temperature of the micro twin-screw extruder was 230° C., the rotation speed was 80 r / min, the blending time was 5 min, and the antibacterial nylon material was obtained after extrusion.

[0087] Example 10.

[0088] S1: The preparation method of α-amino-ε-caprolactam is the same as the preparation method and steps described in S1 in Example 1.

[0089] S2: Dissolve 2 mol of α-amino-ε-caprolactam prepared in S1 in 10 L of acetonitrile, continue to add 4.5 mol of K2CO3 and 4 mol of di(2-chloroethyl)amine hydrochloride, react at 80°C for 12 h, filter after the reaction to remove the solid, concentrate the filtrate, add water and extract with dichloromethane, spin dry the organic phase, and recrystallize with ethyl acetate to obtain piperazine-based seven-membered cyclic lysine monomer with a yield of 75%. According to H-NMR analysis, its purity is 96%. 1 H NMR (300MHz CDC13) δ6.01 (s, 1H), 3.43-3.51 (m, 1H), 3.19-3.33 (m, 2H), 2.65-2.76 (m, 8H), 2.41-2.52 (m, 1H), 1.43-1.66 (m, 6H).

[0090] S3: Add 100mmol of the piperazine-based seven-membered cyclic lysine monomer prepared in S2 into a reactor, continue to add 0.1mmol of water, replace with nitrogen and maintain a nitrogen atmosphere, react under pressure at 180℃ and 0.8MPa for 4h, continue to heat to 210℃, react under normal pressure for 4h, finally heat to 230℃, and react under reduced pressure at -0.1MPa for 8h; after the reaction is completed, cool to room temperature, add the product to methanol to dissolve, add 200mmol of iodomethane, stir at 40℃ for 8h, and further precipitate the product in an ethyl acetate-ether mixed solution, wherein the volume ratio of ethyl acetate to ether is 1:1; then filter and dry to obtain a polymer antibacterial agent (in Formula I, R1, R2 and N together form a piperazine ring, R3 is methyl, and X is iodine) with a yield of 80%.

[0091] S4: 1 g of the polymer antibacterial agent prepared in S3 and 100 g of nylon 6 sample were mixed, and then added into a micro twin-screw extruder for melt blending. The screw temperature of the micro twin-screw extruder was 230°C, the rotation speed was 80 r / min, the blending time was 5 min, and the antibacterial nylon material was obtained after extrusion.

[0092] Example 11.

[0093] S1: The preparation method of α-amino-ε-caprolactam is the same as the preparation method and steps described in S1 in Example 1.

[0094] S2: The preparation method of the piperazine seven-membered cyclic lysine monomer is the same as the preparation method and steps described in S2 in Example 10.

[0095] S3: 100 mmol of the piperazine-based seven-membered cyclic lysine monomer prepared in S2 was added to a reactor, and then 0.1 mmol of water was added, and the nitrogen atmosphere was replaced and maintained, and the reaction was carried out under pressure at 180°C and 0.8 MPa for 4 h, and the temperature was further raised to 210°C, and the reaction was carried out under normal pressure for 4 h, and finally the temperature was raised to 230°C, and the reaction was carried out under reduced pressure at -0.1 MPa for 8 h; after the reaction was completed, it was cooled to room temperature, the product was added to methanol for dissolution, and then 200 mmol of acetic acid was added. After stirring at room temperature for 8 h, the product was further precipitated in an ethyl acetate-ether mixed solution, wherein the volume ratio of ethyl acetate to ether was 1:1; it was then filtered and dried to obtain a polymer antibacterial agent (in Formula I, R1, R2 and N together form a piperazine ring, R3 is hydrogen, and X is acetate) with a yield of 80%.

[0096] S4: 1 g of the polymer antibacterial agent prepared in S3 and 100 g of nylon 6 sample were mixed, and then added into a micro twin-screw extruder for melt blending. The screw temperature of the micro twin-screw extruder was 230° C., the rotation speed was 80 r / min, the blending time was 5 min, and the antibacterial nylon material was obtained after extrusion.

[0097] Example 12.

[0098] S1: The preparation method of α-amino-ε-caprolactam is the same as the preparation method and steps described in S1 in Example 1.

[0099] S2: The preparation method of the piperazine seven-membered cyclic lysine monomer is the same as the preparation method and steps described in S2 in Example 10.

[0100] S3: 100 mmol of the piperazine-based seven-membered cyclic lysine monomer prepared in S2 was added to the reactor, and 0.1 mmol of water was added, and the nitrogen atmosphere was replaced with nitrogen. The reaction was carried out under pressure at 180°C and 0.8 MPa for 4 h, and the temperature was further raised to 210°C, and the reaction was carried out under normal pressure for 4 h. Finally, the temperature was raised to 230°C, and the reaction was carried out under reduced pressure at -0.1 MPa for 8 h. After the reaction was completed, the reaction was cooled to room temperature, the product was dissolved in methanol, and 200 mmol of benzyl bromide was added. After stirring at 80°C for 8 h, the product was further precipitated in an ethyl acetate-ether mixed solution, wherein the volume ratio of ethyl acetate to ether was 1:1. The product was then filtered and dried to obtain a polymer antibacterial agent (in Formula I, R1, R2 and N together form a piperazine ring, R3 is benzyl, and X is bromine) with a yield of 82%.

[0101] S4: 1 g of the polymer antibacterial agent prepared in S3 and 100 g of nylon 6 sample were mixed, and then added into a micro twin-screw extruder for melt blending. The screw temperature of the micro twin-screw extruder was 230° C., the rotation speed was 80 r / min, the blending time was 5 min, and the antibacterial nylon material was obtained after extrusion.

[0102] Example 13.

[0103] S1: Add 50 mol lysine and 50 L methanol into a 100 L reactor, stir and react for 3 h under a nitrogen atmosphere at a reaction temperature of 190 ° C; after the reaction is completed, cool to room temperature, evaporate and concentrate to remove the solvent, recover methanol, and extract with ethyl acetate to obtain the intermediate product α-amino-ε-caprolactam with a yield of 96%. According to H NMR analysis, its purity is 99%. 1 HNMR (300MHz, D2O) δ3.69-3.72 (dd, 1H), 3.22-3.26 (m, 2H), 1.26-1.99 (m, 6H).

[0104] S2: Dissolve 2 mol of α-amino-ε-caprolactam prepared in S1 in 10 L of methanol, add 2 mol of benzaldehyde, stir and react at room temperature for 3 h, then continue to add 2.1 mol of sodium borohydride, reflux and react for 5 h, spin-dry the methanol to obtain a seven-membered cyclic lysine monomer protected by a single benzyl group. Then add 10 L of acetonitrile, 2 mol of iodomethane and 2.1 mol of K2CO3, react at 80°C for 8 h, then filter and remove solid impurities, concentrate the filtrate, add water and extract with dichloromethane, spin-dry the organic phase, and recrystallize with ethyl acetate to obtain a seven-membered cyclic lysine monomer with benzyl and methyl groups, with a yield of 70%, and a purity of 96% according to H NMR analysis. 1 H NMR(300MHz CDCl3) δ7.19-7.31, (m, 5H), 6.02 (s, 1H), 3.72 (s, 1H), 3.48-3.56 (m, 2H), 3.27-3 .36 (m, 1H), 3.14-3.19 (m, 1H), 2.48-2.62 (m, 1H), 2.26 (s, 3H), 1.43-1.68 (m, 5H).

[0105] S3: 100 mmol of the seven-membered cyclic lysine monomer with benzyl and methyl groups prepared in S2 was added to a reactor, and 0.5 mmol of sodium hydride and 0.5 mmol of an activator (in Formula II, R4 is a phenyl group) were added, and the mixture was stirred for reaction for 3 h under a nitrogen atmosphere at a reaction temperature of 180°C. After the reaction, the product was dissolved in methanol, and 100 mmol of ethyl bromide was added, and the mixture was refluxed for 8 h. The mixture was cooled to room temperature, and the product was further precipitated in an ethyl acetate-ether mixed solution, wherein the volume ratio of ethyl acetate to ether was 1:1. The mixture was then filtered and dried to obtain a polymer antibacterial agent (in Formula I, R1 is a benzyl group, R2 is a methyl group, R3 is an ethyl group, and X is bromine) with a yield of 92%.

[0106] S4: 2 g of the polymer antibacterial agent prepared in S3 and 100 g of nylon 6 sample were mixed, and then added into a micro twin-screw extruder for melt blending. The screw temperature of the micro twin-screw extruder was 230° C., the rotation speed was 80 r / min, the blending time was 5 min, and the antibacterial nylon material was obtained after extrusion.

[0107] Example 14.

[0108] S1: 14.6 kg of lysine fermentation liquid (lysine content is 50%) and 40 L of methanol were added to a 100 L reactor, and the mixture was stirred for reaction for 3 h under a nitrogen atmosphere at a reaction temperature of 190°C. After the reaction was completed, the mixture was cooled to room temperature, evaporated and concentrated to remove the solvent, and the methanol was recovered and extracted with ethyl acetate to obtain the intermediate product α-amino-ε-caprolactam with a yield of 92%. According to H-NMR analysis, the purity was 99%. 1 H NMR (300MHz, D2O) δ3.69-3.72 (dd, 1H), 3.22-3.26 (m, 2H), 1.26-1.99 (m, 6H).

[0109] S2: Dissolve 2 mol of α-amino-ε-caprolactam prepared in S1 in 10 L of acetonitrile, continue to add 4.5 mol of K2CO3 and 4 mol of 1,4-dibromobutane, react at 80°C for 8 h, then filter to remove solid impurities, concentrate the filtrate, add water and extract with dichloromethane, spin dry the organic phase, and recrystallize with ethyl acetate to obtain a seven-membered cyclic lysine monomer with a cyclopentyl group, with a yield of 75%. According to H-NMR analysis, its purity is 96%. 1 H NMR (300MHz CDC13) δ6.01 (s, 1H), 3.44-3.59 (m, 2H), 3.24-3.32 (m, 1H), 2.65-2.82 (m, 4H), 2.23-2.35 (m, 1H), 1.41-1.69 (m, 9H).

[0110] S3: 100 mmol of the seven-membered cyclic lysine monomer with a cyclopentyl group prepared in S2 was added to a reactor, and 0.5 mmol of sodium hydride and 0.5 mmol of an activator (in Formula II, R4 is a phenyl group) were added, and the mixture was stirred for reaction for 3 h under a nitrogen atmosphere at a reaction temperature of 180°C. After the reaction, the product was dissolved in methanol, and 100 mmol of ethyl bromide was added, and the mixture was refluxed for 8 h. The mixture was cooled to room temperature, and the product was further precipitated in an ethyl acetate-ether mixed solution, wherein the volume ratio of ethyl acetate to ether was 1:1. The mixture was then filtered and dried to obtain a polymer antibacterial agent (in Formula I, R1, R2 and N together form a five-membered ring, R3 is an ethyl group, and X is bromine) with a yield of 92%.

[0111] S4: 2 g of the polymer antibacterial agent prepared in S3 and 100 g of nylon 6 sample were mixed, and then added into a micro twin-screw extruder for melt blending. The screw temperature of the micro twin-screw extruder was 230° C., the rotation speed was 80 r / min, the blending time was 5 min, and the antibacterial nylon material was obtained after extrusion.

[0112] Comparative Example 1.

[0113] The dried nylon 6 sample was added into a micro twin-screw extruder for melting. The screw temperature of the micro twin-screw extruder was 230°C, the rotation speed was 80r / min, and the blending time was 5min. After extrusion, a conventional nylon material was obtained.

[0114] Comparative Example 2.

[0115] 0.1 g of the polymer antibacterial agent prepared in Example 1S1-S3 (in Formula I, R1 and R2 are methyl, R3 is hydrogen, and X is trifluoroacetate) and 100 g of nylon 6 sample were mixed, and then added to a micro twin-screw extruder for melt blending. The screw temperature of the micro twin-screw extruder was 230°C, the rotation speed was 80 r / min, the blending time was 5 min, and the antibacterial nylon material was obtained after extrusion.

[0116] Comparative Example 3.

[0117] Weigh 40 g of the polymer antibacterial agent prepared in Example 1S1-S3 (in Formula I, R1 and R2 are methyl, R3 is hydrogen, and X is trifluoroacetate) and 100 g of nylon 6 sample, mix them well and add them into a micro twin-screw extruder for melt blending. The screw temperature of the micro twin-screw extruder is 230°C, the rotation speed is 80 r / min, the blending time is 5 min, and the antibacterial nylon material is obtained after extrusion.

[0118] Antibacterial effect test:

[0119] The antibacterial effect test was carried out in accordance with the method specified in the Chinese national standard GB / T 31402-2023, and some conditions were adjusted according to the actual situation. The specific operation was as follows: the nylon materials prepared in Examples 1-14 and Comparative Examples 1-3 were respectively pressed into 5 cm × 5 cm square sheets, sprayed with 75% alcohol and then dried, irradiated under ultraviolet light for 30 min for sterilization, and then 0.4 mL of 6 × 10 5 CFU / mL of bacterial solution was covered with PET film and cultured at 37°C for 24 hours. The bacterial solution was rinsed and diluted with 10mL of SCDLP liquid culture medium, and mixed with PCA culture medium after gradient dilution. The culture was continued at 37°C for 48 hours. The colonies in the culture medium were counted using an automatic colony counter to estimate the bacterial concentration of the bacterial solution after culture. Staphylococcus aureus (S.aureus) ATCC6538 and Escherichia coli (E.coli) ATCC25922 were used as the detection bacteria. Figure 2 The figure is a comparison chart of the antibacterial effects of the conventional nylon material prepared in Comparative Example 1 and the antibacterial nylon material prepared in Example 1 on Staphylococcus aureus; Figure 3 The figure is a comparison of the antibacterial effects of the conventional nylon material prepared in comparative example 1 and the antibacterial nylon material prepared in example 1 on Escherichia coli. It can be seen from the figure that after using the antibacterial nylon material, the colony counts of Staphylococcus aureus and Escherichia coli are significantly reduced, proving that the antibacterial nylon material prepared in the present invention has a significant inhibitory effect on Staphylococcus aureus and Escherichia coli. Among them, the antibacterial rate of the antibacterial nylon material prepared in example 1 on Staphylococcus aureus is 98.5%, and the antibacterial rate on Escherichia coli is 96.3%. The antibacterial rate calculation formula is as follows:

[0120]

[0121] Mechanical properties test:

[0122] The antibacterial nylon materials prepared in the above Examples 1-14 and the nylon materials prepared in Comparative Examples 1-3 were respectively injection molded into 5A-type specimens (the dimensions were prepared in accordance with the Chinese national standard GB / T 1040.2-2022) and subjected to tensile performance tests. The following table shows the antibacterial rates and mechanical performance results of the antibacterial nylon materials prepared in Examples 1-14 and the nylon materials prepared in Comparative Examples 1-3:

[0123]

[0124]

[0125] As shown in the data in the table, since comparative example 1 does not use a high molecular weight antibacterial agent, and comparative example 2 uses only a small amount of a high molecular weight antibacterial agent, the antibacterial rates of the antibacterial nylon materials prepared in Examples 1-14 of the present invention are much higher than those of the nylon materials prepared in Examples 1 and 2, and at the same time, they can achieve mechanical properties equivalent to those of the nylon materials prepared in Examples 1 and 2; since the antibacterial nylon material prepared in Comparative Example 3 uses an excessive amount of a high molecular weight antibacterial agent, its antibacterial rate is slightly higher than that of the high molecular weight antibacterial agent prepared in Example 1, but its tensile strength and elongation at break are greatly reduced. Therefore, the antibacterial nylon materials prepared in Examples 1-14 of the present invention retain the mechanical properties of the nylon material to the greatest extent while enhancing the antibacterial effect.

[0126] In summary, the present invention uses renewable, low-cost lysine resources as raw materials, combined with simple, low-risk melt blending technology, to prepare antibacterial nylon materials with excellent mechanical properties and long-lasting, stable antibacterial effects. This preparation process not only optimizes the cost structure, but also significantly reduces the energy consumption in the preparation process, does not require the use of high-risk chemicals or complex equipment, ensures people's needs for the safety and environmental protection of antibacterial nylon materials, and is suitable for large-scale industrial production.

[0127] The above embodiments are only used to help understand the method and core idea of ​​the present invention. It should be noted that, for those skilled in the art, several improvements and modifications can be made to the present invention without departing from the principles of the present invention, and these improvements and modifications also fall within the scope of protection of the claims of the present invention.

[0128] The above description of the disclosed embodiments enables those skilled in the art to implement or use the present invention. Various modifications to these embodiments will be apparent to those skilled in the art, and the general principles defined herein may be implemented in other embodiments without departing from the spirit or scope of the present invention. Therefore, the present invention will not be limited to the embodiments shown herein, but rather to the widest range consistent with the principles and novel features disclosed herein.

Claims

1. A polymer antibacterial agent, characterized in that: Its structural formula is shown in formula (I): In the formula (I), the R1 group and the R2 group are respectively substituted or unsubstituted straight chain or branched C 1-20 Aliphatic, substituted or unsubstituted C 312 Any of alicyclic hydrocarbon groups, substituted or unsubstituted aryl groups, substituted or unsubstituted aralkyl groups, or R1 and R2 groups on the same nitrogen atom together with the connected nitrogen atom form a 5-7 membered saturated or unsaturated heterocyclic ring; In the formula (I), the R3 group is -H, a substituted or unsubstituted straight or branched chain C 1-20 Aliphatic, substituted or unsubstituted C 3 12 Any one of an alicyclic hydrocarbon group, a substituted or unsubstituted aryl group, and a substituted or unsubstituted aralkyl group; In the formula (I), X is chlorine, bromine, iodine, sulfonate, substituted or unsubstituted benzoate, C 1 5 Any one of monobasic organic acid radicals, trifluoroacetate radicals, trifluoromethanesulfonate radicals, and oxygen-containing acid radicals of sulfur, nitrogen or phosphorus; In the formula (I), the value range of n is 10≤n≤1000.

2. A method for preparing a polymer antibacterial agent as claimed in claim 1, characterized in that: The following steps are involved: S1: adding a raw material containing lysine and methanol to a reaction kettle, stirring under a nitrogen atmosphere to dehydrate the mixture into a ring; cooling to room temperature after the reaction, filtering to remove insoluble impurities, then evaporating and concentrating to remove the solvent, recovering methanol, and extracting with ethyl acetate to obtain an intermediate product α-amino-ε-caprolactam; S2: adding a solvent to the α-amino-ε-caprolactam prepared in S1, further reacting with the corresponding aldehyde and / or halogenated hydrocarbon compound containing the R1 and / or R2 groups in the formula (I), and performing post-treatment after the reaction to obtain a seven-membered cyclic lysine monomer; S3: Add the seven-membered cyclic lysine monomer prepared in S2 into a reactor for ring-opening polymerization, and continue to react the product with a halogenated hydrocarbon containing the R3 group in the formula (I) or the corresponding acid. After the reaction, the product is precipitated in an ethyl acetate-ether mixed solution, and then filtered and dried to obtain a polymer antibacterial agent.

3. The method for preparing the polymer antibacterial agent according to claim 2, characterized in that: The raw material containing lysine in S1 is one of lysine, lysine hydrochloride, lysine sulfate, and an aqueous solution containing lysine, or a combination of at least two of them; when the raw material containing lysine is lysine hydrochloride or lysine sulfate, an equimolar amount of sodium hydroxide needs to be added before the reaction; the temperature of the stirring reaction is 120-200° C., and the stirring reaction time is 1-6 hours.

4. The method for preparing the polymer antibacterial agent according to claim 2, characterized in that: The solvent in S2 is one of methanol, ethanol, dichloromethane, chloroform, acetonitrile, acetone, tetrahydrofuran, toluene, xylene, mesitylene, dioxane, N,N-dimethylformamide, N,N-dimethylacetamide, and dimethyl sulfoxide, or a combination of at least two of them; the aldehydes or halogenated hydrocarbons include any one of paraformaldehyde, p-methoxybenzyl chloride, di(2-chloroethyl) ether, and di(2-chloroethyl)amine hydrochloride; the reaction temperature is -40 to 200°C, and the reaction time is 1 to 24 hours; the post-treatment method is one of filtration, washing, solvent extraction, recrystallization, vacuum distillation, vacuum sublimation, and column chromatography, or a combination of at least two of them.

5. The method for preparing the polymer antibacterial agent according to claim 2, characterized in that: The ring-opening polymerization reaction in S3 adopts hydrolysis polymerization or anion polymerization; The hydrolysis polymerization method is to add water and an optional molecular weight regulator to the reactants; the molecular weight regulator is any one of acetic acid, adipic acid, and benzoic acid; the molar ratio of the seven-membered cyclic lysine monomer, water, and molecular weight regulator is 100:0.1-5:0-5; The anionic polymerization method comprises adding an activator and a catalyst to the reactants; the catalyst is one or a combination of at least two of alkali metals, alkali metal oxides, alkali metal hydroxides, alkali metal hydrides, alkali metal alkoxides, alkaline earth metals, alkaline earth metal oxides, alkaline earth metal hydroxides, alkaline earth metal hydrides, alkaline earth metal alkoxides, carbene reagents, guanidine reagents, amidine reagents, and phosphazene reagents; the structural formula of the activator is as shown in formula (II), wherein R4 in formula (II) is a substituted or unsubstituted straight chain or branched C 1-5 Aliphatic hydrocarbon group, substituted or unsubstituted aromatic group; the molar ratio of the seven-membered cyclic lysine monomer, the activator and the catalyst is 100: 0.1-5: 0.1-5; 6. The method for preparing the polymer antibacterial agent according to claim 5, characterized in that: The hydrolysis polymerization method includes three stages: pressure reaction, normal pressure reaction and reduced pressure reaction; the reaction temperature of the pressure reaction stage is 140°C to 230°C, the reaction time is 2h to 24h, and the reaction pressure is 0.3MPa to 5MPa; the reaction temperature of the normal pressure reaction stage is 180°C to 280°C, the reaction time is 0.5h to 10h, and the reaction pressure is -0.05MPa to 0.1MPa; the reaction temperature of the reduced pressure reaction stage is 200°C to 320°C, the reaction time is 2h to 36h, and the reaction pressure is -0.1MPa to 0MPa; The polymerization temperature of the anionic polymerization method is 140-230° C., and the polymerization time is 1-6 hours; the catalyst includes any one of sodium hydride, potassium hydride, phosphazene base, potassium tert-butoxide, sodium methoxide, potassium methoxide, sodium, and potassium.

7. An antibacterial nylon material, characterized in that: It is made by melt blending high molecular antibacterial agent and nylon 6.

8. A method for preparing the antibacterial nylon material according to claim 7, characterized in that: The method comprises the following steps: mixing a polymer antibacterial agent and a nylon 6 sample, then adding the mixture into a micro twin-screw extruder for melt blending, and obtaining an antibacterial nylon material after extrusion.

9. The method for preparing the antibacterial nylon material according to claim 8, characterized in that: The mass ratio of the polymer antibacterial agent to nylon 6 is 0.5-30:100; the temperature of the melt blending is 200-300°C, and the melt blending time is 2-60 minutes.

10. An application of the antibacterial nylon material according to claim 7 or the antibacterial nylon material prepared by the preparation method according to claim 8 or 9, characterized in that: Used in the preparation of antibacterial products such as textiles, daily necessities, and packaging materials.

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