Antibacterial nylon material as well as preparation method and application thereof

Abstract

The invention discloses an antibacterial nylon material as well as a preparation method and application thereof, relates to the technical field of antibacterial high polymer materials, and solves the problems of poor antibacterial performance and difficulty in industrial production of existing antibacterial nylon 6. The preparation method comprises the following steps: mixing a seven-membered cyclic lysine derivative monomer with lactam, and carrying out hydrolytic polymerization by taking water as an initiator to obtain copolyamide; and placing the copolyamide in an acid solution, heating and stirring to carry out protonation reaction, and purifying the reaction product to obtain the antibacterial nylon material. The seven-membered cyclic lysine derivative monomer is an unprotected cyclic lysine monomer (aminocaprolactam), a single protected cyclic lysine monomer or a salified cyclic lysine monomer. The method can be widely applied to the fields with antibacterial requirements, such as fabrics, plates, pipes, packaging and various panels.

Description

Technical Field

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

[0002] Various harmful microorganisms such as bacteria, fungi, and viruses are widely present in the natural environment. All activities in daily life may be contaminated by harmful microorganisms. In severe cases, they may cause malignant infections, which in turn pose a threat to human health and even life. Antibacterial polymer materials can inhibit and kill bacteria, fungi and other microorganisms attached to their surfaces, and have been widely used in the fields of health, medical care, and environmental protection. In recent years, with the enhancement of people's awareness of hygiene and their continued attention to their own health, the demand for antibacterial polymer materials has increased.

[0003] Nylon is a polymer material containing repeated amide groups in its molecular chain. It has excellent comprehensive properties and has been widely used in personal care, fabrics, automobiles, engineering plastics, packaging and other fields. It is almost everywhere in our daily life. However, under the environmental conditions of daily storage and use, traditional nylon materials are prone to breed harmful microorganisms such as bacteria, fungi, viruses, etc., which endanger people's living environment and health. At present, commercial antibacterial nylon materials are mainly prepared by blending polyamide with small molecule antibacterial agents (such as silver ions, copper ions, etc.). However, this type of antibacterial nylon material still has many problems in terms of safety, environmental friendliness, and high efficiency and durability of antibacterial properties. Therefore, it is still of great significance to develop environmentally friendly, safe, durable and efficient antibacterial nylon materials.

[0004] Lysine (also known as 2,6-diaminohexanoic acid) is a natural renewable resource with abundant production and low price. A seven-membered cyclic lysine derivative monomer can be obtained through lysine cyclization. It has the same ring structure as caprolactam and can be ring-opened copolymerized with other lactams. Functional groups are introduced into the side chains of polyamides, and antibacterial properties are given to them through post-modification, which provides a new idea for the preparation of antibacterial nylon materials. In this regard, the document ACS Macro Lett. 2022, 11, 46-52 uses a seven-membered cyclic lysine derivative monomer with a dimethylamino group to open the ring copolymerize with caprolactam, introduces a dimethylamino group into the side chain of nylon 6, and further uses ethyl bromide to quaternize it to obtain an antibacterial nylon 6 material, but the mechanical properties of this material are poor. Chinese invention patent document CN115707727A also reports a method for preparing antibacterial nylon 6 material by first using a seven-membered cyclic lysine derivative monomer and caprolactam for ring-opening copolymerization, and then using a halogenated alkane for quaternization treatment. In this method, hydrochloric acid is also tried to be used instead of a halogenated alkane to protonate the copolyamide, but its antibacterial performance is poor. In addition, the above methods all require amino-double-protected seven-membered cyclic lysine derivative monomers as raw materials, and after polymerization, trifluoroethanol is used to dissolve the copolyamide, and then the quaternization reaction is carried out with a halogenated alkane. There are problems such as complicated preparation process, low production efficiency, and high production cost, which are not conducive to the industrial production of antibacterial nylon 6 materials. Summary of the invention

[0005] In order to solve the problems of poor antibacterial performance and difficulty in industrial production of existing antibacterial nylon 6, the present invention provides an antibacterial nylon material and a preparation method and application thereof.

[0006] The technical solution of the present invention is as follows:

[0007] An antibacterial nylon material, the molecular structure of which comprises two different repeating units as shown in the following formula I and formula II respectively:

[0008]

[0009] Wherein, R is selected from hydrogen, C 1～28 Substituted / unsubstituted straight chain / branched, saturated / unsaturated aliphatic hydrocarbon group, substituted / unsubstituted, saturated / unsaturated C 3～15 Alicyclic hydrocarbon, substituted / unsubstituted C 6～22 Aryl, substituted / unsubstituted, saturated / unsaturated C 7～35 One of the aralkyl groups; the substitution refers to halogen, nitro, C 118 One or more substituents in a straight or branched alkyl group;

[0010] n is any natural number from 1 to 8;

[0011] x and y represent the molar ratio of the corresponding repeating units, x is selected from 0.01 to 0.50, y is selected from 0.50 to 0.99, and x+y=1.

[0012] Preferably, R is selected from one of hydrogen, methyl, ethyl, propyl, isopropyl, butyl, tert-butyl, hexyl, cyclohexyl, dodecyl, phenyl and benzyl.

[0013] The present invention also provides a method for preparing the above antibacterial nylon material, comprising the following steps:

[0014] Step 1: mixing a seven-membered cyclic lysine derivative monomer with lactam, using water as an initiator, and performing hydrolysis polymerization to obtain a copolyamide;

[0015] Step 2: placing the copolyamide in an acid solution, heating and stirring to perform a protonation reaction, and purifying the reaction product to obtain an antibacterial nylon material;

[0016] The seven-membered cyclic lysine derivative monomer is a structure as shown in Formula III, or a salt-forming cyclic lysine monomer obtained by reacting the exocyclic amino group (or single-protected amino group) in the structure of Formula III with an acid:

[0017]

[0018] Specifically, when R is hydrogen, it is referred to as an unprotected cyclic lysine monomer; when R is other substituents, it is referred to as a single-protected cyclic lysine monomer.

[0019] The structural formula of the lactam is shown in Formula IV:

[0020]

[0021] The acid is selected from halogen hydrides or oxygen-containing acids, sulfur, nitrogen or phosphorus hydrides or oxygen-containing acids, C 1～35 One of the 1-5-valent carboxylic acids, hydroxycarboxylic acids and sulfonic acids.

[0022] Preferably, the seven-membered cyclic lysine derivative monomer is prepared by the following steps:

[0023] Lysine or lysine hydrochloride is mixed with methanol, an equimolar amount of sodium hydroxide is added or not, and a dehydration cyclization reaction is carried out at 125°C to 200°C, followed by extraction with ethyl acetate to obtain aminocaprolactam (unprotected cyclic lysine monomer, R in formula III is H);

[0024] Or aminocaprolactam is further reacted with corresponding acids, aldehydes or halogenated hydrocarbons having an R group to obtain a monoprotected cyclic lysine monomer;

[0025] Alternatively, an unprotected or singly protected cyclic lysine monomer is reacted with an acid to obtain a salt-forming cyclic lysine monomer.

[0026] Preferably, the molar ratio of the seven-membered cyclic lysine derivative monomer to the lactam in step 1 is 0.01 to 1:1; more preferably 0.01 to 0.8:1;

[0027] The mass ratio of the total mass of the seven-membered cyclic lysine derivative monomer and the lactam to water is 10 to 200:1, and more preferably 20 to 100:1.

[0028] Preferably, a catalyst is added in step 1, wherein the catalyst is selected from halogen hydrides or oxygen-containing acids, sulfur, nitrogen or phosphorus oxygen-containing acids, C 1～35 One or a mixture of at least two of 1-5-carboxylic acids, hydroxy acids, amino acids, sulfonic acids or phosphoric acids, hydroxides, carbonates, bicarbonates, basic carbonates of alkali metals or alkaline earth metals;

[0029] The molar ratio of the catalyst to the total amount of the seven-membered cyclic lysine-derived monomer and the lactam is 0.001 to 0.1:1.

[0030] Preferably, the hydrolysis polymerization conditions in step 1 are: polymerization temperature is 140° C. to 320° C., polymerization time is 2 h to 96 h, and polymerization pressure is -0.1 MPa to 5 MPa.

[0031] Preferably, the hydrolysis polymerization can be divided into three stages: pressure reaction, normal pressure reaction and reduced pressure reaction, and the reaction conditions of each stage are as follows:

[0032] Pressurized reaction stage: polymerization temperature is 140°C to 230°C, polymerization time is 2h to 24h, and polymerization pressure is 0.3MPa to 5MPa;

[0033] Normal pressure reaction stage: polymerization temperature is 180℃~280℃, polymerization time is 0.5h~10h, polymerization pressure is -0.05MPa~0.1MPa;

[0034] Reduced pressure reaction stage: polymerization temperature is 200°C to 320°C, polymerization time is 2h to 36h, and polymerization pressure is -0.1MPa to 0MPa.

[0035] Preferably, the solute in the acid solution in step 2 is selected from hydrides or oxygen-containing acids of halogens, hydrides or oxygen-containing acids of sulfur, nitrogen or phosphorus, C 1～35The invention further comprises one or a combination of at least two of 1-5-valent carboxylic acids, hydroxycarboxylic acids, and sulfonic acids; further preferably, one or a combination of at least two of hydrochloric acid, hydrobromic acid, sulfuric acid, nitric acid, phosphoric acid, formic acid, acetic acid, propionic acid, butyric acid, caproic acid, octanoic acid, hexadecanoic acid, benzoic acid, lactic acid, mandelic acid, salicylic acid, tartaric acid, malic acid, citric acid, methanesulfonic acid, and p-toluenesulfonic acid; further preferably, one or a combination of at least two of hydrochloric acid, phosphoric acid, acetic acid, benzoic acid, tartaric acid, citric acid, and p-toluenesulfonic acid.

[0036] The solvent in the acid solution is selected from one or a combination of at least two of ether, methyl tert-butyl ether, tetrahydrofuran, ethylene carbonate, propylene carbonate, acetonitrile, methyl ethyl ketone, acetone, methanol, ethanol, butanol, dichloromethane, carbon disulfide, chloroform, ethyl acetate, ethyl isovalerate, N,N-dimethylformamide, N,N-dimethylacetamide, and dimethyl sulfoxide.

[0037] Preferably, in step 2, the amount of solvent required for protonation of each gram of copolyamide is 0.1 mL to 20 mL, and the amount of acid is 0.01 g to 10 g; the heating temperature is 20° C. to 180° C.; and the stirring time is 10 min to 48 h.

[0038] Preferably, the purification method in step 2 is washing, and the washing solvent is selected from one or a combination of at least two of water, methanol, ethanol, dichloromethane, acetone, and ethyl acetate; the washing time is 0.1h to 24h, and the washing temperature is 25°C to 100°C.

[0039] The present invention also provides an application of the antibacterial nylon material, which can be specifically applied to the preparation of antibacterial nylon products. The antibacterial nylon products include fabrics, plates, pipes, packaging materials and panels.

[0040] Compared with the prior art, the specific beneficial effects of the present invention are:

[0041] 1. The present invention aims at the deficiencies in the existing antibacterial nylon material preparation technology, and utilizes unprotected, single-protected or salified cyclic lysine and lactam to obtain copolyamide by ring-opening copolymerization, and then undergoes protonation reaction with an acid solution to prepare an antibacterial nylon material. The antibacterial nylon material has a highly efficient antibacterial effect, and can be processed and formed by injection molding, blow molding, extrusion molding, spinning, etc., and has mechanical properties that are basically equivalent to conventional nylon materials, and can be widely used in fields that require antibacterial properties, such as fabrics, plates, pipes, packaging, various panels, etc.

[0042] 2. Compared with the prior art, the preparation method provided by the present invention does not require the addition of an antibacterial agent, avoids complex operations such as melt blending, and does not require the use of trifluoroethanol to dissolve the copolyamide during the post-modification process, nor does it require the use of halogenated alkanes for quaternization reaction, which can effectively reduce the use of reagents such as halogenated alkanes and solvents such as trifluoroethanol. It has the advantages of simple preparation process, high production efficiency, low production cost, etc., and is suitable for the industrial production of antibacterial nylon materials. BRIEF DESCRIPTION OF THE DRAWINGS

[0043] Figure 1 This is the nuclear magnetic resonance hydrogen spectrum of the antibacterial nylon material in Example 1;

[0044] Figure 2 This is the nuclear magnetic resonance hydrogen spectrum of the antibacterial nylon material in Example 2;

[0045] Figure 3 This is the nuclear magnetic resonance hydrogen spectrum of the antibacterial nylon material in Example 3;

[0046] Figure 4 This is the nuclear magnetic resonance hydrogen spectrum of the antibacterial nylon material in Example 4;

[0047] Figure 5 This is a diagram showing the antibacterial effect of the antibacterial nylon material in Example 1 on Staphylococcus aureus;

[0048] Figure 6 This is a diagram showing the antibacterial effect of the antibacterial nylon material in Comparative Example 1 on Staphylococcus aureus. DETAILED DESCRIPTION

[0049] 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.

[0050] Any specific numerical value disclosed herein (including the endpoint of the numerical range) is not limited to the exact value of the numerical value, but should be understood to also cover values ​​close to the exact value, such as all possible numerical values ​​within the range of ±5% of the exact value. In addition, for the disclosed numerical range, the endpoint values ​​of the range, the endpoint values ​​and the specific point values ​​in the range, and the specific point values ​​can be arbitrarily combined to obtain one or more new numerical ranges, and these new numerical ranges should also be regarded as specifically disclosed herein.

[0051] Unless otherwise specified, the terms used herein have the same meaning as commonly understood by those skilled in the art. If a term is defined herein and its definition is different from the commonly understood meaning in the art, the definition herein shall prevail.

[0052] In this document, except for the contents explicitly described, any matters or items not mentioned are directly applicable to those known in the art without any changes. Moreover, any embodiment described in this document can be freely combined with one or more other embodiments described in this document, and the technical solutions or technical ideas formed thereby are regarded as part of the original disclosure or original record of the present invention, and should not be regarded as new contents not disclosed or anticipated in this document, unless a person skilled in the art considers that the combination is obviously unreasonable.

[0053] Example 1.

[0054] (1) Preparation of aminocaprolactam (unprotected cyclic lysine, R=H in formula III):

[0055] In a 5L reactor, add 640g (3.5mol) lysine hydrochloride, 140g (3.5mol) sodium hydroxide and 3.5L methanol, and stir at 150°C for 6h. Cool to room temperature, remove insoluble matter by suction filtration, evaporate to dryness and recover methanol, extract with ethyl acetate to obtain aminocaprolactam, the yield is 94%, and the purity is 99% according to nuclear magnetic resonance hydrogen spectrum analysis. Nuclear magnetic resonance hydrogen spectrum test results: 1 H NMR (300MHz, D2O): δ3.69-3.72(dd,1H), 3.22-3.26(m,2H), 1.26-1.99(m,6H).

[0056] (2) Preparation of copolyamide:

[0057] Weigh 50g (400mmol) of aminocaprolactam prepared in step (1), 450g of caprolactam (3960mmol), heat and melt in a reactor, add 15mL (830mmol) of water, react under pressure at 190°C, 0.8MPa for 6h, react at 210°C, 0MPa for 1h, react under reduced pressure at 210°C, -0.1MPa for 1h, discharge, pelletize, and obtain a copolyamide product with a yield of 80%. The number average molecular weight measured by GPC is 27.8kDa. Nuclear magnetic resonance hydrogen spectrum test results: 1 H NMR (500MHz, TFA / CDCl3, 1:5, v:v): δ3.27-3.09(m,4H), 3.06-2.99(m,1H), 2.35-2.14(m,2H), 1.74-1.15(m,12H).

[0058] (3) Preparation of antibacterial nylon:

[0059] Weigh 100 g of the copolyamide pellets prepared in step (2), add 500 mL of ethanol and 30 g of acetic acid, heat and reflux at 70°C for 5 h, and filter. Put the pellets into 1000 mL of water and wash them at 70°C for 5 h to obtain antibacterial nylon pellets. The yield is 98%. 1 The HNMR spectrum shows that the molar percentage of the protonated seven-membered cyclic lysine derivative in the antibacterial nylon material is 9.5%.

[0060] Example 2.

[0061] (1) Preparation of copolyamide:

[0062] Weigh 25g (200mmol) of aminocaprolactam prepared in step (1) of Example 1, 475g of caprolactam (4180mmol), heat and melt in a reactor, add 15mL (830mmol) of water, react under pressure at 180°C and 0.8MPa for 5h, react under normal pressure at 210°C and 0MPa for 1h, react under reduced pressure at 210°C and -0.1MPa for 1h, discharge, pelletize, and obtain a copolyamide product with a yield of 83%. The number average molecular weight measured by GPC is 20.1kDa. Nuclear magnetic resonance hydrogen spectrum test results: 1 H NMR (500MHz, TFA / CDCl3, 1:5, v:v): δ3.28-3.09(m,4H), 3.07-3.04(m,1H), 2.36-2.12(m,2H), 1.74-1.16(m,12H).

[0063] (2) Preparation of antibacterial nylon:

[0064] Weigh 100 g of the copolyamide pellets prepared in step (2), add 500 mL of ethanol and 30 g of acetic acid, heat and reflux at 70°C for 5 h, and filter. Put the pellets into 1000 mL of water and wash them at 70°C for 5 h to obtain antibacterial nylon pellets. The yield is 99%. 1 The HNMR spectrum shows that the molar percentage of the protonated seven-membered cyclic lysine derivative in the antibacterial nylon material is 4%.

[0065] Example 3.

[0066] (1) Preparation of copolyamide:

[0067] Weigh 75g (590mmol) of aminocaprolactam prepared in step (1) of Example 1, 425g of caprolactam (3740mmol), heat and melt in a reactor, add 15mL (830mmol) of water, react under pressure at 200°C, 1.0MPa for 6h, react under normal pressure at 210°C, 0MPa for 1h, react under reduced pressure at 210°C, -0.1MPa for 2h, discharge, pelletize, and obtain a copolyamide product with a yield of 85%. The number average molecular weight measured by GPC is 35.6kDa. Nuclear magnetic resonance hydrogen spectrum test results: 1 H NMR (500MHz, TFA / CDCl3, 1:5, v:v): δ3.30-3.08(m,4H), 3.05-2.99(m,1H), 2.36-2.10(m,2H), 1.78-1.16(m,12H).

[0068] (2) Preparation of antibacterial nylon:

[0069] Weigh 100 g of the copolyamide pellets prepared in step (2), add 500 mL of ethanol and 30 g of acetic acid, heat and reflux at 70°C for 5 h, and filter. Put the pellets into 1000 mL of water and wash them at 70°C for 5 h to obtain antibacterial nylon pellets. The yield is 96%. 1 The HNMR spectrum shows that the molar percentage of the protonated seven-membered cyclic lysine derivative in the antibacterial nylon material is 14%.

[0070] Example 4.

[0071] (1) Preparation of copolyamide:

[0072] Weigh 100g (780mmol) of aminocaprolactam prepared in step (1) of Example 1, 400g of caprolactam (3520mmol), heat and melt in a reactor, add 15mL (830mmol) of water, react under pressure at 190°C, 0.8MPa for 6h, react under normal pressure at 220°C, 0MPa for 1h, react under reduced pressure at 220°C, -0.1MPa for 1.5h, discharge, pelletize, and obtain a copolyamide product with a yield of 88%. The number average molecular weight measured by GPC is 41.7kDa. Nuclear magnetic resonance hydrogen spectrum test results: 1 H NMR (500MHz, TFA / CDCl3, 1:5, v:v): δ3.28-2.99(m,5H), 2.36-2.18(m,2H), 1.77-1.10(m,12H).

[0073] (2) Preparation of antibacterial nylon:

[0074] Weigh 100 g of the copolyamide pellets prepared in step (2), add 500 mL of ethanol and 50 g of acetic acid, heat and reflux at 70°C for 5 h, and filter. Put the pellets into 1000 mL of water and wash them at 70°C for 5 h to obtain antibacterial nylon pellets. The yield is 99%. 1 The HNMR spectrum shows that the molar percentage of the protonated seven-membered cyclic lysine derivative in the antibacterial nylon material is 18.7%.

[0075] Example 5.

[0076] (1) Preparation of copolyamide:

[0077] Weigh 125g (1000mmol) of aminocaprolactam prepared in step (1) of Example 1, 375g of caprolactam (3320mmol), heat and melt in a reactor, add 15mL (830mmol) of water, react under pressure at 210°C, 1.2MPa for 8h, react under normal pressure at 230°C, 0MPa for 1h, react under reduced pressure at 230°C, -0.1MPa for 3h, discharge, pelletize, and obtain a copolyamide product with a yield of 86%. The number average molecular weight measured by GPC is 53.9kDa. Nuclear magnetic resonance hydrogen spectrum test results: 1 H NMR (500MHz, TFA / CDCl3, 1:5, v:v): δ3.29-3.04(m,4H), 3.03-2.98(m,1H), 2.34-2.10(m,2H), 1.70-1.09(m,12H).

[0078] (2) Preparation of antibacterial nylon:

[0079] Weigh 100 g of the copolyamide pellets prepared in step (2), add 500 mL of ethanol and 80 g of acetic acid, heat and reflux at 70°C for 5 h, and filter. Put the pellets into 1000 mL of water and wash them at 70°C for 5 h to obtain antibacterial nylon pellets. The yield is 95%. 1 The HNMR spectrum shows that the molar percentage of the protonated seven-membered cyclic lysine derivative in the antibacterial nylon material is 24.3%.

[0080] Example 6.

[0081] (1) Preparation of copolyamide:

[0082] Weigh 25g (200mmol) of aminocaprolactam prepared in step (1) of Example 1, 475g of caprolactam (4180mmol), heat and melt in a reactor, add 30mL (1660mmol) of water, react under pressure at 190°C and 0.8MPa for 6h, react under normal pressure at 210°C and 0MPa for 1h, react under reduced pressure at 210°C and -0.1MPa for 1h, discharge, pelletize, and obtain a copolyamide product with a yield of 85%. The number average molecular weight measured by GPC is 15.1kDa. Nuclear magnetic resonance hydrogen spectrum test results: 1 H NMR (500MHz, TFA / CDCl3, 1:5, v:v): δ3.31-3.10(m,4H), 3.08-3.06(m,1H), 2.35-2.13(m,2H), 1.73-1.18(m,12H).

[0083] (2) Preparation of antibacterial nylon:

[0084] Weigh 100 g of the copolyamide pellets prepared in step (2), add 500 mL of ethanol and 30 g of acetic acid, heat and reflux at 70°C for 5 h, and filter. Put the pellets into 1000 mL of water and wash them at 70°C for 5 h to obtain antibacterial nylon pellets. The yield is 98%. 1 The HNMR spectrum shows that the molar percentage of the protonated seven-membered cyclic lysine derivative in the antibacterial nylon material is 4.3%.

[0085] Example 7.

[0086] Weigh 100 g of the copolyamide pellets prepared in step (2) of Example 2, add 500 mL of methanol and 50 g of benzoic acid, heat and reflux at 60°C for 5 h, and filter. Put the pellets into 1000 mL of water and wash with ethanol at 70°C for 5 h to obtain antibacterial nylon pellets. The yield is 94%. 1 The H NMR spectrum shows that the molar percentage of the protonated seven-membered cyclic lysine derivative in the antibacterial nylon material is 4.5%.

[0087] Example 8.

[0088] Weigh 100 g of the copolyamide pellets prepared in step (2) of Example 2, add 500 mL of tetrahydrofuran and 70 g of citric acid, heat and reflux at 70°C for 5 h, and filter. Put the pellets into 1000 mL of water and wash them at 70°C for 5 h to obtain antibacterial nylon pellets. The yield is 96%. 1 The HNMR spectrum shows that the molar percentage of the protonated seven-membered cyclic lysine derivative in the antibacterial nylon material is 3.8%.

[0089] Example 9.

[0090] (1) Preparation of monomethylaminocaprolactam (monoprotected cyclic lysine, R=CH3 in formula III):

[0091] Weigh 100g (780mmol) of aminocaprolactam prepared in step (1) of Example 1, add 1L of n-hexane, 55mL (860mmol) of methyl formate, heat and reflux for 5h under the condition of a water separator, filter, dissolve the filtered solid in 500mL of methanol, add 44g of sodium borohydride (1170mmol), react for 3h and recrystallize to obtain the product. The yield is 75%, and the purity is 98% according to H NMR analysis. H NMR test results: 1 H NMR (300MHz, D2O): δ3.68-3.73(dd,1H),3.38(s,3H),3.21-3.27(m,5H),1.30-2.01(m,6H).

[0092] (2) Preparation of copolyamide:

[0093] Weigh 50g (350mmol) of monomethylaminocaprolactam prepared in step (1), 450g of caprolactam (3960mmol), heat and melt in a reactor, add 15mL (830mmol) of water, react under pressure at 190°C, 0.8MPa for 6h, react at 210°C, 0MPa for 1h, react under reduced pressure at 210°C, -0.1MPa for 1h, discharge, pelletize, and obtain a copolyamide product with a yield of 80%. The number average molecular weight measured by GPC is 18.6kDa. Nuclear magnetic resonance hydrogen spectrum test results: 1 H NMR (500MHz, TFA / CDCl3, 1:5, v:v): δ3.36 (s, 3H), 3.25-3.08 (m, 4H), 3.06-2.98 (m, 1H), 2.32-2.18 (m, 2H), 1.79-1.13 (m, 12H).

[0094] (3) Preparation of antibacterial nylon:

[0095] Weigh 100 g of the copolyamide pellets prepared in step (2), add 500 mL of acetonitrile and 30 g of acetic acid, heat and reflux at 70°C for 5 h, and filter. Put the pellets into 1000 mL of water and wash them at 70°C for 5 h to obtain antibacterial nylon pellets. The yield is 96%. 1 The HNMR spectrum shows that the molar percentage of the protonated seven-membered cyclic lysine derivative in the antibacterial nylon material is 8.7%.

[0096] Example 10.

[0097] (1) Preparation of monoethylaminocaprolactam (monoprotected cyclic lysine, R=CH2CH3 in formula III):

[0098] Weigh 100g (780mmol) of aminocaprolactam prepared in step (1) of Example 1, add 1L of methanol, 105mL (940mmol) of ethanol solution of acetaldehyde, 105g (1000mmol) of anhydrous sodium carbonate, heat to reflux for 5h, filter, add 44g of sodium borohydride (1170mmol) to the filtrate, react for 3h and recrystallize to obtain the product. The yield is 63%, and the purity is 95% according to H NMR spectrum analysis. H NMR spectrum test results: 1 H NMR (300MHz, D2O): δ3.69-3.72(dd,1H),3.22-3.26(m,2H),2.59(m,2H),1.26-1.99(m,6H),1.13(t,3H).

[0099] (2) Preparation of copolyamide:

[0100] Weigh 50g (320mmol) of monoethylaminocaprolactam prepared in step (1), 450g of caprolactam (3960mmol), heat and melt in a reactor, add 15mL (830mmol) of water, react under pressure at 190°C, 0.8MPa for 6h, react under normal pressure at 210°C, 0MPa for 1h, react under reduced pressure at 210°C, -0.1MPa for 1h, discharge, pelletize, and obtain a copolyamide product with a yield of 79%. The number average molecular weight measured by GPC is 19.5kDa. Nuclear magnetic resonance hydrogen spectrum test results: 1 H NMR (500MHz, TFA / CDCl3, 1:5, v:v): δ3.28-2.95(m,5H), 2.61(m,2H), 2.30-2.09(m,2H), 1.80-1.12(m,15H).

[0101] (3) Preparation of antibacterial nylon:

[0102] Weigh 100 g of the copolyamide pellets prepared in step (2), add 500 mL of tetrahydrofuran and 30 g of acetic acid, heat and reflux at 70°C for 5 h, and filter. Put the pellets into 1000 mL of water and wash them at 70°C for 5 h to obtain antibacterial nylon pellets. The yield is 98%. 1 The H NMR spectrum shows that the molar percentage of the protonated seven-membered cyclic lysine derivative in the antibacterial nylon material is 8.5%.

[0103] Example 11.

[0104] (1) Preparation of monobenzylaminocaprolactam (monoprotected cyclic lysine, R=CH2Ph ​​in formula III):

[0105] Weigh 100g (780mmol) of aminocaprolactam prepared in step (1) of Example 1, add 1.5L methanol, 100mL (980mmol) benzaldehyde, 105g (1000mmol) anhydrous sodium carbonate, heat to reflux for 4h, filter, add 44g sodium borohydride (1170mmol) to the filtrate, react for 3h and recrystallize to obtain the product. The yield is 70%, and the purity is 97% according to H NMR spectrum analysis. H NMR spectrum test results: 1 H NMR (300MHz, D2O): δ7.50-7.31(m,5H),4.62(s,2H),3.65-3.70(dd,1H),3.21-3.27(m,2H),1.20-1.97(m,6H).

[0106] (2) Preparation of copolyamide:

[0107] Weigh 70g (320mmol) of the monobenzylaminocaprolactam prepared in step (1) and 450g of caprolactam (3960mmol), heat and melt in a reactor, add 15mL (830mmol) of water, react under pressure at 190°C and 0.8MPa for 6h, react under normal pressure at 210°C and 0MPa for 1h, react under reduced pressure at 210°C and -0.1MPa for 1h, discharge, pelletize, and obtain a copolyamide product with a yield of 82%. The number average molecular weight measured by GPC is 20.1kDa. Nuclear magnetic resonance hydrogen spectrum test results: 1 H NMR (500MHz, TFA / CDCl3, 1:5, v:v): δ7.52-7.34(m,5H),3.81(s,2H),3.24-3.09(m,4H),3.05-2.97(m,1H),2.40-2.18(m,2H),1.79-1.12(m,12H).

[0108] (3) Preparation of antibacterial nylon:

[0109] Weigh 100 g of the copolyamide pellets prepared in step (2), add 500 mL of acetonitrile and 30 g of acetic acid, heat and reflux at 70°C for 5 h, and filter. Put the pellets into 1000 mL of water and wash them at 70°C for 5 h to obtain antibacterial nylon pellets. The yield is 98%. 1 The HNMR spectrum shows that the molar percentage of the protonated seven-membered cyclic lysine derivative in the antibacterial nylon material is 7.5%.

[0110] Example 12.

[0111] (1) Monododecylaminocaprolactam (monoprotected cyclic lysine, R=(CH2) in formula III) 11 Preparation of CH3):

[0112] Weigh 100g (780mmol) of aminocaprolactam prepared in step (1) of Example 1, add 1L of water, 80g (940mmol) of sodium bicarbonate, 3g of sodium dodecylsulfonate, 225mL (940mmol) of dodecane bromide, heat and reflux at 80°C for 5h, filter, wash the filtrate three times with 2L of dichloromethane, and recrystallize the organic phase after drying. The yield is 45%, and the purity is 92% according to H NMR spectrum analysis. H NMR spectrum test results: 1 H NMR (300MHz, D2O): δ3.69-3.72(dd,1H),3.22-3.26(m,2H),2.53(t,2H),1.26-1.99(m,26H),0.88(t,3H).

[0113] (2) Preparation of copolyamide:

[0114] Weigh 100g (340mmol) of monododecylaminocaprolactam prepared in step (1), 450g of caprolactam (3960mmol), heat and melt in a reactor, add 15mL (830mmol) of water, react under pressure at 190°C, 0.8MPa for 6h, react under normal pressure at 210°C, 0MPa for 1h, react under reduced pressure at 210°C, -0.1MPa for 1h, discharge, pelletize, and obtain a copolyamide product with a yield of 81%. The number average molecular weight measured by GPC is 30.5kDa. Nuclear magnetic resonance hydrogen spectrum test results: 1 H NMR (500MHz, TFA / CDCl3, 1:5, v:v): δ3.28-3.07(m,4H), 3.03-2.90(m,1H), 2.55-2.19(m,4H), 1.74-0.87(m,35H).

[0115] (3) Preparation of antibacterial nylon:

[0116] Weigh 100 g of the copolyamide pellets prepared in step (2), add 500 mL of chloroform and 30 g of acetic acid, heat and reflux at 70°C for 5 h, and filter. Put the pellets into 1000 mL of ethanol and wash at 70°C for 5 h to obtain antibacterial nylon pellets. The yield is 96%. 1 The H NMR spectrum shows that the molar percentage of the protonated seven-membered cyclic lysine derivative in the antibacterial nylon material is 6.3%.

[0117] Example 13.

[0118] (1) Preparation of aminocaprolactam hydrochloride (salified cyclic lysine, R=H in formula III):

[0119] Weigh 100 g (780 mmol) of aminocaprolactam prepared in step (1) of Example 1, add 500 mL of acetone, add 80 mL (960 mmol) of concentrated hydrochloric acid, stir and react for 2 h, filter and obtain the product. The yield is 90%, and the purity is 99% according to H NMR spectrum analysis. H NMR spectrum test results: 1 H NMR (300MHz, D2O): δ3.75-3.80(dd,1H), 3.23-3.28(m,2H), 1.27-2.01(m,6H).

[0120] (2) Preparation of copolyamide:

[0121] Weigh 50g (300mmol) of aminocaprolactam hydrochloride prepared in step (1), 450g of caprolactam (3960mmol), heat and melt in a reactor, add 15mL (830mmol) of water, react under pressure at 190°C, 0.8MPa for 6h, react at 210°C, 0MPa for 1h, react under reduced pressure at 210°C, -0.1MPa for 1h, discharge, pelletize, and obtain a copolyamide product with a yield of 80%. The number average molecular weight measured by GPC is 25.7kDa. Nuclear magnetic resonance hydrogen spectrum test results: 1 H NMR (500MHz, TFA / CDCl3, 1:5, v:v): δ3.29-2.97(m,5H), 2.36-2.18(m,2H), 1.75-1.19(m,12H).

[0122] (3) Preparation of antibacterial nylon:

[0123] Weigh 100 g of the copolyamide pellets prepared in step (2), add 500 mL of ethyl acetate and 20 g of acetic acid, heat and reflux at 70°C for 5 h, and filter. Put the pellets into 1000 mL of water and wash them at 70°C for 5 h to obtain antibacterial nylon pellets. The yield is 99%. 1 The H NMR spectrum shows that the molar percentage of the protonated seven-membered cyclic lysine derivative in the antibacterial nylon material is 10.2%.

[0124] Example 14.

[0125] (1) Preparation of aminocaprolactam benzoate (salified cyclic lysine, R=H in formula III)

[0126] Weigh 100 g (780 mmol) of aminocaprolactam prepared in step (1) of Example 1, add 500 mL of acetone, add 117 g (960 mmol) of benzoic acid, stir and react for 2 h, filter and obtain the product. The yield is 90%, and the purity is 99% according to H NMR analysis. H NMR test results: 1 H NMR (300MHz, D2O): δ7.33-7.56(m,5H), 3.76-3.83(dd,1H), 3.24-3.31(m,2H), 1.28-2.00(m,6H).

[0127] (2) Preparation of copolyamide:

[0128] Weigh 75g (300mmol) of aminocaprolactam benzoate prepared in step (1), 450g of caprolactam (3960mmol), heat and melt in a reactor, add 15mL (830mmol) of water, react under pressure at 190°C, 0.8MPa for 6h, react at 210°C, 0MPa for 1h, react under reduced pressure at 210°C, -0.1MPa for 1h, discharge, pelletize, and obtain a copolyamide product with a yield of 80%. The number average molecular weight measured by GPC is 29.8kDa. Nuclear magnetic resonance hydrogen spectrum test results: 1 H NMR (500MHz, TFA / CDCl3, 1:5, v:v): δ7.37-7.59(m,5H), 3.32-2.96(m,5H), 2.34-2.17(m,2H), 1.78-1.19(m,12H).

[0129] (3) Preparation of antibacterial nylon:

[0130] Weigh 100 g of the copolyamide pellets prepared in step (2), add 500 mL of acetone and 20 g of acetic acid, heat and reflux at 70°C for 5 h, and filter. Put the pellets into 1000 mL of water and wash them at 70°C for 5 h to obtain antibacterial nylon pellets. The yield is 98%. 1 The HNMR spectrum shows that the molar percentage of the protonated seven-membered cyclic lysine derivative in the antibacterial nylon material is 11%.

[0131] Example 15.

[0132] (1) Preparation of monomethylaminocaprolactam hydrochloride (salt-forming cyclic lysine, R=CH3 in formula III):

[0133] Weigh 100 g (700 mmol) of monomethylaminocaprolactam prepared in step (1) of Example 9, add 500 mL of acetone, add 80 mL (960 mmol) of concentrated hydrochloric acid, stir and react for 2 h, filter and obtain the product. The yield is 92%, and the purity is 99% according to H NMR spectrum analysis. H NMR spectrum test results: 1 H NMR (300MHz, D2O): δ3.78-3.84(dd,1H),3.45(s,3H),3.25-3.29(m,2H),1.22-2.04(m,6H).

[0134] (2) Preparation of copolyamide:

[0135] Weigh 50g (280mmol) of monomethylaminocaprolactam hydrochloride prepared in step (1), 450g of caprolactam (3960mmol), heat and melt in a reactor, add 15mL (830mmol) of water, react under pressure at 190°C, 0.8MPa for 6h, react at 210°C, 0MPa for 1h, react under reduced pressure at 210°C, -0.1MPa for 1h, discharge, pelletize, and obtain a copolyamide product with a yield of 80%. The number average molecular weight measured by GPC is 25.4kDa. Nuclear magnetic resonance hydrogen spectrum test results: 1 H NMR (500MHz, TFA / CDCl3, 1:5, v:v): δ3.49 (s, 3H), 3.28-3.08 (m, 4H), 3.06-2.95 (m, 1H), 2.36-2.14 (m, 2H), 1.73-1.18 (m, 12H).

[0136] (3) Preparation of antibacterial nylon:

[0137] Weigh 100 g of the copolyamide pellets prepared in step (2), add 500 mL of ethanol and 20 g of acetic acid, heat and reflux at 70°C for 5 h, and filter. Put the pellets into 1000 mL of water and wash them at 70°C for 5 h to obtain antibacterial nylon pellets. The yield is 95%. 1 The HNMR spectrum shows that the molar percentage of the protonated seven-membered cyclic lysine derivative in the antibacterial nylon material is 10.4%.

[0138] Example 16.

[0139] (1) Preparation of copolyamide:

[0140] Weigh 50g (400mmol) of aminocaprolactam prepared in step (1) of Example 1, 450g of valerolactam (4500mmol), heat and melt in a reactor, add 15mL (830mmol) of water, react under pressure at 190°C, 0.8MPa for 6h, react under normal pressure at 220°C, 0MPa for 1h, react under reduced pressure at 220°C, -0.1MPa for 1.5h, discharge, pelletize, and obtain a copolyamide product with a yield of 78%. The number average molecular weight measured by GPC is 25.7kDa. Nuclear magnetic resonance hydrogen spectrum test results: 1 H NMR (500MHz, TFA / CDCl3, 1:5, v:v): δ3.29-2.99(m,5H), 2.35-2.22(m,2H), 1.76-1.13(m,10H).

[0141] (2) Preparation of antibacterial nylon:

[0142] Weigh 100 g of the copolyamide pellets prepared in step (2), add 500 mL of ethanol and 50 g of acetic acid, heat and reflux at 70°C for 5 h, and filter. Put the pellets into 1000 mL of water and wash them at 70°C for 5 h to obtain antibacterial nylon pellets. The yield is 98%. 1 The HNMR spectrum shows that the molar percentage of the protonated seven-membered cyclic lysine derivative in the antibacterial nylon material is 19.5%.

[0143] Example 17.

[0144] (1) Preparation of copolyamide:

[0145] Weigh 50g (400mmol) of aminocaprolactam prepared in step (1) of Example 1, 450g of enantholactam (3540mmol), heat and melt in a reactor, add 15mL (830mmol) of water, react under pressure at 190°C, 0.8MPa for 6h, react under normal pressure at 220°C, 0MPa for 1h, react under reduced pressure at 220°C, -0.1MPa for 1.5h, discharge, pelletize, and obtain a copolyamide product with a yield of 81%. The number average molecular weight measured by GPC is 36.9kDa. Nuclear magnetic resonance hydrogen spectrum test results: 1 H NMR (500MHz, TFA / CDCl3, 1:5, v:v): δ3.31-3.02(m,5H), 2.35-2.19(m,2H), 1.78-1.02(m,14H).

[0146] (2) Preparation of antibacterial nylon:

[0147] Weigh 100 g of the copolyamide pellets prepared in step (2), add 500 mL of ethanol and 50 g of acetic acid, heat and reflux at 70°C for 5 h, and filter. Put the pellets into 1000 mL of water and wash them at 70°C for 5 h to obtain antibacterial nylon pellets. The yield is 98%. 1 The HNMR spectrum shows that the molar percentage of the protonated seven-membered cyclic lysine derivative in the antibacterial nylon material is 16.3%.

[0148] Example 18.

[0149] (1) Preparation of copolyamide:

[0150] Weigh 50g (400mmol) of aminocaprolactam prepared in step (1) of Example 1, 450g of capryllactam (3180mmol), heat and melt in a reactor, add 15mL (830mmol) of water, react under pressure at 190°C, 0.8MPa for 6h, react under normal pressure at 220°C, 0MPa for 1h, react under reduced pressure at 220°C, -0.1MPa for 1.5h, discharge, pelletize, and obtain a copolyamide product with a yield of 83%. The number average molecular weight measured by GPC is 52.3kDa. Nuclear magnetic resonance hydrogen spectrum test results: 1 H NMR (500MHz, TFA / CDCl3, 1:5, v:v): δ3.27-3.05(m,5H), 2.39-2.16(m,2H), 1.83-1.15(m,16H).

[0151] (2) Preparation of antibacterial nylon:

[0152] Weigh 100 g of the copolyamide pellets prepared in step (2), add 500 mL of ethanol and 50 g of acetic acid, heat and reflux at 70°C for 5 h, and filter. Put the pellets into 1000 mL of water and wash them at 70°C for 5 h to obtain antibacterial nylon pellets. The yield is 99%. 1 The HNMR spectrum shows that the molar percentage of the protonated seven-membered cyclic lysine derivative in the antibacterial nylon material is 17.2%.

[0153] Comparative Example 1.

[0154] Weigh 500g of caprolactam (4400mmol), heat and melt in a reactor, add 15mL (830mmol) of water, react under pressure at 190℃, 0.8MPa for 6h, react at 210℃, 0MPa for 1h, react under reduced pressure at 210℃, -0.1MPa for 1h, discharge, pelletize, and obtain homopolymerized nylon product with a yield of 85%. The number average molecular weight measured by GPC is 26.3kDa. Nuclear magnetic resonance hydrogen spectrum test results: 1H NMR (500MHz, TFA / CDCl3, 1:5, v:v): δ3.25-3.17(m,2H), 2.25-2.19(m,2H), 1.78-1.16(m,6H).

[0155] Comparative Example 2.

[0156] (1) Preparation of copolyamide:

[0157] Weigh 350g (2450mmol) of aminocaprolactam prepared in step (1) of Example 1, 250g of caprolactam (2200mmol), heat and melt in a reactor, add 18mL (1000mmol) of water, react under pressure at 190°C and 0.8MPa for 6h, react at 210°C and 0MPa for 1h, react under reduced pressure at 210°C and -0.1MPa for 1h, discharge, pelletize, and obtain a copolyamide product with a yield of 80%. The product is insoluble in hexafluoroisopropanol and cannot be measured by GPC. Nuclear magnetic resonance hydrogen spectrum test results: 1 H NMR (500MHz, TFA / CDCl3, 1:5, v:v): δ3.32-2.90(m,5H), 2.37-2.16(m,2H), 1.73-1.20(m,12H).

[0158] (2) Preparation of antibacterial nylon:

[0159] Weigh 100 g of the copolyamide pellets prepared in step (3), add 1000 mL of ethanol and 500 g of acetic acid, heat under reflux at 70° C. for 5 h, and filter. Put the pellets into 1000 mL of water and wash them at 70° C. for 5 h. The yield is 98%, and the molar percentage of the protonated seven-membered cyclic lysine derivative in the antibacterial nylon material is 56%.

[0160] Comparative Example 3.

[0161] (1) Preparation of copolyamide:

[0162] Weigh 2.5 g (20 mmol) of aminocaprolactam prepared in step (1) of Example 1, 497.5 g of caprolactam (4370 mmol), heat and melt in a reactor, add 15 mL (830 mmol) of water, react under pressure at 190° C., 0.8 MPa for 6 h, react under normal pressure at 210° C., 0 MPa for 1 h, react under reduced pressure at 210° C., -0.1 MPa for 1 h, discharge, pelletize, and obtain a copolyamide product with a yield of 80%. The number average molecular weight measured by GPC is 17.8 kDa. Nuclear magnetic resonance hydrogen spectrum test results: 1H NMR (500MHz, TFA / CDCl3, 1:5, v:v): δ3.26-3.08(m,5H), 2.30-2.18(m,2H), 1.74-1.19(m,12H).

[0163] (2) Preparation of antibacterial nylon:

[0164] Weigh 100 g of the copolyamide pellets prepared in step (3), add 1000 mL of methanol and 20 g of acetic acid, heat and reflux at 70° C. for 5 h, and filter. Put the pellets into 1000 mL of water and wash them at 70° C. for 5 h. The yield is 97%, and the molar percentage of the protonated seven-membered cyclic lysine derivative in the antibacterial nylon material is 0.4%.

[0165] Effect example.

[0166] Antibacterial effect test:

[0167] The antibacterial effect test was carried out according to the method of Chinese national standard GB / T 314022023, and some conditions were adjusted according to the actual situation. The specific operation was as follows: the antibacterial nylon material prepared in Example 118 and the nylon material prepared in Comparative Example 13 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 dripped with 6×10 5 0.4 mL of bacterial solution with CFU / mL was covered with PET film and cultured at 37°C for 24 hours. The slices were rinsed with 10 mL of SCDLP liquid culture medium, the bacterial solution was diluted, and the mixture was mixed with PCA culture medium after gradient dilution, and cultured at 37°C for 48 hours. The colonies in the culture medium were counted using a fully automatic colony counter to estimate the bacterial concentration of the bacterial solution after culture. The conventional nylon material obtained in Comparative Example 1 was used as the control group. Figure 5 and Figure 6 The comparison photos of the antibacterial effect of the nylon material prepared in Example 1 and Comparative Example 1 on Staphylococcus aureus are shown, and the dilution ratio is 100 times. The spots shown therein are surviving colonies. It can be clearly seen from the figure that compared with the conventional nylon material prepared in Comparative Example 1, the antibacterial nylon material of the present invention has a significant inhibitory effect on Staphylococcus aureus. The detection bacteria used are Staphylococcus aureus (S.aureus) ATCC6538 and Escherichia coli (E.coli) ATCC25922. The test results are shown in Table 1.

[0168] The antibacterial rate calculation formula is as follows:

[0169]

[0170] Mechanical properties test:

[0171] The antibacterial nylon materials prepared in the above Examples 1 to 18 and the nylon materials prepared in Comparative Examples 1 to 3 were respectively injection molded into 5A type specimens (for dimensions, see Chinese national standard GB / T 1040.2-2022), and tensile properties were tested. The results are shown in Table 1.

[0172] As shown in the data of Table 1, the antibacterial nylon material of the present invention has significant antibacterial effect and mechanical properties substantially equivalent to those of conventional nylon materials (Comparative Example 1). In contrast, the mechanical properties of the nylon material of Comparative Example 2 are poor, and the antibacterial properties of the nylon material of Comparative Example 3 are insufficient.

[0173] Table 1

[0174]

[0175]

[0176] The preferred embodiments of the present invention are described in detail above. However, the present invention is not limited to the specific details in the above embodiments. Within the technical concept of the present invention, a variety of simple modifications can be made to the technical solution of the present invention, and these simple modifications all belong to the protection scope of the present invention.

[0177] It should also be noted that the various specific technical features described in the above specific embodiments can be combined in any suitable manner without contradiction. In order to avoid unnecessary repetition, the present invention will not further describe various possible combinations.

[0178] In addition, various embodiments of the present invention may be arbitrarily combined, and as long as they do not violate the concept of the present invention, they should also be regarded as the content protected by the present invention.

Claims

1. An antibacterial nylon material, characterized in that: The molecular structure contains two different repeating units as shown in the following formula I and formula II: Wherein, R is selected from hydrogen, C 1～28 Substituted / unsubstituted straight chain / branched, saturated / unsaturated aliphatic hydrocarbon group, substituted / unsubstituted, saturated / unsaturated C 3～15 Alicyclic hydrocarbon, substituted / unsubstituted C 6～22 Aryl, substituted / unsubstituted, saturated / unsaturated C 7～35 One of the aralkyl groups; the substitution refers to halogen, nitro, C 1～18 One or more substituents in a straight or branched alkyl group; n is any natural number from 1 to 8; x and y represent the molar ratio of the corresponding repeating units, x is selected from 0.01 to 0.50, y is selected from 0.50 to 0.99, and x+y=1.

2. A method for preparing the antibacterial nylon material according to claim 1, characterized in that: The following steps are involved: Step 1: mixing a seven-membered cyclic lysine derivative monomer with lactam, using water as an initiator, and performing hydrolysis polymerization to obtain a copolyamide; Step 2: placing the copolyamide in an acid solution, heating and stirring to perform a protonation reaction, and purifying the reaction product to obtain an antibacterial nylon material; The seven-membered cyclic lysine derivative monomer is a structure as shown in Formula III, or a salt-forming cyclic lysine monomer obtained by reacting the exocyclic amino group (or single-protected amino group) in the structure of Formula III with an acid: The structural formula of the lactam is shown in Formula IV:

3. The method for preparing the antibacterial nylon material according to claim 2, characterized in that: The seven-membered cyclic lysine derivative monomer is prepared by the following steps: Lysine or lysine hydrochloride is mixed with methanol, an equimolar amount of sodium hydroxide is added or not, a dehydration ring reaction is carried out at 125°C to 200°C, and then extracted with ethyl acetate to obtain; Or by further reacting aminocaprolactam with corresponding acids, aldehydes or halogenated hydrocarbons having an R group; Or it can be obtained by reacting unprotected or single-protected cyclic lysine monomer with acid.

4. The method for preparing the antibacterial nylon material according to claim 2, characterized in that: The molar ratio of the seven-membered cyclic lysine derivative monomer to the lactam in step 1 is 0.01 to 1:1; The mass ratio of the total mass of the seven-membered cyclic lysine derivative monomer and the lactam to water is 10 to 200:

1.

5. The method for preparing the antibacterial nylon material according to claim 2, characterized in that: In step 1, a catalyst is added, wherein the catalyst is selected from halogen hydrides or oxygen-containing acids, sulfur, nitrogen or phosphorus oxygen-containing acids, C 1～35 A mixture of one or at least two of 1-5-carboxylic acids, hydroxy acids, amino acids, sulfonic acids or phosphoric acids, hydroxides, carbonates, bicarbonates, basic carbonates of alkali metals or alkaline earth metals; The molar ratio of the catalyst to the total amount of the seven-membered cyclic lysine-derived monomer and the lactam is 0.001 to 0.1:

1.

6. The method for preparing the antibacterial nylon material according to claim 2, characterized in that: The hydrolysis polymerization conditions described in step 1 are: polymerization temperature of 140° C. to 320° C., polymerization time of 2 h to 96 h, and polymerization pressure of -0.1 MPa to 5 MPa.

7. The method for preparing the antibacterial nylon material according to claim 2, characterized in that: The hydrolysis polymerization in step 1 is divided into three stages: pressure reaction, normal pressure reaction and reduced pressure reaction. The reaction conditions of each stage are as follows: Pressurized reaction stage: polymerization temperature is 140°C to 230°C, polymerization time is 2h to 24h, and polymerization pressure is 0.3MPa to 5MPa; Normal pressure reaction stage: polymerization temperature is 180℃~280℃, polymerization time is 0.5h~10h, polymerization pressure is -0.05MPa~0.1MPa; Reduced pressure reaction stage: polymerization temperature is 200°C to 320°C, polymerization time is 2h to 36h, and polymerization pressure is -0.1MPa to 0MPa.

8. The method for preparing the antibacterial nylon material according to claim 2, characterized in that: The acid in the acid solution in step 2 is selected from halogen hydrides or oxygen-containing acids, sulfur, nitrogen or phosphorus hydrides or oxygen-containing acids, C 1～35 One or a mixture of at least two of 1-5-valent carboxylic acids, hydroxycarboxylic acids, and sulfonic acids; The solvent in the acid solution is selected from one of ether, methyl tert-butyl ether, tetrahydrofuran, ethylene carbonate, propylene carbonate, acetonitrile, methyl ethyl ketone, acetone, methanol, ethanol, butanol, dichloromethane, carbon disulfide, chloroform, ethyl acetate, ethyl isovalerate, N,N-dimethylformamide, N,N-dimethylacetamide, and dimethyl sulfoxide, or a mixture of at least two thereof.

9. The method for preparing the antibacterial nylon material according to claim 2, characterized in that: In step 2, the amount of solvent required for protonation of each gram of copolyamide is 0.1 mL to 20 mL, and the amount of acid is 0.01 g to 10 g; the heating temperature is 20° C. to 180° C.; and the stirring time is 10 min to 48 h.

10. An application of the antibacterial nylon material according to claim 1 or the antibacterial nylon material prepared by the preparation method according to any one of claims 2 to 9, characterized in that: The invention is applied to the preparation of antibacterial nylon products, wherein the antibacterial nylon products include fabrics, plates, pipes, packaging materials and panels.

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