An antibacterial agent, its preparation method and use

Abstract

The application provides an antibacterial agent and a preparation method and application thereof, the antibacterial agent comprises two different repeating units; the structural formula of the antibacterial agent is or by adopting the technical scheme of the application, the antibacterial agent prepared by adopting a copolymerization method has excellent antibacterial performance and long-acting stability, and can meet the requirement of products on long-acting antibacterial performance of the antibacterial agent.

Description

Technical Field

[0001] This invention relates to the field of antibacterial agent technology, and in particular to an antibacterial agent, its preparation method, and its application. Background Technology

[0002] Polyamide (nylon) is one of the most widely produced, varied, and applied engineering plastics. Due to its excellent physical and chemical properties, including high mechanical strength, good electrical properties, wear resistance, oil resistance, resistance to weak acids, weak alkalis, and weakly polar organic solvents, and good processing flowability, it is widely used in construction, automotive, communications, packaging, personal care, and textile industries. With the development of production technology, various base nylon resins and modification techniques have rapidly advanced, endowing nylon with various functional characteristics beyond mechanical properties, such as antibacterial properties, low-temperature resistance, and high-temperature resistance. Functionalized nylon materials have further expanded its application areas.

[0003] Nylon products are prone to contamination and growth of various microorganisms, including pathogens, during processing and use, posing a certain threat to human health. Particularly in applications such as clothing, food packaging, and medicine, the highly efficient, broad-spectrum, long-lasting, and safe antibacterial properties of nylon materials have received significant attention.

[0004] Traditional antibacterial nylon materials are mainly achieved by adding organic antibacterial agents (quaternary ammonium salts, chitosans, guanidine salts, etc.) and inorganic antibacterial agents (zinc oxide, nano-silver, etc.). For example, invention patent 202111357991.5 achieves highly efficient antibacterial properties of nylon 6 fibers by adding 0.1-1 wt% of organic antibacterial agents such as quaternary ammonium salts to nylon 6. Invention patent 202011491219.8 achieves antibacterial properties of nylon composite materials by adding inorganic antibacterial agents such as nano-silver to copolymerized nylon. However, this strategy of achieving antibacterial efficacy in nylon materials by adding antibacterial agents inevitably leads to shortcomings in the prepared materials due to the inherent defects of the antibacterial agents themselves. Organic antibacterial agents have relatively good compatibility with nylon matrix resin and can be uniformly dispersed. However, they are prone to decomposition and failure during the high-temperature processing of nylon. In addition, organic antibacterial agents often have strong toxicity and are prone to causing bacterial resistance. In contrast, inorganic antibacterial agents have good high-temperature stability, but they are prone to leaching during long-term use, which can lead to a decrease or even failure of antibacterial effect. Furthermore, antibacterial agents leached in implantable devices, food packaging, and other fields can cause secondary pollution.

[0005] To improve upon the shortcomings of traditional methods for preparing antibacterial nylon, this invention designs and prepares a polyamide-specific antibacterial agent. This agent is itself a type of polyamide material with intrinsic antibacterial function and exhibits excellent compatibility with commercial polyamides. During the processing and preparation of polyamide products, it is easy to achieve uniform dispersion and solves the problems of decreased antibacterial performance and antibacterial agent contamination caused by antibacterial agent precipitation during long-term use. As a result, the prepared antibacterial polyamide is endowed with good long-lasting antibacterial properties. Summary of the Invention

[0006] To overcome the shortcomings of the prior art, the present invention aims to provide an antibacterial agent, its preparation method, and its application. By introducing a Schiff base structure with antibacterial activity into the polyamide backbone, an antibacterial agent with broad-spectrum antibacterial properties is obtained. This agent can be directly added to polyamide materials as an antibacterial agent, exhibiting good fusion performance. It solves the problems of decreased antibacterial performance and antibacterial agent contamination caused by antibacterial agent precipitation. The production method is simple, the cost is low, and the application is flexible and diverse.

[0007] To achieve the above objectives, the present invention provides the following technical solution: an antibacterial agent comprising compounds as shown in formula (I) or formula (II):

[0008]

[0009] Where n and m are both integers between 1 and 200; the ratio of n to m is 1:60 to 60:1.

[0010] Furthermore, the structural formula of the antibacterial agent is shown below:

[0011]

[0012] Among them, R1 and R3 are benzene rings, C1-C 10 R4 is a straight-chain hydrocarbon group, selected from furan ring, pyrazine ring, and C1-C3 straight-chain hydrocarbon group. 3i It is a C5 straight-chain hydrocarbon group.

[0013] Furthermore, R1 and R3 are benzene rings, C1-C 10 R4 is a straight-chain hydrocarbon group, selected from furan ring, pyrazine ring, and C1-C3 straight-chain hydrocarbon group. 3i It is a C5 straight-chain hydrocarbon group.

[0014] Furthermore, R1 and R3 are the same, i.e., R1 = R3; or, R1 and R3 are different, i.e., R1 ≠ R3; or, R4 is a furan ring, but in this case, R1 ≠ R3.

[0015] Further, the number-average molecular weight of the antibacterial agent is ≥5000 g / mol; and / or, the weight-average molecular weight of the antibacterial agent is ≥10 kg / mol. Preferably, the number-average molecular weight is ≥10000 g / mol; more preferably, ≥20000 g / mol; or, the weight-average molecular weight is ≥10 kg / mol, or ≥20 kg / mol, or ≥100 kg / mol.

[0016] Preferably, the antibacterial agent has an antibacterial rate of 100% against Escherichia coli and / or Staphylococcus aureus.

[0017] To achieve another objective, the present invention also provides a method for preparing the above-mentioned antibacterial agent, wherein raw materials A, B, C and D are dissolved in an organic solvent and mixed evenly, and then stirred and reacted at 50-70°C for 12-24 hours to carry out a copolymerization reaction to obtain the antibacterial agent; and / or, after the copolymerization reaction is completed, the solids in the reaction system are separated by filtration or vacuum filtration, which is the antibacterial agent.

[0018] Furthermore, the intrinsic antibacterial nylon is prepared using raw materials A, B, C, and D;

[0019] The structural formula of raw material A is shown in formula (VI):

[0020]

[0021] R1 is a benzene ring, a C1-C10 straight-chain hydrocarbon group.

[0022] Raw material B is furan dicarboxaldehyde.

[0023] The raw material C is an acylhydrazine or a diamine, and the structural formula of the acylhydrazine is shown in formula (VII).

[0024]

[0025] R3 is a benzene ring, a C1-C10 straight-chain hydrocarbon group;

[0026] The structural formula of the diamine is shown in formula (VI).

[0027]

[0028] Where R 3i It is a C5 straight-chain hydrocarbon group;

[0029] The raw material D is a dialdehyde; the structural formula of the dialdehyde is shown in formula (IX):

[0030]

[0031] Wherein, R4 is a furan ring, benzene ring, pyrazine ring, or a straight-chain hydrocarbon group of C1-C3; however, when R1 and R3 are the same, R4 is a benzene ring, pyrazine ring, or a straight-chain hydrocarbon group of C1-C3.

[0032] Preferably, the molar ratio of raw material A, raw material B, raw material C and raw material D satisfies the following conditions: raw material A: raw material B = 1:1, raw material C: raw material D = 1:1 and (raw material A + raw material B) : (raw material C + raw material D) = 1:60 to 60:1.

[0033] In some preferred embodiments, raw material B and / or raw material D are 2,5-furandicarboxaldehyde or terephthalaldehyde or 1,4-pyrazinedicarboxaldehyde, or malondialdehyde or butanedialdehyde or glutaraldehyde.

[0034]

[0035] Preferably, the organic solvent comprises any one or more combinations of diethyl ether, tetrahydrofuran, dimethyl sulfoxide, ethylene glycol dimethyl ether, anisole, m-nitrobenzene, p-chloroanisole, methyl isobutyl ketone, acetophenone, p-chloroacetophenone, o-nitrobenzene, sulfolane, dichloromethane, chloroform, 1,2-dichloroethane, chlorobenzene, α-chloronaphthalene, acetonitrile, propionitrile, benzene, toluene, cyanobenzene, nitrobenzene, nitrobenzene, ethyl acetate, and methyl benzoate.

[0036] The antibacterial agent provided by the above technical solution can be added as an additive to nylon resin in the prior art to improve the antibacterial properties of nylon materials. Preferably, the amount of the antibacterial agent added to the nylon resin is 0.5% to 5.0% by mass percentage.

[0037] Preferably, in the solution casting method, hexafluoroisopropanol (HFIP) is used to dissolve the antibacterial agent and commercial nylon resin before casting to obtain the relevant products. In the incorporation extrusion method, processing aids, modifying aids, antibacterial agents, and commercial nylon resin are mixed together, added to a twin-screw extruder, and then compounded and extruded to obtain antibacterial nylon. The twin-screw extrusion processing temperature is 240–270°C.

[0038] Preferably, the processing aids and modifying aids include, but are not limited to, plasticizers, flame retardants, lubricants, ultraviolet absorbers, antioxidants, fillers, etc., and the nylon resins include, but are not limited to, nylon 66, nylon 6T66, nylon 6I6T, and nylon 6. The nylon resins are all selected from commercial products, for example, from companies such as Swiss company Emans, Solvay, DuPont, and BASF.

[0039] This invention tested and verified the antibacterial properties of sheets, films, or coatings prepared using the above-mentioned antibacterial agent, and compared them with commercially available Nylon 6 and Nylon 66 products under the same conditions. The results showed that the antibacterial agent prepared by this invention has outstanding antibacterial properties, especially against Escherichia coli and Staphylococcus aureus, with a 100% antibacterial rate compared with existing technologies.

[0040] Technical effects of the present invention:

[0041] 1. By adopting the technical solution of the present invention, the antibacterial agent prepared by copolymerization has excellent antibacterial properties and long-term antibacterial stability, which can meet the requirements of the product for the long-term antibacterial properties of the antibacterial agent.

[0042] 2. The antibacterial agent provided by the technical solution of the present invention has a simple preparation process, high yield, safety and environmental protection, and low cost.

[0043] 3. The antibacterial agent provided by the technical solution of the present invention has a similar structure to nylon material. When used as an antibacterial agent, it can be uniformly dispersed in nylon matrix resin and can solve the problems of incompatibility and precipitation of traditional antibacterial agents, effectively ensuring the long-lasting antibacterial performance of the formed antibacterial nylon material.

[0044] 4. The antibacterial agent provided by the technical solution of the present invention is applied to nylon materials and has the characteristics of flexible and diverse processing methods. It can be processed by melt extrusion injection molding, solution film formation and other methods. The methods are simple to operate and easy to control, making them very suitable for industrial production. Attached Figure Description

[0045] Figure 1 The nuclear magnetic resonance (H-NMR) spectrum of Embodiment 1 of the present invention. Detailed Implementation

[0046] To make the objectives, technical solutions, and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention are clearly and completely described. Obviously, the described embodiments are only some embodiments of this application, not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those skilled in the art without creative effort are within the protection scope of the present invention.

[0047] All patent and non-patent literature publications cited in this invention are incorporated herein by reference.

[0048] The terms “comprising,” “including,” “containing,” “covering,” “having,” “with,” or any other variations thereof, as used in this invention, are intended to cover non-exclusive inclusion. For example, a process, method, article of manufacture, or apparatus that includes a list of elements is not necessarily limited to those elements, but may include other elements not expressly listed or inherent to the process, method, article of manufacture, or apparatus. Furthermore, unless expressly stated otherwise, “or” means inclusive “or” rather than exclusive “or.” For example, condition A or B satisfies any of the following: A is real (or exists) and B is fictitious (or does not exist); A is fictitious (or does not exist) and B is real (or exists); and both A and B are real (or exist). The phrase “one or more” is intended to cover non-exclusive inclusion. For example, one or more A, B, and C means any of the following: A alone, B alone, C alone, a combination of A and B, a combination of B and C, a combination of A and C, or a combination of A, B, and C.

[0049] Additionally, the terms "an" or "a" are used to describe the elements and components described herein. This is done solely for convenience and to provide a general meaning regarding the scope of the invention. This description should be understood to include one or at least one, one or at least one, and the singular includes the plural unless explicitly stated otherwise.

[0050] As used herein, the term “bio-derived” is used interchangeably with “bio-based” or “derived from organisms” and refers to chemical compounds, including monomers and polymers, obtained in whole or in any part from any renewable resource, including but not limited to plant, animal, marine, or forestry materials. The “bio-based content” of any such compound should be understood as the percentage of carbon content that determines whether the compound has been obtained from or derived from such renewable resources.

[0051] As used herein, the term "furandicarboxaldehyde" is used interchangeably with 2,5-dicarboxyfuran and 2,5-furandicarboxaldehyde. As used herein, 2,5-furandicarboxaldehyde (DFF) is an oxidized furan derivative with the structural formula shown below:

[0052]

[0053] Some embodiments of the present invention provide a method for preparing an antibacterial agent, comprising: dissolving equimolar amounts of raw materials A and B, and equimolar amounts of raw materials C and D in the same solvent system, then pouring them into the same reaction vessel and mixing them, and stirring the mixture at 50-70°C for 12-24 hours to carry out a copolymerization reaction; after the reaction is completed, filtering the reaction system to obtain a precipitate, which is the antibacterial agent; and / or, after the copolymerization reaction is completed, filtering to separate the solids in the reaction system, which is the antibacterial agent.

[0054] In raw material A, the structural formula of the acylhydrazine is: R1 is a benzene ring, a C1-C10 straight-chain hydrocarbon group.

[0055] Raw material B is furanyl dicarboxaldehyde.

[0056] Raw material C is an acylhydrazine or a diamine, and the structural formula of the acylhydrazine is shown in formula (VII).

[0057]

[0058] R3 is a benzene ring, a C1-C10 straight-chain hydrocarbon group.

[0059] The structural formula of the diamine is shown in formula (VIII).

[0060]

[0061] Where R 3i It is a C5 straight-chain hydrocarbon group; at the same time

[0062] Raw material D is a dialdehyde; the structural formula of the dialdehyde is shown in formula (VII):

[0063]

[0064] R4 is a straight-chain hydrocarbon group consisting of a furan ring, a benzene ring, a pyrazine ring, or a C1-C3 ring. However, when R1 and R3 are the same, R4 is a straight-chain hydrocarbon group consisting of a benzene ring, a pyrazine ring, or a C1-C3 ring.

[0065] The antibacterial agent prepared using the above method and raw materials contains two not completely identical repeating units, namely a first repeating unit and a second repeating unit; the structural formula of the first repeating unit is:

[0066] Wherein, R1 is a benzene ring, a C1-C10 straight-chain hydrocarbon group;

[0067] The structure of the second repeating unit is:

[0068] Wherein, R3 is a benzene ring, C1-C 10 The straight-chain hydrocarbon group, R4 is selected from furan ring, pyrazine ring, C1-C3 straight-chain hydrocarbon group, R 3i It is a C5 straight-chain hydrocarbon group;

[0069] Furthermore, n and m are both integers between 1 and 200; the ratio of n to m is 1:60 to 60:1.

[0070] Furthermore, the structural formula of the antibacterial agent is shown below:

[0071]

[0072] Where n and m are both integers between 1 and 200; R1 and R3 are benzene rings, C1-C 10 R4 is a straight-chain hydrocarbon group, selected from furan ring, pyrazine ring, and C1-C3 straight-chain hydrocarbon group. 3i It is a C5 straight-chain hydrocarbon group.

[0073] In some embodiments of the present invention, R1 and R3 are the same, that is, R1 = R3.

[0074] In some embodiments of the present invention, R1 and R3 are different, i.e., R1≠R3; or, R4 is a furan ring, but in this case R1≠R3.

[0075] In some implementations, a series of antibacterial agents are obtained by controlling the types of R1, R3, and R4 in the raw materials, the solvent, the reaction temperature, and the reaction time. These agents are then added to a polyurethane system, and products such as sheets, films, and coatings are obtained by selecting appropriate processing techniques such as casting or melt extrusion.

[0076] In some embodiments, the structural formula of raw material A is: Wherein, R1 in raw material A is any one of benzene ring, -CH2-, -CH2CH2-, -CH2CH2CH2CH2-, -CH2CH2CH2CH2CH2-, -CH2CH2CH2CH2CH2CH2-, -CH2CH2CH2CH2CH2CH2CH2-, -CH2CH2CH2CH2CH2CH2CH2CH2-, -CH2CH2CH2CH2CH2CH2CH2CH2-, -CH2CH2CH2CH2CH2CH2CH2CH2CH2-.

[0077] R 3i It is -CH2CH2CH2CH2CH2-.

[0078] R4 is selected from any one of the following: furan ring, pyrazine ring, benzene ring, -CH2-, -CH2CH2-, -CH2CH2CH2-.

[0079] In some implementations, R1 and R3 are the same, i.e., R1 = R3.

[0080] In other implementations, R1 and R3 are different, i.e., R1≠R3.

[0081] In other embodiments, R4 is a furan ring, but in this case R1≠R3.

[0082] In other implementations, R 3i It is a C5 straight-chain hydrocarbon group.

[0083] In some implementations, furanyl dicarboxaldehyde and / or pentanediamine are derived from biomass materials.

[0084] In some embodiments, the antibacterial agent prepared using the technical solution of the present invention is added to nylon material to obtain nylon material products with antibacterial function, which are obtained by twin-screw melt extrusion and injection molding, with a processing temperature between 240 and 270°C.

[0085] In some embodiments, antibacterial nylon material products are formed by dissolving the material in hexafluoroisopropanol (HFIP) and then coating the solution onto the surface of metal substrates such as stainless steel, carbon steel, and aluminum. After the solvent evaporates, an antibacterial nylon material coating is formed.

[0086] In some embodiments, the antibacterial nylon material is obtained by dissolving it in hexafluoroisopropanol (HFIP), casting the solution into a polytetrafluoroethylene or glass petri dish, and peeling it off after the solvent evaporates.

[0087] In some embodiments, the prepared antibacterial nylon material was further subjected to an accelerated aging test for antibacterial performance; wherein the accelerated aging test lasted for 500 to 1000 hours; and the conditions for the accelerated aging test were a humidity of ≥99% and a temperature of 30°C.

[0088] In some comparative examples, the nylon resins used for comparison, including but not limited to nylon 66, nylon 6T66, nylon 6I6T and nylon 6, were selected from commercial products and purchased from companies such as E. Mann, Solvay, DuPont and BASF.

[0089] In some implementations, furanyl dicarboxaldehyde can be obtained from renewable resources.

[0090] During the processing, processing aids and modifiers commonly used in the field are also used, such as plasticizers, flame retardants, lubricants, ultraviolet absorbers, antioxidants, and fillers.

[0091] Specifically, plasticizers include, but are not limited to, one or more mixtures of dioctyl phthalate, didecyl phthalate, liquid paraffin, wax, dimethyl phthalate, diethyl phthalate, phosphate esters, etc.

[0092] And / or, flame retardants include, but are not limited to, one or more mixtures of bis(hexachlorocyclopentadiene), cyclooctane, ammonium polyphosphate, decabromodiphenyl ether, bis(hydroxyethyl)methylphosphine oxide, cyanuric acid, melamine, etc.

[0093] And / or, lubricants include, but are not limited to, one or more mixtures of vinyl bis-stearamide, butyl stearate, etc.

[0094] And / or, the ultraviolet absorbers include, but are not limited to, one or more mixtures of 2-hydroxy-4-methoxybenzophenone, 2,2-dihydroxy-4-methoxybenzophenone, 2-(2-hydroxy-5-methylphenyl)benzotriazole, ethylene-2-cyano-3,3-diphenylacrylate, 2-(2-hydroxy-3-tert-butyl-5-methylphenyl)-5-chlorobenzotriazole, and 2-(2-hydroxy-5-methylphenyl)benzotriazole.

[0095] And / or, antioxidants include, but are not limited to, one or more mixtures of: 4-hydroxymethyl-2,6-di-tert-butylphenol, 3,5-di-tert-butyl-4-hydroxybenzyl phosphate diethyl ester, 1,1-thiobis-(2-naphthol), 4,4-butylene-bis(6-tert-butyl-m-cresol), 2,2-thiobis-(4-methyl-6-tert-butylphenol), etc.

[0096] And / or, the fillers include, but are not limited to, one or more mixtures of glass fiber, asbestos, wollastonite, calcium silicate, talc, montmorillonite, etc.

[0097] Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this disclosure pertains. While similar or equivalent methods and materials described herein may be used in the practice or testing of embodiments of the disclosed compositions, suitable methods and materials are those described below. All publications, patent applications, patents, and other references mentioned herein are incorporated herein by reference in their entirety, unless specific paragraphs are quoted. In case of any conflict, this specification and its included definitions shall prevail. Furthermore, materials, methods, and examples are illustrative only and not limiting.

[0098] The technical solution, implementation process, and principle of the present invention will be further explained and illustrated below through specific embodiments. It should be noted that the following detailed descriptions are exemplary and intended to provide further explanation of the present invention. The described embodiments are merely some embodiments of the present invention, and not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those skilled in the art without creative effort are within the scope of protection of the present invention. Unless otherwise stated, the reagents and raw materials used in the following embodiments are commercially available, and the test methods without specific conditions are generally performed under conventional conditions or according to the conditions recommended by the respective manufacturers. Furthermore, unless otherwise stated, the experimental methods, detection methods, and preparation methods disclosed in the present invention all employ conventional techniques in this technical field. These techniques have been well described in existing literature.

[0099] The testing standards or methods involved in the examples and / or comparative examples are as follows:

[0100] 1. Molecular weight test

[0101] The number-average molecular weight and weight-average molecular weight of the product were determined using a GPC column.

[0102] Specifically, the size exclusion chromatography system, Alliance 2695™ (Waters Corporation, Milford, MA), was equipped with a Waters 414™ differential refractive index detector, a DAWN Heleos II multi-angle light scattering spectrophotometer (Wyatt Technologies, Santa Barbara, CA), and a ViscoStar™ differential capillary viscometer detector (Wyatt). The software used for data acquisition and simplification was version 5.4 from Wyatt. The column used had a size exclusion limit of 2 × 10⁻⁶. 7 Furthermore, the theoretical plate size is two Shodex GPC HFIP-806M™ styrene-divinylbenzene columns with a theoretical plate size of 8,000 / 30 cm; and the exclusion limit is 2 × 10⁻⁶. 5 Furthermore, the theoretical plate size is 10,000 / 30cm for a single Shodex GPC HFIP-804MTM styrene-divinylbenzene column.

[0103] The sample was dissolved in 1,1,1,3,3,3-hexafluoro-2-propanol (HFIP) containing 0.01 M sodium trifluoroacetate, and stirred moderately at 50 °C for four hours. The solution was then filtered through a 0.45 μm PTFE filter. The concentration of the solution was approximately 2 mg / mL.

[0104] The chromatograph was set to 35℃; flow rate was 0.5 mL / min; data collection was performed; injection volume was 100 μL; and run time was 80 min. Data were imported from all three detectors and simplified. Eight scattering angles were used for the light scattering detector. Column calibration standards were not involved in data processing.

[0105] 2. 1 H-NMR spectroscopy

[0106] The antibacterial nylon materials prepared in Examples 1-8 were recorded using a 400 MHz NMR instrument in deuterated dimethyl sulfoxide (DMSO-d6) or deuterated dichloromethane (CD2Cl2). 1 H-NMR spectroscopy. The chemical shift of protons was recorded in ppm at a low magnetic field using the resonance of the deuterated solvent as an internal standard.

[0107] 3. Antibacterial test

[0108] The antibacterial test method is conducted according to the test method of "GBT 31402-2015 Plastics - Antibacterial Properties of Plastic Surfaces". The test bacteria selected for the antibacterial test include one or two of Escherichia coli and Staphylococcus aureus.

[0109] The antibacterial agents used in the following embodiments are mainly prepared by the following method: dissolving the raw materials in repeating units one and two in a solvent in proportion, mixing them, and stirring the mixture at 50-70°C for 12-24 hours to obtain the antibacterial agent; and / or, after the reaction is completed, filtering and separating the solids in the reaction system, which is the antibacterial agent. The method involves adjusting the ratios of R1, R3 / R in the raw materials. 3i By varying the types of R4, solvents, reaction temperatures, and reaction times, a series of antibacterial agent materials can be obtained. By selecting appropriate processing techniques such as casting and melt extrusion, products such as sheets, films, and coatings can be obtained. The general structural formulas of these antibacterial agent resins are shown in formula (IV) or formula (V).

[0110]

[0111] The technical solution of the present invention will be described in detail below through specific embodiments.

[0112] Example 1

[0113] The antibacterial agent provided in this embodiment is designated as antibacterial agent 1#.

[0114] In this embodiment, the raw materials are as follows:

[0115] Raw material A is adipic acid dihydrazide, with the structural formula as follows: R1 is -CH2CH2CH2CH2-;

[0116] Raw material B is furanyl dicarboxaldehyde;

[0117] Raw material C is adipic acid dihydrazide;

[0118] Raw material D is 1,4-pyrazinedicarboxaldehyde.

[0119] The feed ratio for preparation is 1:1:3:3, where the molar ratio of raw material A, raw material B, raw material C and raw material D is 1:1:3:3.

[0120] The preparation method involves mixing raw materials A, B, C, and D, dissolving them in an organic solvent, specifically a mixed solution of tetrahydrofuran and dimethyl sulfoxide at a volume ratio of 1:10, and reacting at 65°C for 24 hours. After the reaction is complete, the reaction system is filtered, and the precipitate obtained is the antibacterial agent 1# of this embodiment.

[0121] The structural formula of antibacterial agent #1 is:

[0122] The ratio of n to m is 1:3.

[0123] The number-average molecular weight of antibacterial agent 1# was determined to be 22022 and the weight-average molecular weight was 27748 using GPC column chromatography.

[0124] The structure of antibacterial agent 1# prepared in this embodiment was characterized. (See attached document.) Figure 1 , is the nuclear magnetic resonance of Example 1 1 ¹H-NMR spectra. The proton peak a on the acylhydrazone structure formed after the reaction is located at 11-12 ppm; the proton peak b on the imine bond linked to the furan ring after the reaction is located at 8.5 ppm; and the proton peak c on the imine bond linked to the pyrazine ring after the reaction is located at 7.9 ppm. Figure 1 It can be seen that the technical solution of Example 1 can produce a structure with the following structural formula:

[0125] Antibacterial agent #1.

[0126] Example 2

[0127] The antibacterial agent provided in this embodiment is designated as antibacterial agent 2#.

[0128] In this embodiment, the raw materials are as follows:

[0129] Raw material A is adipic acid dihydrazide, with the structural formula as follows: R1 is -CH2CH2CH2CH2-;

[0130] Raw material B is furanyl dicarboxaldehyde;

[0131] Raw material C is adipic acid dihydrazide;

[0132] Raw material D is glutaraldehyde.

[0133] The feed ratio for preparation is 1:1:37:37, where raw materials A, B, C and D are in a molar ratio of 1:1:37:37.

[0134] The preparation method includes mixing raw materials A, B, C, and D, dissolving them in an organic solvent (dimethyl sulfoxide), and reacting at 70°C for 20 hours. After the reaction is complete, the reaction system is filtered, and the precipitate obtained is the antibacterial agent 2# of this embodiment.

[0135] The structural formula of antibacterial agent #2 is:

[0136] The ratio of n to m is 1:37.

[0137] The number-average molecular weight of antibacterial agent 2# was determined to be 18098 and the weight-average molecular weight was 27509 by GPC column chromatography.

[0138] Example 3

[0139] The antibacterial agent provided in this embodiment is designated as antibacterial agent 3#.

[0140] In this embodiment, the raw materials are as follows:

[0141] Raw material A is octanoic acid dihydrazide, with the structural formula as follows: R1 is -CH2CH2CH2CH2CH2CH2CH2CH2CH2-;

[0142] Raw material B is furanyl dicarboxaldehyde;

[0143] Raw material C is octanoic acid dihydrazide;

[0144] Raw material D is 1,4-pyrazinedicarboxaldehyde.

[0145] The feed ratio for preparation is 3:3:1:1, where the molar ratio of raw material A, raw material B, raw material C and raw material D is 3:3:1:1.

[0146] The preparation method involves mixing raw materials A, B, C, and D, dissolving them in an organic solvent, specifically a mixture of dichloromethane and dimethyl sulfoxide in a ratio of 1:10, and reacting at 65°C for 20 hours. After the reaction is complete, the reaction system is filtered, and the precipitate obtained is the antibacterial agent 3# of this embodiment.

[0147] The structural formula of antibacterial agent #3 is:

[0148] The ratio of n to m is 3:1.

[0149] The number-average molecular weight of antibacterial agent 3# was determined to be 35263 and the weight-average molecular weight was 40552 by GPC column chromatography.

[0150] Example 4

[0151] The antibacterial agent provided in this embodiment is designated as antibacterial agent 4#.

[0152] In this embodiment, the raw materials are as follows:

[0153] Raw material A is succinic dihydrazide, with the structural formula as follows: R1 is -CH2CH2-;

[0154] Raw material B is furanyl dicarboxaldehyde;

[0155] Raw material C is pentandiamine;

[0156] Raw material D is furanyl dicarboxaldehyde.

[0157] The feed ratio for preparation is 1:1:1:1, where the molar ratio of raw material A, raw material B, raw material C and raw material D is 1:1:1:1.

[0158] The preparation method includes mixing raw materials A, B, C, and D, dissolving them in an organic solvent, specifically a mixed solution of benzene and dimethyl sulfoxide in a ratio of 1:10, and reacting at 55°C for 12 hours. After the reaction is complete, the reaction system is filtered, and the precipitate obtained is the antibacterial agent 4# of this embodiment.

[0159] The structural formula of antibacterial agent #4 is:

[0160] n∶m=1∶1.

[0161] The number-average molecular weight of antibacterial agent #4 was determined to be 16687 and the weight-average molecular weight was 21360 by GPC column chromatography.

[0162] Example 5

[0163] The antibacterial agent provided in this embodiment is designated as antibacterial agent 5#.

[0164] In this embodiment, the raw materials are as follows:

[0165] Raw material A is succinic dihydrazide, with the structural formula as follows: R1 is -CH2CH2-;

[0166] Raw material B is furanyl dicarboxaldehyde;

[0167] Raw material C is succinic dihydrazide;

[0168] Raw material D is malondialdehyde.

[0169] The feed ratio for preparation is 33:33:1:1, where the molar ratio of raw material A, raw material B, raw material C and raw material D is 33:33:1:1.

[0170] The preparation method involves mixing raw materials A, B, C, and D, dissolving them in an organic solvent, specifically a mixture of tetrahydrofuran, ethyl acetate, and chloroform in a ratio of 1:2:10, and reacting at 70°C for 12 hours. After the reaction is complete, the reaction system is filtered, and the precipitate obtained is the antibacterial agent 5# of this embodiment.

[0171] The structural formula of antibacterial agent #5 is:

[0172] The ratio of n to m is 33 to 1.

[0173] The number-average molecular weight of antibacterial agent 5# was determined to be 39946 and the weight-average molecular weight was 49932 by GPC column chromatography.

[0174] Example 6

[0175] The antibacterial agent provided in this embodiment is designated as antibacterial agent 6#.

[0176] In this embodiment, the raw materials are as follows:

[0177] Raw material A is adipic acid dihydrazide, with the structural formula as follows: R1 is -CH2CH2CH2CH2-;

[0178] Raw material B is furanyl dicarboxaldehyde;

[0179] Raw material C is pentandiamine;

[0180] Raw material D is furanyl dicarboxaldehyde.

[0181] The feed ratio for preparation is 1:1:1:1, where the molar ratio of raw material A, raw material B, raw material C and raw material D is 1:1:1:1.

[0182] The preparation method involves mixing raw materials A, B, C, and D, dissolving them in an organic solvent (chloroform), and reacting at 70°C for 24 hours. After the reaction is complete, the reaction system is filtered, and the precipitate obtained is the antibacterial agent 6# of this embodiment.

[0183] The structural formula of antibacterial agent 6# is:

[0184] n∶m=1∶1.

[0185] The number-average molecular weight of antibacterial agent 6# was determined to be 15001 and the weight-average molecular weight was 16080 by GPC column chromatography.

[0186] Example 7

[0187] The antibacterial agent provided in this embodiment is designated as antibacterial agent 7#.

[0188] In this embodiment, the raw materials are as follows:

[0189] Raw material A is malondihydrazide, with the structural formula as follows: R1 is -CH2-;

[0190] Raw material B is furanyl dicarboxaldehyde;

[0191] Raw material C is octanediamine;

[0192] Raw material D is terephthalaldehyde.

[0193] The feed ratio for preparation is 1:1:9:9, where the molar ratio of raw material A, raw material B, raw material C and raw material D is 1:1:9:9.

[0194] The preparation method includes mixing raw materials A, B, C, and D, dissolving them in an organic solvent (dimethyl sulfoxide), and reacting at 70°C for 24 hours. After the reaction is complete, the reaction system is filtered, and the precipitate obtained is the antibacterial agent 7# of this embodiment, with the structural formula [structural formula would be inserted here].

[0195] The ratio of n to m is 1:9.

[0196] The number-average molecular weight of antibacterial agent 7# was determined to be 12802 and the weight-average molecular weight was 18820 by GPC column chromatography.

[0197] Example 8

[0198] The antibacterial agent provided in this embodiment is designated as antibacterial agent 8#.

[0199] In this embodiment, the raw materials are as follows:

[0200] Raw material A is adipic acid dihydrazide, with the structural formula as follows: R1 is -CH2CH2CH2CH2-;

[0201] Raw material B is furanyl dicarboxaldehyde;

[0202] Raw material C is pentandiamine;

[0203] Raw material D is terephthalaldehyde.

[0204] The feed ratio for preparation is 1:1:1:1, where the molar ratio of raw material A, raw material B, raw material C and raw material D is 1:1:1:1.

[0205] The preparation method includes mixing raw materials A, B, C, and D, dissolving them in an organic solvent, specifically a mixed solution of dimethyl sulfoxide and toluene, and reacting at 70°C for 24 hours. After the reaction is complete, the reaction system is filtered, and the precipitate obtained is the antibacterial agent 8# of this embodiment, with the structural formula [structure omitted].

[0206] The ratio of n to m is 1:1.

[0207] The number-average molecular weight of antibacterial agent 8# was determined to be 9043 and the weight-average molecular weight was 16081 by GPC column chromatography.

[0208] Antibacterial nylon can be prepared using the antibacterial agents in this embodiment. The corresponding preparation method includes: adding commercial nylon resin, antibacterial agent, antioxidant and deacidifying agent into a high-speed mixer and mixing for 10-15 minutes, then adding the uniformly mixed material into a twin-screw extruder for mixing and extrusion to obtain antibacterial nylon. The twin-screw extrusion processing temperature is 240-270℃.

[0209] Commercial nylon resins include, but are not limited to, nylon 6, nylon 66, nylon 6T66, nylon 10T, etc.

[0210] Sheets were extruded and injection molded using a screw extruder. The sheet specifications were 6cm*6cm*0.1cm, and its antibacterial properties were tested according to GBT 31402-2015.

[0211] The antibacterial agent products prepared using Examples 1-8 can be used to prepare antibacterial nylon coatings or membrane materials. The corresponding preparation methods include: uniformly mixing the antibacterial agent and commercial nylon, dissolving them in hexafluoroisopropanol, coating them onto the surface of aluminum metal with a coating rod, and air-drying them at room temperature to obtain an antibacterial nylon coating with a film thickness controlled between 100-200 μm; or pouring it into a polytetrafluoroethylene mold, air-drying it at room temperature to obtain an antibacterial nylon membrane material, and testing its antibacterial properties according to GBT 31402-2015.

[0212] The proportions of commercial nylon resin, antibacterial agent, antioxidant, and deacidifying agent, as well as the types of commercial nylon resin, antioxidant, and deacidifying agent, and the extrusion temperature, can be adjusted according to actual production needs. In this invention, after blending with antioxidants, lubricants, plasticizers, flame retardants, and other additives, the types and proportions of antioxidants and other additives selected are those commonly used in ordinary nylon processing. The amounts of additives and antibacterial agents added are shown in Table 1. Unless otherwise specified, the amounts of antibacterial agents and additives added in this invention are all expressed as a percentage by mass.

[0213] Table 2 provides the antimicrobial properties of commercial nylon resins without the addition of other additives, only the antimicrobial agent.

[0214] Table 3 provides the antimicrobial properties of commercial nylon resins without the antimicrobial agent of this invention.

[0215] Table 1. Comparison of antibacterial properties of nylon products with added additives and antibacterial agents.

[0216]

[0217] Note: The data shown in columns D and F of Table 1 are the average values ​​after testing multiple samples.

[0218] Table 2. Comparison of antibacterial properties of nylon products with added antibacterial agents only.

[0219]

[0220]

[0221] Note: The data shown in columns D and E of Table 2 are the average values ​​after testing multiple samples.

[0222] Table 3 Comparison of antibacterial properties of different commercial nylon resins

[0223]

[0224]

[0225] Note: The data shown in columns E and F of Table 3 are the average values ​​after testing multiple samples.

[0226] As can be seen from the comparison in Tables 1-3, the nylon materials prepared using the antibacterial agents prepared in Examples 1-8, such as films, sheets, or coatings, achieve 100% antibacterial performance against Escherichia coli and Staphylococcus aureus. Compared with nylon 6, nylon 66, nylon 6T66, nylon 10T, etc. in the prior art, they exhibit significantly superior antibacterial properties. Furthermore, the antibacterial performance of the antibacterial agent of this invention is not affected after adding the amount of additives used in the prior art.

[0227] The antibacterial agent prepared by this invention exhibits excellent antibacterial properties when added at a concentration of 0.5%. When the addition concentration reaches 1%, the antibacterial properties against Escherichia coli and Staphylococcus aureus can reach 100%. In actual production, the amount of antibacterial agent added can be adjusted according to actual needs. Preferably, the amount of antibacterial agent added is 0.5% to 5%, and more preferably, it is 1.2% to 2%.

[0228] The above are merely preferred embodiments of the present invention and do not limit the scope of protection of the present invention. For those skilled in the art, the present invention can have various modifications and variations. Any changes, modifications, substitutions, integrations, and parameter alterations to these embodiments within the spirit and principles of the present invention, achieved through conventional substitutions or by achieving the same function without departing from the principles and spirit of the present invention, fall within the scope of protection of the present invention.

Claims

1. The application of an antibacterial agent in the preparation of nylon products with antibacterial function; the antibacterial agent comprises two not completely identical repeating units, namely a first repeating unit and a second repeating unit; the structural formula of the first repeating unit is: Equation (Ⅰ); in, m is an integer between 1 and 200; R1 is a benzene ring or a C1-C1 ring. 10 It is a straight-chain hydrocarbon group; The second repeating unit structure is as follows: Equation (II), or, Equation (Ⅲ); where n is an integer between 1 and 200, and n:m is 1:60 to 60:1; R3 is a benzene ring or a C1-C 10 The straight-chain hydrocarbon group, R4 is selected from furan ring, benzene ring, pyrazine ring or C1-C3 straight-chain hydrocarbon group, R 3i It is a C5 straight-chain hydrocarbon group; When R4 is a furan ring, R1≠R3.

2. The application according to claim 1, characterized in that, The structural formula of the antibacterial agent is shown below: Formula (Ⅳ) or Formula (V); Wherein, R1 and R3 are benzene rings or C1-C rings, respectively. 10 R4 is a straight-chain hydrocarbon group, selected from furan ring, benzene ring, pyrazine ring, or C1-C3 straight-chain hydrocarbon group. 3i It is a C5 straight-chain hydrocarbon group.

3. The application as described in claim 2, characterized in that, The number-average molecular weight of the antibacterial agent is ≥5000 g / mol; and / or, the weight-average molecular weight of the antibacterial agent is ≥10 kg / mol.

4. The application as described in any one of claims 1-3, characterized in that, The antibacterial agent has a 100% antibacterial rate against Escherichia coli and / or Staphylococcus aureus.

5. The application as described in any one of claims 1-3, characterized in that, The method for preparing the antibacterial agent includes: using a copolymerization method, dissolving raw materials A, B, C and D in an organic solvent and mixing them evenly, then stirring and reacting at 50~70℃ for 12~24h to carry out a copolymerization reaction to obtain the antibacterial agent; and / or, after the reaction is completed, filtering or vacuum filtering to separate the solids in the reaction system, which are the antibacterial agent. The raw material A is an acylhydrazine; the structural formula of the acylhydrazine is shown in formula (VI): Formula (VI); Wherein, R1 is a benzene ring or a C1-C10 straight-chain hydrocarbon group; Raw material B is furan dicarboxaldehyde. The raw material C is an acylhydrazine or a diamine, and the structural formula of the acylhydrazine is shown in formula (VII): Formula (VII); Where R3 is a benzene ring or a C1-C10 straight-chain hydrocarbon group; The structural formula of the diamine is as shown in formula ( As shown in the image: Mode( ) Where R 3i It is a C5 straight-chain hydrocarbon group; The raw material D is a dialdehyde; the structural formula of the dialdehyde is as shown in formula ( As shown in the image: Mode( ); Wherein, R4 is a furan ring, benzene ring, pyrazine ring, or a C1-C3 straight-chain hydrocarbon group, and when R4 is a furan ring, R1 ≠ R 3。 6. The application as described in claim 5, characterized in that, The molar ratio of raw material A, raw material B, raw material C and raw material D satisfies the following conditions: raw material A: raw material B = 1:1, raw material C: raw material D = 1:1, and (raw material A + raw material B): (raw material C + raw material D) = 1:60~60:

1.

7. An antibacterial nylon material, characterized in that, The antibacterial nylon material contains an antibacterial agent, and the amount of the antibacterial agent added is 0.5-5.0% by mass. The antibacterial agent comprises two not entirely identical repeating units, namely a first repeating unit and a second repeating unit; the structural formula of the first repeating unit is: Equation (Ⅰ); Where m is an integer between 1 and 200; R1 is a benzene ring or a C1-C1 ring. 10 It is a straight-chain hydrocarbon group; The second repeating unit structure is as follows: Equation (II), or, Equation (Ⅲ); where n is an integer between 1 and 200, and n:m is 1:60 to 60:1; R3 is a benzene ring or a C1-C 10 The straight-chain hydrocarbon group, R4 is selected from furan ring, benzene ring, pyrazine ring or C1-C3 straight-chain hydrocarbon group, R 3i It is a C5 straight-chain hydrocarbon group; When R4 is a furan ring, R1≠R3.

8. The antibacterial nylon material as described in claim 7, characterized in that, Films, sheets, coatings, or molded products are prepared by solution casting or melt extrusion injection molding.

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