Antibacterial nylon 6 material, method of preparation thereof, and its applications

Abstract

The present invention relates to an antibacterial nylon 6 material, a preparation method thereof and its use. The antibacterial nylon 6 material has a structure represented by formula (I), and each R group and each R group are represented by C 1-24 Linear or branched aliphatic hydrocarbyl groups, substituted or unsubstituted C 3-12 Alicyclic hydrocarbyl groups, substituted or unsubstituted C 6-18 Aryl groups and substituted or unsubstituted C 7-30 aralkyl groups, or the R1 and R2 groups on the same nitrogen atom together with the attached N atom form a 5- to 7-membered saturated or unsaturated heterocycle; each R3 group is independently selected from the group consisting of hydrogen (H), C 1-24 Linear or branched aliphatic hydrocarbyl groups, substituted or unsubstituted C 3-12 Alicyclic hydrocarbyl groups, substituted or unsubstituted C 6-18 Aryl groups, and substituted or unsubstituted C 7-30 x is in the range of 0.02 to 0.30, y is in the range of 0.70 to 0.98, and x+y=1. The antibacterial nylon 6 material of the present invention has a wide range of high antibacterial effects and good antibacterial durability, and can be widely used as a public health material in textile products, daily necessities, building materials, packaging materials, various panels, etc. [Formula 1] JPEG2024531376000033.jpg37169

Description

Technical Field

[0001] The present invention relates to the technical field of antibacterial polymer materials, and particularly relates to an antibacterial nylon 6 material, a preparation method therefor and an application thereof. Background Art

[0002] There are a wide variety of microorganisms existing in nature. In daily life, microorganisms are closely and indiscriminately related to human beings, and some of bacteria, fungi, viruses and the like are pathogenic, which significantly endanger human health and even life. For example, highly pathogenic avian influenza virus (H5N1), tuberculosis, SARS, and novel coronavirus (2019-nCoV are all caused by the spread of bacteria or microorganisms. After suffering from outbreaks, people have increasingly paid attention to the harm caused by bacteria or microorganisms to human health and living environment, and the requirements for the quality and functions of used products are also getting higher and higher. Therefore, the development of new antibacterial materials has become important. Antibacterial polymer materials can inhibit and kill microorganisms such as bacteria and fungi present on the materials, and are widely used in the fields of hygiene, medical treatment, environmental protection and the like.

[0003] Polycaprolactam (commonly known as nylon or chinlon) has excellent properties such as light weight, high strength, wear resistance, resistance to weak acidic solvents, weak basic solvents and some organic solvents, and ease of molding processing, and is widely used in the fields of fibers, engineering plastics, films and the like. However, due to the presence of strongly polar amide groups in the molecular chain segments of nylon 6 (PA-6), it is easy to form hydrogen bonds with water molecules and absorb moisture from the environment, thereby becoming an ideal breeding ground for bacteria and fungi. Nylon 6 materials exist everywhere in daily life, so developing nylon 6 materials with antibacterial function can effectively reduce or avoid the infection and transmission of bacteria, and has important significance for improving people's living environment and reducing the incidence of diseases.

[0004] Currently, commercially available antimicrobial nylon 6 materials are mainly prepared by compounding polycaprolactam with low molecular weight antimicrobial agents; see, for example, CN107652669, CN107793748, and CN108047709. These antimicrobial nylon 6 materials have many problems in terms of safety, environmental friendliness, antimicrobial effect, and durability.

[0005] Therefore, the development of novel antimicrobial nylon 6 materials that are environmentally friendly and possess sustainable and efficient antimicrobial properties is extremely important. [Overview of the project]

[0006] The object of the present invention is to provide a novel nylon 6-based material having antibacterial properties, a method for preparing the same, and its applications. This nylon 6-based material overcomes the drawbacks of antibacterial nylon 6-based materials obtained by compounding, such as low antibacterial durability and low stability, and is low-cost, easy to prepare, and suitable for mass production.

[0007] [ka] Here, each R1 group and each R2 group are C 1-24 Linear or branched aliphatic hydrocarbyl groups, substituted or unsubstituted C 3-12 Alicyclic hydrocarbyl group, substituted or unsubstituted C 6-18 Aryl groups, and substituted or unsubstituted C 7-30 Independently selected from the group consisting of aralkyl groups, or R1 and R2 groups on the same nitrogen atom, together with the bonded N atom, form a 5-7 member saturated or unsaturated heterocycle; Each R3 group consists of hydrogen (H) and C 1-24 Linear or branched aliphatic hydrocarbyl groups, substituted or unsubstituted C 3-12 Alicyclic hydrocarbyl group, substituted or unsubstituted C 6-18 Aryl groups, and substituted or unsubstituted C 7-30 Independently selected from the group consisting of aralkyl groups; and x and y each represent, relative to the total amount of repeating units in formula (I),

Chemical Formula

Chemical Formula

[0008] In another aspect, the present invention provides a nylon 6 composition comprising 70 wt% or more and less than 100 wt% of the antibacterial nylon 6 material according to the present invention, and 0 wt% or more and 30 wt% or less of at least one polymer different from the antibacterial nylon 6 material, the polymer comprising repeating units having the structure of

Chemical Formula

Chemical Formula

[0009] In another aspect, the present invention provides a method for preparing an antibacterial nylon 6 material, the method comprising the following steps: 1) a step of providing a cyclic lysine monomer having a structure represented by the following formula (II),

Chemical Formula

[0010] The antibacterial nylon 6 material according to the present invention has a broad and high antibacterial effect, good antibacterial durability and stability, and can be widely used as a public health material in textile products, daily necessities, building materials, packaging materials, various panels, etc. It is low cost, simple to prepare, and easy to mass-produce.

[0011] In yet another embodiment, the present invention provides an article comprising an antimicrobial nylon 6 material according to the present invention, a nylon 6 composition according to the present invention, or an antimicrobial nylon 6 material obtained by a method according to the present invention.

[0012] Preferably, the articles are selected from the group consisting of textile products, daily necessities, building materials, packaging materials, and panels.

[0013] Other features and advantages of the present invention will be described in detail below in the detailed description herein. The drawings, which constitute part of this specification, are provided to aid in understanding the invention and should not be considered limiting. The invention can be interpreted by referring to the drawings in conjunction with the following detailed description herein. [Brief explanation of the drawing]

[0014] [Figure 1] This is a schematic diagram showing the synthesis route of the antibacterial nylon 6 material according to the present invention. [Figure 2] This shows the nuclear magnetic resonance spectra of the copolymers of dimethyl-protected cyclic lysine monomer and caprolactam monomer obtained in Example 1. [Figure 3] This is a DSC melting point test diagram of the antibacterial nylon 6 material obtained in Example 1. [Figure 4] This is a DSC melting point test diagram of the antibacterial nylon 6 material obtained in Example 2. [Figure 5] This is a DSC melting point test diagram of the antibacterial nylon 6 material obtained in Example 3. [Figure 6] This is a DSC melting point test diagram of the antibacterial nylon 6 material obtained in Example 4. [Figure 7] This is a DSC melting point test diagram of the antibacterial nylon 6 material obtained in Example 5. [Figure 8A] This photograph shows the antibacterial effect of the nylon 6 material obtained in Comparative Example 1 against Staphylococcus aureus. [Figure 8B] This photograph shows the antibacterial effect of the nylon 6 material obtained in Example 5 against Staphylococcus aureus. [Modes for carrying out the invention]

[0015] The present invention will be described in further detail below with reference to the drawings and their specific embodiments. It should be noted that the specific embodiments of the present invention are provided for illustrative purposes only and are not intended to be limiting in any way.

[0016] Any specific numerical value including an endpoint of a numerical range described in the context of the present invention should be interpreted as encompassing not only its exact value but also all values ​​close to that exact value, for example, all values ​​within ±5% of that exact value. Furthermore, with respect to any numerical range described herein, one or more new numerical ranges can be provided by creating any combination between the endpoints of the range, between each endpoint and any specific value within the range, or between any two specific values ​​within the range, where such new numerical ranges should also be deemed to be specifically described in this specification.

[0017] Unless otherwise specified, terms used herein have the same meaning as commonly understood by those skilled in the art. If a term is defined herein and that definition differs from the common understanding in the art, the definition provided herein shall prevail.

[0018] In the present invention, the term "substitution" means that the base is C 1-18 Linear or branched alkyl groups, preferably C 1-12 Linear or branched alkyl groups, more preferably C 1-6 This means that it is substituted with one or more substituents selected from linear or branched alkyl groups.

[0019] In the context of the present invention, matters or topics not explicitly described, in addition to those explicitly described, are considered to be the same as those known in the art without any modification. Furthermore, any embodiment described herein may be freely combined with one or more other embodiments described herein, and any technical solution or idea thus obtained shall be considered part of the original disclosure or description of this application and shall not be considered novel matter not disclosed or anticipated herein unless such combination is clearly unreasonable to a person skilled in the art.

[0020] All patent and non-patent documents (including, but not limited to, reference books and journal articles) cited herein are incorporated herein by reference in their entirety.

[0021] As described above, in the first embodiment, the present invention provides an antibacterial nylon 6 material having a structure represented by the following formula (I): [ka] Here, each R1 group and each R2 group are C 1-24 Linear or branched aliphatic hydrocarbyl groups, substituted or unsubstituted C 3-12 Alicyclic hydrocarbyl group, substituted or unsubstituted C 6-18 Aryl groups, and substituted or unsubstituted C 7-30 Independently selected from the group consisting of aralkyl groups, or R1 and R2 groups on the same nitrogen atom, together with the bonded N atom, form a 5-7 member saturated or unsaturated heterocycle; Each R3 group consists of hydrogen (H) and C 1-24 Linear or branched aliphatic hydrocarbyl groups, substituted or unsubstituted C 3-12 Alicyclic hydrocarbyl group, substituted or unsubstituted C 6-18 Aryl groups, and substituted or unsubstituted C 7-30 Independently selected from the group consisting of aralkyl groups; and x and y are, respectively, the total amount of repeating units in equation (I). [ka] The molar ratio of repeating units having the structure and [ka] This represents the molar ratio of repeating units having the structure, where x is in the range of 0.02 to 0.30, y is in the range of 0.70 to 0.98, and x + y = 1.

[0022] In a preferred embodiment, each R1 group and each R2 group are C 1-12 Linear or branched aliphatic hydrocarbyl groups (e.g., alkyl or alkenyl groups, preferably alkyl groups, C) 1-8 Linear or branched aliphatic hydrocarbyl groups, C 1-6 Linear or branched aliphatic hydrocarbyl groups, C 1-4 Linear or branched aliphatic hydrocarbyl groups), substituted or unsubstituted C 3-6 Alicyclic hydrocarbyl group, substituted or unsubstituted C 6-10 Aryl groups, and substituted or unsubstituted C 7-16 R1 and R2 groups, independently selected from the group consisting of aralkyl groups, or located on the same nitrogen atom, together with the bonded N atom, form a 5-6 member saturated or unsaturated heterocycle; and each R3 group is composed of hydrogen (H) and C. 1-12 Linear or branched aliphatic hydrocarbyl groups (e.g., alkyl or alkenyl groups, preferably alkyl groups, C) 1-8 Linear or branched aliphatic hydrocarbyl groups, C 1-6 Linear or branched aliphatic hydrocarbyl groups, C 1-4 Linear or branched aliphatic hydrocarbyl groups), substituted or unsubstituted C 3-6 Alicyclic hydrocarbyl group, substituted or unsubstituted C 6-10 Aryl groups, and substituted or unsubstituted C 7-16 It is independently selected from the group consisting of aralkyl groups.

[0023] In a more preferred embodiment, each R1 group and each R2 group are independently selected from the group consisting of methyl, ethyl, propyl, butyl, hexyl, octyl, dodecyl, allyl, phenyl, and benzyl, or R1 and R2 groups on the same nitrogen atom, together with the bonded N atom, form a tetrahydropyrrolyl group or a hexahydropyridyl group; and each R3 group is independently selected from the group consisting of hydrogen (H), methyl, ethyl, propyl, butyl, hexyl, octyl, dodecyl, cyclohexyl, phenyl, and benzyl.

[0024] In a more preferred embodiment, the R1 and R2 groups are all the same and selected from the group consisting of methyl, ethyl, propyl, butyl, hexyl, octyl, dodecyl, allyl, and benzyl, or the R1 and R2 groups on the same nitrogen atom, together with the bonded N atom, form a tetrahydropyrrolyl group or a hexahydropyridyl group; and the R3 group is all the same and selected from the group consisting of hydrogen (H), methyl, ethyl, propyl, butyl, hexyl, octyl, dodecyl, cyclohexyl, and benzyl.

[0025] In a particularly preferred embodiment, all R1 and R2 groups are the same and selected from the group consisting of methyl, ethyl, propyl, butyl, dodecyl, allyl, and benzyl, especially ethyl, propyl, butyl, and benzyl, or R1 and R2 groups on the same nitrogen atom, together with the bonded N atom, form a hexahydropyridyl group; and all R3 groups are the same and selected from the group consisting of hydrogen (H), ethyl, cyclohexyl, and benzyl, especially ethyl.

[0026] In a preferred embodiment, in equation (I), x is in the range of 0.03 to 0.25, more preferably in the range of 0.04 to 0.20, for example, 0.08 to 0.20, 0.12 to 0.20, or 0.16 to 0.20; y is in the range of 0.75 to 0.97, more preferably in the range of 0.80 to 0.96, for example, 0.80 to 0.92, 0.88 to 0.80, or 0.84 to 0.80, and x + y = 1.

[0027] In a preferred embodiment, the total number of repeating units of the antimicrobial nylon 6 material represented by formula (I) is in the range of 10 to 2500, preferably 20 to 1000, and more preferably 20 to 500.

[0028] In a preferred embodiment, the antibacterial nylon 6 material has a weight-average molecular weight of 2,000 to 500,000, preferably 5,000 to 200,000, and more preferably 5,000 to 100,000.

[0029] In a second aspect, the present invention provides an antibacterial nylon 6 material according to the present invention in a quantity of 70% by weight or more and less than 100% by weight, and a different antibacterial nylon 6 material in a quantity of 0% or more and 30% or less, [ka] Repeating units having the structure and / or [ka] We provide a nylon 6 composition comprising at least one polymer having repeating units having the structure, wherein groups R1, R2, and R3 are as defined herein above.

[0030] In a preferred embodiment, the nylon 6 composition includes 80% by weight or more and less than 100% by weight, more preferably 90% by weight or more and less than 100% by weight, for example 91% by weight, 92% by weight, 93% by weight, 94% by weight, 95% by weight, 96% by weight, 97% by weight, 98% by weight, and 99% by weight of the antimicrobial nylon 6 material according to the present invention, and at least one polymer different from the aforementioned antimicrobial nylon 6 material, in amounts exceeding 0% by weight and up to 20% by weight, more preferably exceeding 0% by weight and up to 10% by weight, for example 0.1% by weight, 0.2% by weight, 0.3% by weight, 0.4% by weight, 0.5% by weight, 0.6% by weight, 0.7% by weight, 0.8% by weight, 0.9% by weight, 1% by weight, 2% by weight, 3% by weight, 4% by weight, 5% by weight, 6% by weight, 7% by weight, 8% by weight, and 9% by weight.

[0031] In some specific embodiments, polymers different from antimicrobial nylon 6 materials have a structure similar to formula (I), except that x is outside the range of 0.02 to 0.30, y is outside the range of 0.70 to 0.98, and x + y = 1.

[0032] In a preferred embodiment, the nylon 6 composition according to the present invention further comprises additives selected from the group consisting of reinforcing agents, fillers, toughening agents, plasticizers, flame retardants, colorants, fluorescent whitening agents, light stabilizers, antioxidants, heat stabilizers, lubricants, mold release agents, and combinations thereof, in amounts of 0% to 30% by weight, preferably 0% to 20% by weight, and more preferably 0% to 10% by weight, for example, 0.1% by weight, 0.2% by weight, 0.3% by weight, 0.4% by weight, 0.5% by weight, 0.6% by weight, 0.7% by weight, 0.8% by weight, 0.9% by weight, 1% by weight, 2% by weight, 3% by weight, 4% by weight, 5% by weight, 6% by weight, 7% by weight, 8% by weight, and 9% by weight.

[0033] The additives suitable for use in the compositions of the present invention may be any additives conventionally used in the manufacture and processing of nylon, and are not particularly limited in the present invention. For example, suitable fillers for use in the compositions of the present application may include, but are not limited to, activated calcium carbonate, talc, wollastonite, mica, and others that are commonly used in the art; suitable antioxidants for use in the compositions of the present application may include, but are not limited to, phenolic antioxidants, phosphite ester antioxidants, and others that are commonly used in the art.

[0034] In a third embodiment, the present invention provides a method for preparing an antimicrobial nylon 6 material, comprising the following steps: 1) A step of providing a cyclic lysine monomer having a structure represented by the following formula (II): [ka] Here, the R1 and R2 groups are C 1-24 Linear or branched aliphatic hydrocarbyl groups, substituted or unsubstituted C 3-12 Alicyclic hydrocarbyl group, substituted or unsubstituted C 6-18 Aryl groups, and substituted or unsubstituted C 7-30 A process in which R1 and R2 groups are independently selected from the group consisting of aralkyl groups, or together with the bonded N atom, form a 5-7 member saturated or unsaturated heterocycle; 2) A step of subjecting a cyclic lysine monomer and a caprolactam monomer to ring-opening polymerization in a molar ratio of 2:98 to 30:70 to obtain a copolymer having a structure represented by the following formula (III), [ka] 3) The copolymer is reacted with a halide having the structure represented by the following formula (IV): R3-Hal (IV) Here, the R3 group consists of hydrogen (H) and C. 1-24Linear or branched aliphatic hydrocarbyl groups, substituted or unsubstituted C 3-12 Alicyclic hydrocarbyl group, substituted or unsubstituted C 6-18 Aryl groups, and substituted or unsubstituted C 7-30 Selected from the group consisting of aralkyl groups, Hal represents halogen, A step to obtain antibacterial nylon 6 having a structure represented by formula (I). [ka]

[0035] Figure 1 is a schematic diagram showing the synthesis route for preparing the antibacterial nylon 6 material according to the present invention.

[0036] In a preferred embodiment, the R1 and R2 groups are C 1-12 Linear or branched aliphatic hydrocarbyl groups (e.g., alkyl or alkenyl groups, preferably alkyl groups, C) 1-8 Linear or branched aliphatic hydrocarbyl groups, C 1-6 Linear or branched aliphatic hydrocarbyl groups, C 1-4 Linear or branched aliphatic hydrocarbyl groups), substituted or unsubstituted C 3-6 Alicyclic hydrocarbyl group, substituted or unsubstituted C 6-10 Aryl groups, and substituted or unsubstituted C 7-16 The R1 and R2 groups are independently selected from the group consisting of aralkyl groups, or together with the bonded N atom, they form a 5-6 member saturated or unsaturated heterocycle; the R3 group consists of hydrogen (H) and C 1-12 Linear or branched aliphatic hydrocarbyl groups (e.g., alkyl or alkenyl groups, preferably alkyl groups, C) 1-8 Linear or branched aliphatic hydrocarbyl groups, C 1-6 Linear or branched aliphatic hydrocarbyl groups, C 1-4 Linear or branched aliphatic hydrocarbyl groups), substituted or unsubstituted C 3-6 Alicyclic hydrocarbyl group, substituted or unsubstituted C 6-10Aryl groups, and substituted or unsubstituted C 7-16 Selected from the group consisting of aralkyl groups; and Hal represents chlorine, bromine, or iodine.

[0037] In a more preferred embodiment, the R1 and R2 groups are independently selected from the group consisting of methyl, ethyl, propyl, butyl, hexyl, octyl, dodecyl, allyl, phenyl, and benzyl, or the R1 and R2 groups, together with the bonded N atom, form a tetrahydropyrrolyl group or a hexahydropyridyl group; the R3 group is selected from the group consisting of hydrogen (H), methyl, ethyl, propyl, butyl, hexyl, octyl, dodecyl, cyclohexyl, phenyl, and benzyl; and Hal represents chlorine, bromine, or iodine.

[0038] In a more preferred embodiment, the R1 and R2 groups are the same and selected from the group consisting of methyl, ethyl, propyl, butyl, hexyl, octyl, dodecyl, allyl, and benzyl, or the R1 and R2 groups, together with the bonded N atom, form a tetrahydropyrrolyl group or a hexahydropyridyl group; the R3 group is selected from the group consisting of hydrogen (H), methyl, ethyl, propyl, butyl, hexyl, octyl, dodecyl, cyclohexyl, and benzyl, where Hal represents chlorine, bromine, or iodine.

[0039] In a particularly preferred embodiment, the R1 and R2 groups are the same and selected from the group consisting of methyl, ethyl, propyl, butyl, dodecyl, allyl, and benzyl, especially ethyl, propyl, butyl, and benzyl, or the R1 and R2 groups, together with the bonded N atom, form a hexahydropyridyl group; the R3 group is selected from the group consisting of hydrogen (H), ethyl, cyclohexyl, and benzyl, especially ethyl; and Hal represents chlorine or bromine, preferably bromine.

[0040] In a preferred embodiment of the method according to the present invention, the cyclic lysine monomer is provided in step 1) by protecting the primary amine group on an aminocaprolactam represented by formula (V) with a protecting group. [ka]

[0041] For example, protecting groups may be the R1 and R2 groups defined above in this specification, which are not described in detail here.

[0042] In a more preferred embodiment, step 1) is carried out by reacting the aminocaprolactam with a corresponding aldehyde and / or halogenated hydrocarbon having R1 and / or R2 groups, preferably by reacting the aminocaprolactam with a reagent selected from the group consisting of formaldehyde, acetaldehyde, propionaldehyde, butyraldehyde, benzyl chloride, 1,5-dibromopentane, allyl bromide, dodecyl bromide, or a combination thereof.

[0043] In certain more preferred embodiments, the aminocaprolactam used in step 1) can be prepared from L-lysine hydrochloride as follows: i) Methyl esterification of L-lysine hydrochloride to obtain methylated L-lysine, preferably using methanol as the solvent, a methyl esterification reagent and concentrated sulfuric acid as catalysts, and reacting under reflux conditions for 8 to 10 hours to obtain methylated L-lysine; ii) Reacting the methylated L-lysine with a basic solution in methanol solvent to obtain aminocaprolactam, preferably reacting at room temperature for 10 to 12 hours, followed by concentration and recrystallization to obtain aminocaprolactam.

[0044] In a preferred embodiment, the molar ratio of the cyclic lysine monomer to the caprolactam monomer used in step 2) is 3:97 to 25:75, more preferably 4:96 to 20:80.

[0045] In a preferred embodiment, step 2) is carried out in the presence of a catalyst, which is preferably selected from the group consisting of carbene reagents, guanidine reagents, amidine reagents, phosphazene reagents, alkali metals, alkali metal oxides, alkali metal hydroxides, alkali metal hydrides, alkali metal alkoxides, alkaline earth metals, alkaline earth metal oxides, alkaline earth metal hydroxides, alkaline earth metal hydrides, alkaline earth metal alkoxides, or combinations thereof. More preferably, the catalyst is selected from the group consisting of sodium hydride, potassium hydride, phosphazene base (t-BuP4), potassium tert-butoxide, sodium methoxide, potassium methoxide, DBU (1,8-diazabicyclo[5.4.0]undeca-7-ene), TBD (1,5,7-triazabicyclo[4,4,0]deca-5-ene), sodium, potassium, or combinations thereof.

[0046] In a more preferred embodiment, the molar ratio of the total amount of cyclic lysine monomer and caprolactam monomer to the catalyst used in step 2) is (10-50):1, preferably (10-30):1.

[0047] In a more preferred embodiment, the ring-opening polymerization in step 2) is carried out in the presence of an activator having the following structure: [ka] Here, R is selected from the group consisting of methyl, ethyl, phenyl, t-butylphenyl, and trifluoromethylphenyl.

[0048] More preferably, the molar ratio of the total amount of cyclic lysine monomer and caprolactam monomer to the activator used in step 2) is (10-50):1, preferably (10-30):1.

[0049] In a preferred embodiment, the reaction conditions for step 2) include a polymerization temperature of 140-180°C and a reaction time of 3-6 hours.

[0050] In a preferred embodiment, the halogen having the structure represented by formula (IV) used in step 3) is selected from the group consisting of hydrochloric acid, methyl iodide, ethyl bromide, butyl bromide, hexyl bromide, cyclohexyl bromide, benzyl bromide, or a combination thereof, and more preferably selected from hydrochloric acid, ethyl bromide, cyclohexyl bromide, benzyl bromide, or a combination thereof.

[0051] In a preferred embodiment, the reaction in step 3) is carried out in a solvent selected from the group consisting of methanol, ethanol, trifluoroethanol, benzyl alcohol, ethylene glycol, cyclohexanol, or a combination thereof, more preferably in a trifluoroethanol solvent. Even more preferably, the reaction conditions for step 3) include a reaction temperature of 40-70°C and a reaction time of 10-12 hours.

[0052] In some preferred embodiments, step 3) further includes precipitating the reaction product of the copolymer and the halide in ethyl acetate, centrifuging, and drying to obtain an antimicrobial nylon 6 material.

[0053] In a fourth embodiment, the present invention provides an article comprising an antimicrobial nylon 6 material according to the present invention, a nylon 6 composition according to the present invention, or an antimicrobial nylon 6 material obtained by a method according to the present invention.

[0054] In some preferred embodiments, at least a portion of the article is made from antimicrobial nylon 6 material.

[0055] In a preferred embodiment, the article is selected from the group consisting of textile products, daily necessities, building materials, packaging materials, and panels, such as masks, protective clothing, towels, carpets, cling films, and bicycle handlebars.

[0056] According to the present invention, articles or parts thereof can be manufactured using the antibacterial nylon 6 material or nylon 6 composition according to the present invention by conventional methods, such as injection molding, blow molding, extrusion molding, calendering, etc. The operations and conditions are well known to those skilled in the art and can be selected according to actual needs, so a detailed explanation is omitted here. [Examples]

[0057] The present invention will be further described with reference to the following examples, but the present invention is not limited thereto.

[0058] Unless otherwise specified, the reagents used in the following examples are commercially available and have analytical grade purity.

[0059] In the following examples and comparative examples, the nuclear magnetic resonance spectra of the obtained aminocaprolactam intermediates and nylon 6 materials were measured at room temperature using a Burker AV-300 liquid superconducting nuclear magnetic resonance spectrometer with a mixed solvent of deuterated dimethyl sulfoxide and trifluoroacetic acid; the weight-average molecular weight was determined using a Waters 515 Gel Permeation Chromatograph (Waters Corporation, USA) with hexafluoroisopropanol containing 0.02 mol / L sodium trifluoroacetate as the eluent.

[0060] In the following examples and comparative examples, the melting point of the obtained nylon 6 material was measured using a Q2000 DSC7 Differential Scanning Calorimeter (DSC) manufactured by TA Instruments, Inc., USA, as follows: 5 mg of the sample was weighed and placed in the sample chamber of the DSC7 Differential Scanning Calorimeter. It was heated from 25°C to 250°C at a heating rate of 10°C / min under a nitrogen stream of 50 ml / min, and the melting point was detected.

[0061] Example 1 (1) Preparation of aminocaprolactam 546 g (3 mol) of L-lysine hydrochloride and 1.5 L of methanol were weighed into a 2 L three-necked flask, and 176 ml (3.3 mol) of concentrated sulfuric acid (98%) was added dropwise using a pressure-equalizing dropping funnel, and the mixture was mechanically stirred. After the addition of concentrated sulfuric acid, the solution became clear, so it was transferred to a 2 L one-necked flask and reacted under reflux conditions for 8 hours to obtain methylated lysine.

[0062] Methyl esterified lysine was transferred to a 50 L reaction kettle, 28.5 L of methanol was added, and the mixture was mechanically stirred. A sodium hydroxide solution in methanol (a solution of 480 g of sodium hydroxide dissolved in 2 L of methanol) was added dropwise, and the reaction was carried out at room temperature for 10-12 hours. The resulting mixture was concentrated and recrystallized to obtain aminocaprolactam with a purity of 90% by nuclear magnetic resonance hydrogen spectroscopy in 80% yield.

[0063] (2) Preparation of dimethyl-protected aminocaprolactam 30 g (234 mmol) of aminocaprolactam obtained in step (1) was weighed, dissolved in 500 ml of methanol, and 42 g (514 mmol) of formaldehyde solution (37% by mass) and 3 g of 10% palladium-carbon were added. The mixture was reacted under a hydrogen atmosphere for 24 hours. The resulting mixture was filtered by suction, concentrated, and recrystallized to obtain dimethyl-protected aminocaprolactam in 92% yield and 98% purity as determined by nuclear magnetic resonance hydrogen spectroscopy.

[0064] (3) Preparation of antibacterial nylon 6 material 0.5 g (3.2 mmol) of dimethyl-protected aminocaprolactam obtained in step (2), 9.5 g (84 mmol) of caprolactam, and 0.37 g (1.7 mmol) of N-benzoylcaprolactam activator were weighed into a 25 ml round-bottom flask, purged at 40°C for 30 minutes, and then 70 mg (1.7 mmol) of sodium hydride was added. The mixture was reacted under nitrogen protection in an oil bath at 180°C for 6 hours.

[0065] The material was dissolved in 100 ml of trifluoroethanol, and a portion of the resulting material was extracted for nuclear magnetic resonance (NMS) properties evaluation. The results are shown in Figure 2. 1H NMR (DMSO-d6,300MHz) δ 3.70-3.61,3.13-3.02,2.76-2.72,2.51-2.50,1.81-1.18.

[0066] The molar percentage of copolymer units derived from ε-lysine in the obtained copolymer was approximately 4%, which was calculated as the ratio of the integrated area of ​​the f-position peak to the integrated area of ​​the h-position peak in Figure 2. 1 g (19.2 mmol) of ethyl bromide was added to the remaining solution and reacted in an oil bath at 40°C for 12 hours. The reaction mixture was precipitated with ethyl acetate, centrifuged, and dried to obtain an antimicrobial nylon 6 material derived from cationic poly(ε-lysine) represented by general formula (I) in 92% yield. The weight-average molecular weight of this antimicrobial nylon 6 material was 8500, and its melting point was 210.6°C. Its DSC melting point test graph is shown in Figure 3. The molar percentage of copolymer units derived from ε-lysine in the antimicrobial nylon 6 material was approximately 4%.

[0067] Example 2 2 g (12.8 mmol) of dimethyl-protected aminocaprolactam obtained in step (2) of Example 1, 18 g (0.16 mol) of caprolactam, and 0.54 g (3.5 mmol) of N-formyl caprolactam activator were weighed into a 50 ml round-bottom flask, purged at 40°C for 30 minutes, and then 0.14 g (3.5 mmol) of sodium hydride was added. The mixture was reacted under nitrogen protection in an oil bath at 180°C for 6 hours.

[0068] The material was dissolved in 180 ml of trifluoroethanol, and a portion of the resulting material was extracted for nuclear magnetic resonance (NMS) properties evaluation. The results are as follows: 1 H NMR(DMSO-d6,300MHz) δ 3.70-3.61,3.13-3.02,2.76-2.72,2.51-2.50,1.81-1.18.

[0069] 4.2 g (38.4 mmol) of bromoethane was added to the remaining solution and reacted in an oil bath at 40°C for 12 hours. The reaction solution was then precipitated with ethyl acetate, centrifuged, and dried to obtain an antimicrobial nylon 6 material derived from cationic poly(ε-lysine) represented by general formula (I) in 95% yield. The weight-average molecular weight of this antimicrobial nylon 6 material was 10,000, and its melting point was 199.5°C. Its DSC melting point test graph is shown in Figure 4. The molar percentage of copolymer units derived from ε-lysine in the antimicrobial nylon 6 material was approximately 8%.

[0070] Example 3 3 g (19.2 mmol) of dimethyl-protected aminocaprolactam obtained in step (2) of Example 1, 17 g (0.15 mol) of caprolactam, and 0.74 g (3.4 mmol) of N-benzoylcaprolactam activator were weighed into a 50 ml round-bottom flask, purged at 40°C for 30 minutes, and then 0.14 g (3.4 mmol) of sodium hydride was added. The mixture was reacted under nitrogen protection in an oil bath at 180°C for 6 hours.

[0071] The material was dissolved in 150 ml of trifluoroethanol, and a portion of the resulting material was extracted for nuclear magnetic resonance (NMS) properties evaluation. The results are as follows: 1 H NMR(DMSO-d6,300MHz) δ 3.70-3.61,3.13-3.02,2.76-2.72,2.51-2.50,1.81-1.18.

[0072] 6.3 g (57.6 mmol) of ethyl bromide was added to the remaining solution and reacted in an oil bath at 40°C for 12 hours. The reaction solution was then precipitated with ethyl acetate, centrifuged, and dried to obtain an antimicrobial nylon 6 material derived from cationic poly(ε-lysine) represented by general formula (I) in 90% yield. The weight-average molecular weight of this antimicrobial nylon 6 material was 12,000, and its melting point was 185.7°C. Its DSC melting point test graph is shown in Figure 5. The molar percentage of copolymer units derived from ε-lysine in the antimicrobial nylon 6 material was approximately 12%.

[0073] Example 4 4 g (25.6 mmol) of dimethyl-protected aminocaprolactam obtained in step (2) of Example 1, 16 g (0.14 mol) of caprolactam, and 0.56 g (3.3 mmol) of N-acetylcaprolactam activator were weighed into a 50 ml round-bottom flask, purged at 40°C for 30 minutes, and then 0.13 g (3.3 mmol) of sodium hydride was added. The mixture was reacted under nitrogen protection in an oil bath at 180°C for 6 hours.

[0074] The material was dissolved in 180 ml of trifluoroethanol, and a portion of the resulting material was extracted for nuclear magnetic resonance (NMS) properties evaluation. The results are as follows: 1 H NMR(DMSO-d6,300MHz) δ 3.70-3.61,3.13-3.02,2.76-2.72,2.51-2.50,1.81-1.18.

[0075] 8.4 g (77.8 mmol) of bromoethane was added to the remaining solution and reacted in an oil bath at 40°C for 12 hours. The reaction solution was then precipitated with ethyl acetate, centrifuged, and dried to obtain an antimicrobial nylon 6 material derived from cationic poly(ε-lysine) represented by general formula (I) in 89% yield. The weight-average molecular weight of this antimicrobial nylon 6 material was 15,000, and its melting point was 176.3°C. Its DSC melting point test graph is shown in Figure 6. The molar percentage of copolymer units derived from ε-lysine in the antimicrobial nylon 6 material was approximately 16%.

[0076] Example 5 5 g (32 mmol) of dimethyl-protected aminocaprolactam obtained in step (2) of Example 1, 15 g (0.13 mol) of caprolactam, and 0.87 g (3.2 mmol) of N-tert-butylbenzoylcaprolactam activator were weighed into a 50 ml round-bottom flask, purged at 40°C for 30 minutes, and then 0.13 g (3.3 mmol) of sodium hydride was added. The mixture was reacted under nitrogen protection in an oil bath at 180°C for 6 hours.

[0077] The material was dissolved in 160 ml of trifluoroethanol, and a portion of the resulting material was extracted for nuclear magnetic resonance (NMS) properties evaluation. The results are as follows:1 H NMR(DMSO-d6,300MHz) δ 3.70-3.61,3.13-3.02,2.76-2.72,2.51-2.50,1.81-1.18.

[0078] 10.5 g (96 mmol) of bromoethane was added to the remaining solution and reacted in an oil bath at 40°C for 12 hours. The reaction solution was then precipitated with ethyl acetate, centrifuged, and dried to obtain an antimicrobial nylon 6 material derived from cationic poly(ε-lysine) represented by general formula (I) in 85% yield. The weight-average molecular weight of this antimicrobial nylon 6 material was 18,000, and its melting point was 167.5°C. Its DSC melting point test graph is shown in Figure 7. The molar percentage of copolymer units derived from ε-lysine in the antimicrobial nylon 6 material was approximately 20%.

[0079] Example 6 0.5 g (3.2 mmol) of dimethyl-protected aminocaprolactam obtained in step (2) of Example 1, 9.5 g (84 mmol) of caprolactam, and 0.48 g (1.7 mmol) of N-trifluoromethylbenzoylcaprolactam activator were weighed into a 25 ml round-bottom flask, purged at 40°C for 30 minutes, and then 70 mg (1.7 mmol) of sodium hydride was added. The mixture was reacted under nitrogen protection in an oil bath at 180°C for 6 hours.

[0080] The material was dissolved in 100 ml of trifluoroethanol, and a portion of the resulting material was extracted for nuclear magnetic resonance (NMS) properties evaluation. The results are as follows: 1 H NMR(DMSO-d6,300MHz) δ 3.70-3.61,3.13-3.02,2.76-2.72,2.51-2.50,1.81-1.18.

[0081] 100 ml of hydrochloric acid solution (6M) was added to the remaining solution, and the reaction was allowed to proceed at room temperature for 12 hours. The reaction mixture was precipitated with ethyl acetate, centrifuged, and dried to obtain an antimicrobial nylon 6 material derived from cationic poly(ε-lysine) having general formula (I) in 85% yield. The weight-average molecular weight of the antimicrobial nylon 6 material was 6000, and its melting point was 212.4°C. The molar percentage of copolymer units derived from ε-lysine in the antimicrobial nylon 6 material was approximately 4%.

[0082] Example 7 0.5 g (3.2 mmol) of dimethyl-protected aminocaprolactam obtained in step (2) of Example 1, 9.5 g (84 mmol) of caprolactam, and 0.37 g (1.7 mmol) of N-benzoylcaprolactam activator were weighed into a 25 ml round-bottom flask, purged at 40°C for 30 minutes, and then 70 mg (1.7 mmol) of sodium hydride was added. The mixture was reacted under nitrogen protection in an oil bath at 180°C for 6 hours.

[0083] The material was dissolved in 100 ml of trifluoroethanol, and a portion of the resulting material was extracted for nuclear magnetic resonance (NMS) properties evaluation. The results are as follows: 1 H NMR(DMSO-d6,300MHz) δ 3.70-3.61,3.13-3.02,2.76-2.72,2.51-2.50,1.81-1.18.

[0084] 15.6 g (96 mmol) of bromocyclohexane was added to the remaining solution and reacted in an oil bath at 40°C for 12 hours. The reaction mixture was precipitated with ethyl acetate, centrifuged, and dried to obtain an antimicrobial nylon 6 material derived from cationic poly(ε-lysine) represented by general formula (I) in 95% yield. The weight-average molecular weight of the antimicrobial nylon 6 material was 20,000, and its melting point was 208.6°C. The molar percentage of copolymer units derived from ε-lysine in the antimicrobial nylon 6 material was approximately 4%.

[0085] Example 8 0.5 g (3.2 mmol) of dimethyl-protected aminocaprolactam obtained in step (2) of Example 1, 9.5 g (84 mmol) of caprolactam, and 0.37 g (1.7 mmol) of N-benzoylcaprolactam activator were weighed into a 25 ml round-bottom flask, purged at 40°C for 30 minutes, and then 70 mg (1.7 mmol) of sodium hydride was added. The mixture was reacted under nitrogen protection in an oil bath at 180°C for 6 hours.

[0086] The material was dissolved in 100 ml of trifluoroethanol, and a portion of the resulting material was extracted for nuclear magnetic resonance (NMS) properties evaluation. The results are as follows: 1 H NMR(DMSO-d6,300MHz) δ 3.70-3.61,3.13-3.02,2.76-2.72,2.51-2.50,1.81-1.18.

[0087] 16.4 g (96 mmol) of benzyl bromide was added to the remaining solution and reacted in an oil bath at 40°C for 12 hours. The reaction mixture was precipitated with ethyl acetate, centrifuged, and dried to obtain an antimicrobial nylon 6 material derived from cationic poly(ε-lysine) having general formula (I) in 98% yield. The weight-average molecular weight of the antimicrobial nylon 6 material was 50,000, and its melting point was 206.3°C. The molar percentage of copolymer units derived from ε-lysine in the antimicrobial nylon 6 material was approximately 4%.

[0088] Example 9 (1) Preparation of diethyl-protected aminocaprolactam 30 g (234 mmol) of aminocaprolactam was weighed and dissolved in 500 ml of methanol. 56.6 g (514 mmol) of acetaldehyde solution (40% by mass) and 3 g of 10% palladium-carbon were added, and the mixture was reacted under a hydrogen atmosphere for 24 hours. The resulting solution was filtered by suction, concentrated, and recrystallized to obtain diethyl-protected aminocaprolactam in 88% yield. The purity of the diethyl-protected aminocaprolactam was determined to be 95% by nuclear magnetic resonance hydrogen spectroscopy.

[0089] (2) Preparation of antibacterial nylon 6 0.59 g (3.2 mmol) of the diethyl-protected aminocaprolactam obtained in step (1), 9.5 g (84 mmol) of caprolactam, and 0.37 g (1.7 mmol) of N-benzoylcaprolactam activator were weighed into a 25 ml round-bottom flask, purged at 40°C for 30 minutes, and then 70 mg (1.7 mmol) of sodium hydride was added. The mixture was reacted under nitrogen protection in an oil bath at 180°C for 6 hours.

[0090] The material was dissolved in 100 ml of trifluoroethanol, and a portion of the resulting material was extracted for nuclear magnetic resonance (NMS) properties evaluation. The results are as follows: 1 H NMR(DMSO-d6,300MHz) δ 3.75-3.63,3.34-3.12,2.78-2.62,2.50-2.40,1.61-1.28.

[0091] To the remaining solution, 1 g (19.2 mmol) of ethyl bromide was added and the mixture was reacted in an oil bath at 40°C for 12 hours. The reaction mixture was precipitated with ethyl acetate, centrifuged, and dried to obtain an antimicrobial nylon 6 material derived from cationic poly(ε-lysine) having general formula (I) in 82% yield. The weight-average molecular weight of the antimicrobial nylon 6 material was 13000, and its melting point was 208.2°C. The molar percentage of copolymer units derived from ε-lysine in the antimicrobial nylon 6 material was approximately 4%.

[0092] Example 10 (1) Preparation of dipropyl-protected aminocaprolactam 30 g (234 mmol) of aminocaprolactam was weighed and dissolved in 500 ml of methanol. 29.9 g (514 mmol) of propionaldehyde and 3 g of 10% palladium-carbon were added, and the mixture was reacted under hydrogen for 24 hours. The resulting mixture was subjected to suction filtration, concentration, and recrystallization to obtain dipropyl-protected aminocaprolactam in 89% yield. The dipropyl-protected aminocaprolactam had a purity of 97% according to nuclear magnetic resonance hydrogen spectroscopy.

[0093] (2) Preparation of antibacterial nylon 6 material 0.68 g (3.2 mmol) of dipropyl-protected aminocaprolactam obtained in step (1), 9.5 g (84 mmol) of caprolactam, and 0.37 g (1.7 mmol) of N-benzoylcaprolactam activator were weighed into a 25 ml round-bottom flask, purged at 40°C for 30 minutes, and then 70 mg (1.7 mmol) of sodium hydride was added. The mixture was reacted under nitrogen protection in an oil bath at 180°C for 6 hours.

[0094] The material was dissolved in 100 ml of trifluoroethanol, and a portion of the resulting material was extracted for nuclear magnetic resonance (NMS) properties evaluation. The results are as follows: 1 H NMR(DMSO-d6,300MHz) δ 3.85-3.53,3.30-3.10,2.88-2.52,2.40-2.28,1.71-1.18.

[0095] To the remaining solution, 1 g (19.2 mmol) of ethyl bromide was added and the mixture was reacted in an oil bath at 40°C for 12 hours. The reaction mixture was precipitated with ethyl acetate, centrifuged, and dried to obtain an antimicrobial nylon 6 material derived from cationic poly(ε-lysine) having general formula (I) in 93% yield. The weight-average molecular weight of the antimicrobial nylon 6 material was 18000, and its melting point was 201.7°C. The molar percentage of copolymer units derived from ε-lysine in the antimicrobial nylon 6 material was approximately 4%.

[0096] Example 11 (1) Preparation of dibutyl-protected aminocaprolactam 30 g (234 mmol) of aminocaprolactam was dissolved in 500 ml of methanol, and 37.1 g (514 mmol) of butyraldehyde and 3 g of 10% palladium-carbon were added. The mixture was reacted under a hydrogen atmosphere for 24 hours. The resulting solution was filtered by suction, concentrated, and recrystallized to obtain dibutyl-protected aminocaprolactam in 86% yield.

[0097] (2) Preparation of antibacterial nylon 6 0.77 g (3.2 mmol) of dibutyl-protected aminocaprolactam obtained in step (1), 9.5 g (84 mmol) of caprolactam, and 0.37 g (1.7 mmol) of N-benzoylcaprolactam activator were weighed into a 25 ml round-bottom flask, purged at 40°C for 30 minutes, and then 70 mg (1.7 mmol) of sodium hydride was added. The mixture was reacted under nitrogen protection in an oil bath at 180°C for 6 hours.

[0098] The material was dissolved in 100 ml of trifluoroethanol, and a portion of the resulting material was extracted for nuclear magnetic resonance (NMS) properties evaluation. The results are as follows: 1 H NMR(DMSO-d6,300MHz) δ 3.95-3.73,3.30-3.10,2.58-2.42,2.30-2.10,1.60-1.08.

[0099] To the remaining solution, 1 g (19.2 mmol) of ethyl bromide was added and the mixture was reacted in an oil bath at 40°C for 12 hours. The reaction mixture was precipitated with ethyl acetate, centrifuged, and dried to obtain an antimicrobial nylon 6 material derived from cationic poly(ε-lysine) having general formula (I) in 86% yield. The weight-average molecular weight of the antimicrobial nylon 6 material was 25,000, and its melting point was 201.1°C. The molar percentage of copolymer units derived from ε-lysine in the antimicrobial nylon 6 material was approximately 4%.

[0100] Example 12 (1) Preparation of dibenzyl-protected aminocaprolactam 30 g (234 mmol) of aminocaprolactam was weighed into 500 ml of acetonitrile, and 56 ml (491 mmol) of benzyl chloride and 46.8 g (351 mmol) of potassium carbonate were added. The mixture was reacted at 80°C for 6 hours with stirring. The resulting mixture was washed with 1 M hydrochloric acid, extracted with dichloromethane, dried over anhydrous sodium sulfate, and then filtered by suction, concentrated, and recrystallized to obtain dibenzyl-protected aminocaprolactam in 85% yield. The purity of the dibenzyl-protected aminocaprolactam was 95% by nuclear magnetic resonance hydrogen spectroscopy.

[0101] (2) Preparation of antibacterial nylon 6 material 0.99 g (3.2 mmol) of dibenzyl-protected aminocaprolactam obtained in step (1), 9.5 g (84 mmol) of caprolactam, and 0.37 g (1.7 mmol) of N-benzoyl caprolactam activator were weighed into a 25 ml round-bottom flask, purged at 40°C for 30 minutes, and then 70 mg (1.7 mmol) of sodium hydride was added. The mixture was reacted under nitrogen protection in an oil bath at 180°C for 6 hours.

[0102] The material was dissolved in 100 ml of trifluoroethanol, and a portion of the resulting material was extracted for nuclear magnetic resonance (NMS) properties evaluation. The results are as follows: 1 H NMR(DMSO-d6,300MHz) δ 7.35-7.12,5.52-5.36,3.75-3.63,3.24-3.10,2.51-2.38,1.81-1.28.

[0103] To the remaining solution, 1 g (19.2 mmol) of ethyl bromide was added and the mixture was reacted in an oil bath at 40°C for 12 hours. The reaction mixture was precipitated with ethyl acetate, centrifuged, and dried to obtain an antimicrobial nylon 6 material derived from cationic poly(ε-lysine) having general formula (I) in 93% yield. The weight-average molecular weight of the antimicrobial nylon 6 material was 50,000, and its melting point was 196.5°C. The molar percentage of copolymer units derived from ε-lysine in the antimicrobial nylon 6 material was approximately 4%.

[0104] Example 13 (1) Preparation of N,N-hexahydropyridylaminocaprolactam 30 g (234 mmol) of aminocaprolactam was weighed into 500 ml of acetonitrile, and 80.7 g (351 mmol) of 1,5-dibromopentane and 46.8 g (351 mmol) of potassium carbonate were added. The mixture was reacted at 80°C for 6 hours with stirring. The resulting mixture was washed with 1 M hydrochloric acid, extracted with dichloromethane, dried over anhydrous sodium sulfate, and then filtered by suction, concentrated, and recrystallized to obtain N,N-hexahydropyridylaminocaprolactam in 75% yield. The purity of the N,N-hexahydropyridylaminocaprolactam was determined to be 90% by nuclear magnetic resonance hydrogen spectroscopy.

[0105] (2) Preparation of antibacterial nylon 6 material 0.63 g (3.2 mmol) of N,N-hexahydropyridylaminocaprolactam, 9.5 g (84 mmol) of caprolactam, and 0.37 g (1.7 mmol) of N-benzoylcaprolactam activator were weighed into a 25 ml round-bottom flask, purged at 40°C for 30 minutes, and then 70 mg (1.7 mmol) of sodium hydride was added. The mixture was then reacted in an oil bath at 180°C for 6 hours under nitrogen protection.

[0106] The material was dissolved in 100 ml of trifluoroethanol, and a portion of the resulting material was extracted for nuclear magnetic resonance (NMS) properties evaluation. The results are as follows: 1 H NMR(DMSO-d6,300MHz) δ 5.53-5.31,3.70-3.53,3.32-3.12,2.55-2.40,1.61-1.18.

[0107] To the remaining solution, 1 g (19.2 mmol) of ethyl bromide was added and the mixture was reacted in an oil bath at 40°C for 12 hours. The reaction mixture was precipitated with ethyl acetate, centrifuged, and dried to obtain an antimicrobial nylon 6 material derived from cationic poly(ε-lysine) having general formula (I) in 88% yield. The weight-average molecular weight of the antimicrobial nylon 6 material was 20,000, and its melting point was 193.8°C. The molar percentage of copolymer units derived from ε-lysine in the antimicrobial nylon 6 material was approximately 4%.

[0108] Example 14 (1) Preparation of diallyl-protected aminocaprolactam 30 g (234 mmol) of aminocaprolactam was weighed into 500 ml of acetonitrile, and 59.4 g (491 mmol) of allyl bromide and 46.8 g (351 mmol) of potassium carbonate were added. The mixture was reacted at 80°C for 6 hours with stirring. The resulting mixture was washed with 1 M hydrochloric acid, extracted with dichloromethane, dried over anhydrous sodium sulfate, then filtered by suction, concentrated, and recrystallized to obtain diallyl-protected aminocaprolactam in 78% yield. The purity of the diallyl-protected aminocaprolactam was 97% by nuclear magnetic resonance hydrogen spectroscopy.

[0109] (2) Preparation of antibacterial nylon 6 0.67 g (3.2 mmol) of diallyl-protected aminocaprolactam, 9.5 g (84 mmol) of caprolactam, and 0.37 g (1.7 mmol) of N-benzoylcaprolactam activator were weighed into a 25 ml round-bottom flask, purged at 40°C for 30 minutes, and then 70 mg (1.7 mmol) of sodium hydride was added. The mixture was then reacted in an oil bath at 180°C for 6 hours under nitrogen protection.

[0110] The material was dissolved in 100 ml of trifluoroethanol, and a portion of the resulting material was extracted for nuclear magnetic resonance (NMS) properties evaluation. The results are as follows: 1 H NMR(DMSO-d6,300MHz) δ 4.53-4.23,3.95-3.73,3.44-3.22,2.53-2.40,1.81-1.38.

[0111] To the remaining solution, 1 g (19.2 mmol) of ethyl bromide was added and the mixture was reacted in an oil bath at 40°C for 12 hours. The reaction mixture was precipitated with ethyl acetate, centrifuged, and dried to obtain an antimicrobial nylon 6 material derived from cationic poly(ε-lysine) having general formula (I) in 92% yield. The weight-average molecular weight of the antimicrobial nylon 6 material was 18,000, and its melting point was 200.3°C. The molar percentage of copolymer units derived from ε-lysine in the antimicrobial nylon 6 material was approximately 4%.

[0112] Example 15 (1) Preparation of didodecyl-protected aminocaprolactam 30 g (234 mmol) of aminocaprolactam was weighed into 500 ml of acetonitrile, and 122.4 g (491 mmol) of dodecyl bromide and 46.8 g (351 mmol) of potassium carbonate were added. The mixture was reacted at 80°C for 6 hours with stirring. The resulting mixture was washed with 1 M hydrochloric acid, extracted with dichloromethane, dried over anhydrous sodium sulfate, and then filtered by suction, concentrated, and recrystallized to obtain didodecyl-protected aminocaprolactam in 70% yield. The purity of the didodecyl-protected aminocaprolactam was 90% by nuclear magnetic resonance hydrogen spectroscopy.

[0113] (2) Preparation of antibacterial nylon 6 material 1.49 g (3.2 mmol) of didodecyl-protected aminocaprolactam obtained in step (1), 9.5 g (84 mmol) of caprolactam, and 0.37 g (1.7 mmol) of N-benzoylcaprolactam activator were weighed into a 25 ml round-bottom flask, purged at 40°C for 30 minutes, and then 70 mg (1.7 mmol) of sodium hydride was added. The mixture was reacted under nitrogen protection in an oil bath at 180°C for 6 hours.

[0114] The material was dissolved in 100 ml of trifluoroethanol, and a portion of the resulting material was extracted for nuclear magnetic resonance (NMS) properties evaluation. The results are as follows: 1 H NMR(DMSO-d6,300MHz) δ 3.65-3.43,3.24-3.02,2.758-2.32,2.20-2.06,1.51-1.18.

[0115] To the remaining solution, 1 g (19.2 mmol) of ethyl bromide was added and the mixture was reacted in an oil bath at 40°C for 12 hours. The reaction mixture was precipitated with ethyl acetate, centrifuged, and dried to obtain an antimicrobial nylon 6 material derived from cationic poly(ε-lysine) having general formula (I) in 89% yield. The weight-average molecular weight of the antimicrobial nylon 6 material was 80,000, and its melting point was 185.6°C. The molar percentage of copolymer units derived from ε-lysine in the antimicrobial nylon 6 material was approximately 4%.

[0116] Comparative Example 1 9.5 g (84 mmol) of caprolactam and 0.37 g (1.7 mmol) of N-benzoyl caprolactam activator were weighed into a 25 ml round-bottom flask, purged at 40°C for 30 minutes, and then 70 mg (1.7 mmol) of sodium hydride was added. The mixture was reacted in an oil bath at 180°C under a nitrogen atmosphere for 6 hours to obtain conventional nylon 6 with a melting point of 222.3°C.

[0117] Comparative Example 2 0.25 g (1.6 mmol) of dimethyl-protected aminocaprolactam obtained in step (2) of Example 1, 36.2 g (320 mmol) of caprolactam, and 1.41 g (6.5 mmol) of N-benzoylcaprolactam activator were weighed into a 25 ml round-bottom flask, purged at 40°C for 30 minutes, and then 260 mg (6.5 mmol) of sodium hydride was added. The mixture was reacted under nitrogen protection in an oil bath at 180°C for 6 hours.

[0118] The material was dissolved in 100 ml of trifluoroethanol, and a portion of the resulting material was extracted for nuclear magnetic resonance (NMS) properties evaluation. The results are as follows: 1 H NMR(DMSO-d6,300MHz) δ 3.70-3.61,3.13-3.02,2.76-2.72,2.51-2.50,1.81-1.18.

[0119] To the remaining solution, 1 g (19.2 mmol) of ethyl bromide was added and the mixture was reacted in an oil bath at 40°C for 12 hours. The reaction mixture was precipitated with ethyl acetate, centrifuged, and dried to obtain a modified nylon 6 material derived from cationic poly(ε-lysine) in 98% yield. The weight-average molecular weight of the modified nylon 6 material was 50,000, and its melting point was 219.5°C. The molar percentage of copolymer units derived from ε-lysine in the modified nylon 6 material was approximately 0.5%.

[0120] Comparative Example 3 15.6 g (100 mmol) of dimethyl-protected aminocaprolactam obtained in step (2) of Example 1, 11.3 g (100 mmol) of caprolactam, and 0.87 g (4 mmol) of N-benzoylcaprolactam activator were weighed into a 25 ml round-bottom flask, purged at 40°C for 30 minutes, and then 160 mg (4 mmol) of sodium hydride was added. The mixture was reacted under nitrogen protection in an oil bath at 180°C for 6 hours.

[0121] The material was dissolved in 100 ml of trifluoroethanol, and a portion of the resulting material was extracted for nuclear magnetic resonance (NMS) properties evaluation. The results are as follows: 1 H NMR(DMSO-d6,300MHz) δ 3.70-3.61,3.13-3.02,2.76-2.72,2.51-2.50,1.81-1.18.

[0122] 65.3 g (600 mmol) of ethyl bromide was added to the remaining solution and reacted in an oil bath at 40°C for 12 hours. The reaction mixture was precipitated with ethyl acetate, centrifuged, and dried to obtain a modified nylon 6 material derived from cationic polyε-lysine in 60% yield. The weight-average molecular weight of the modified nylon 6 material was 13500, and the melting point could not be measured due to its amorphous nature. The molar percentage of copolymer units derived from ε-lysine in the modified nylon 6 material was approximately 40%.

[0123] [Table 1]

[0124] Antibacterial efficacy test The antibacterial effect was tested according to the Chinese national standard GB / T 31402-2015, with the culture time and temperature adjusted as needed, as shown below: The antibacterial nylon 6 materials obtained in Examples 1-15 and the nylon 6 materials obtained in Comparative Examples 1-3 were pressed into 0.75 cm × 0.75 cm square sheets, sterilized with an ultraviolet lamp for 30 minutes, then a pre-prepared bacterial solution was dropped onto them, covered with PE film, and cultured at 37°C for 6 hours. Subsequently, the bacterial solution was subjected to a 3-minute supersonic treatment, diluted 100-fold, and cultured on a solid nutrient medium at 37°C for 20 hours. The conventional nylon 6 material obtained in Comparative Example 1 was used as a control. The test bacteria used were Staphylococcus aureus (S. aureus) ATCC6538 and Escherichia coli (E. coli) ATCC25922. The test results are shown in Table 2.

[0125] The antibacterial rate was calculated using the following formula:

number

[0126] Mechanical properties test The antibacterial nylon 6 materials obtained in Examples 1-15 and the nylon 6 materials obtained in Comparative Examples 1-3 were injection molded into 40mm x 4mm x 2mm rods, and tensile tests were performed. The test results are shown in Table 2.

[0127] [Table 2]

[0128] As is clear from the data in Table 2, the antibacterial nylon 6 material of the present invention has substantially the same antibacterial effect as conventional nylon 6 materials and also has good mechanical properties. In contrast, the nylon 6 material of Comparative Example 2 has insufficient antibacterial activity, and the nylon 6 material of Comparative Example 3 has inferior mechanical properties.

[0129] Figures 8A and 8B are photographs comparing the antibacterial effects against Staphylococcus aureus between the nylon 6 material obtained in Comparative Example 1 and the nylon 6 material obtained in Example 5, with the spots shown being live bacterial colonies. As is clear from the figures, the antibacterial nylon 6 material of the present invention has a significantly greater inhibitory effect against Staphylococcus aureus compared to the conventional nylon 6 material obtained in Comparative Example 1.

[0130] The present invention is illustrated in detail above with reference to preferred embodiments, but is not intended to be limited to these embodiments. Various modifications can be made in accordance with the inventive concept of the present invention, and such modifications shall remain within the scope of the invention.

[0131] The various technical features described in the embodiments above can be combined in any suitable way without contradiction, and to avoid unnecessary repetition, various possible combinations are not described in this application, however it should be noted that such combinations are also within the scope of this application.

[0132] Furthermore, various embodiments of the present invention can be combined in any way, as long as the combination does not depart from the spirit of the invention, and such combined embodiments should be considered as disclosures of the present invention.

Claims

1. Antibacterial nylon 6 material having a structure represented by the following formula (I): 【Chemistry 1】 Here, Each R １ Base and each R ２ The group is a C2-24 linear or branched aliphatic hydrocarbyl group, substituted or unsubstituted C ３－１２ Alicyclic hydrocarbyl group, substituted or unsubstituted C ６－１８ Aryl groups, and substituted or unsubstituted carbons ７－３０ R is independently selected from the group consisting of aralkyl groups, or R is located on the same nitrogen atom. １ base and R ２ The group, together with the bonded N atom, forms a 5- to 7-membered saturated or unsaturated heterocycle; Each R ３ groups are independently selected from the group consisting of hydrogen (H), C １－２４ straight-chain or branched aliphatic hydrocarbyl groups, substituted or unsubstituted C ３－１２ alicyclic hydrocarbyl groups, substituted or unsubstituted C ６－１８ aryl groups, and substituted or unsubstituted C ７－３０ aralkyl groups; and x and y are, respectively, the total amount of repeating units in equation (I), 【Chemistry 2】 The molar ratio of repeating units having the structure and 【Transformation 3】 This represents the molar ratio of repeating units having the structure, where x is in the range of 0.02 to 0.30; y is in the range of 0.70 to 0.98, and x + y = 1; Here, the expression "substitution" means that the aforementioned base is C １－１８ An antimicrobial nylon 6 material, meaning it is substituted with one or more substituents selected from the group consisting of linear or branched alkyl groups.

2. An antibacterial nylon 6 material having a structure represented by the following formula (I): 【Chemistry 4】 Here, Each R1 and R2 group is independently selected from the group consisting of C1-24 linear or branched aliphatic hydrocarbyl groups, substituted or unsubstituted C3-12 alicyclic hydrocarbyl groups, substituted or unsubstituted C6-18 aryl groups, and substituted or unsubstituted C7-30 aralkyl groups, or R1 and R2 groups on the same nitrogen atom, together with the bonded N atom, form a 5-7 member saturated or unsaturated heterocycle; Each R3 group is independently selected from the group consisting of hydrogen (H), C1-24 linear or branched aliphatic hydrocarbyl groups, substituted or unsubstituted C3-12 alicyclic hydrocarbyl groups, substituted or unsubstituted C6-18 aryl groups, and substituted or unsubstituted C7-30 aralkyl groups; and x and y are, respectively, the total amount of repeating units in equation (I), 【Transformation 5】 The molar ratio of repeating units having the structure and 【Transformation 6】 This represents the molar ratio of repeating units having the structure, where x is in the range of 0.12 to 0.30; y is in the range of 0.70 to 0.88, and x + y = 1; Here, the term "substituted" means that the group is substituted with one or more substituents selected from the group consisting of C1-18 linear or branched alkyl groups, in the antimicrobial nylon 6 material.

3. The R1 group and the R2 group are each methyl, The antibacterial nylon 6 material according to claim 2, wherein x is in the range of 0.12 to 0.30; y is in the range of 0.70 to 0.88, and x + y = 1.

4. The R1 group and the R2 group are each methyl, The R3 group is ethyl, The antibacterial nylon 6 material according to claim 3, wherein x is in the range of 0.12 to 0.20; y is in the range of 0.80 to 0.88, and x + y = 1.

5. Each R １ Base and each R ２ The base is C １－１２ Linear or branched aliphatic hydrocarbyl groups, substituted or unsubstituted C ３－６ Alicyclic hydrocarbyl group, substituted or unsubstituted C ６－１０ Aryl groups, and substituted or unsubstituted carbons ７－１６ R is independently selected from the group consisting of aralkyl groups, or R is located on the same nitrogen atom. １ base and R ２ The group, together with the bonded N atom, forms a 5-6 member saturated or unsaturated heterocycle; and Each R ３ The base is hydrogen (H), C １－１２ Linear or branched aliphatic hydrocarbyl groups, substituted or unsubstituted C ３－６ Alicyclic hydrocarbyl group, substituted or unsubstituted C ６－１０ Aryl groups, and substituted or unsubstituted C ７－１６ The antibacterial nylon 6 material according to claim 2, independently selected from the group consisting of aralkyl groups.

6. Each R1 group and each R2 group are independently selected from the group consisting of methyl, ethyl, propyl, butyl, hexyl, octyl, dodecyl, allyl, phenyl, and benzyl, or R1 and R2 groups on the same nitrogen atom, together with the bonded N atom, form a tetrahydropyrrolyl group or a hexahydropyridyl group; and The antimicrobial nylon 6 material according to claim 2, wherein each R3 group is independently selected from the group consisting of hydrogen (H), methyl, ethyl, propyl, butyl, hexyl, octyl, dodecyl, cyclohexyl, phenyl, and benzyl.

7. The total number of repeating units in formula (I) is in the range of 10 to 2500; and / or The antibacterial nylon 6 material according to claim 1 or 2, wherein the antibacterial nylon 6 has a weight-average molecular weight of 2,000 to 500,000.

8. The antibacterial nylon 6 material according to claim 1, in an amount of 70% by weight to less than 100% by weight, and different from the antibacterial nylon 6 material, in an amount of 0% by weight to 30% by weight. 【Transformation 7】 Repeating units having the structure and / or 【Transformation 8】 A nylon 6 composition comprising at least one polymer having a repeating unit having the structure R １ , R ２ , and R ３ A nylon 6 composition as defined in claim 1.

9. The nylon 6 composition according to claim 8, further containing 0 to 30% by weight of an additive selected from the group consisting of reinforcing agents, fillers, toughening agents, plasticizers, flame retardants, colorants, fluorescent whitening agents, light stabilizers, antioxidants, heat stabilizers, lubricants, mold release agents, and combinations thereof.

10. The antibacterial nylon 6 material according to Claim 2, in an amount of 70% by weight to less than 100% by weight, and a different material from the antibacterial nylon 6 material, in an amount of 0% by weight to 30% by weight. 【Chemistry 9】 Repeating units having the structure and / or 【Chemistry 10】 A nylon 6 composition comprising at least one polymer having repeating units having the structure, wherein the groups R1, R2, and R3 are as defined in claim 2.

11. The nylon 6 composition according to claim 10, further containing 0 to 30% by weight of an additive selected from the group consisting of reinforcing agents, fillers, toughening agents, plasticizers, flame retardants, colorants, fluorescent whitening agents, light stabilizers, antioxidants, heat stabilizers, lubricants, mold release agents, and combinations thereof.

12. The following steps: 1) A step of providing a cyclic lysine monomer having a structure represented by the following formula (II), 【Chemistry 11】 Here, R １ and R ２ The group is a C2-24 linear or branched aliphatic hydrocarbyl group, substituted or unsubstituted C ３－１２ Alicyclic hydrocarbyl group, substituted or unsubstituted C ６－１８ Aryl groups, and substituted or unsubstituted carbons ７－３０ Independently selected from the group consisting of aralkyl groups, or the R １ and R ２ The group, together with the bonded N atom, forms a saturated or unsaturated heterocycle of 5 to 7 members; 2) A step of subjecting the cyclic lysine monomer and the caprolactam monomer to ring-opening polymerization in a molar ratio of 2:98 to 30:70 to obtain a copolymer having a structure represented by the following formula (III), 【Chemistry 12】 3) The copolymer is reacted with a halogen having a structure represented by the following formula (IV): R ３ -Hal (IV) Here, R ３ The base is hydrogen (H), C １－２４ Linear or branched aliphatic hydrocarbyl groups, substituted or unsubstituted C ３－１２ Alicyclic hydrocarbyl group, substituted or unsubstituted C ６－１８ Aryl groups, and substituted or unsubstituted C ７－３０ Selected from the group consisting of aralkyl groups, Hal represents halogen, A step to obtain antibacterial nylon 6 having a structure represented by the following formula (I), 【Chemistry 13】 A method for preparing an antibacterial nylon 6 material, including, Here, the expression "substitution" means that the aforementioned base is C １－１８ A method in which a molecule is substituted with one or more substituents selected from linear or branched alkyl groups.

13. The following steps: 1) A step of providing a cyclic lysine monomer having a structure represented by the following formula (II), 【Chemistry 14】 Here, the R1 and R2 groups are independently selected from the group consisting of C1-24 linear or branched aliphatic hydrocarbyl groups, substituted or unsubstituted C3-12 alicyclic hydrocarbyl groups, substituted or unsubstituted C6-18 aryl groups, and substituted or unsubstituted C7-30 aralkyl groups, or the R1 and R2 groups, together with the bonded N atom, form a 5-7 member saturated or unsaturated heterocycle; 2) A step of subjecting the cyclic lysine monomer and the caprolactam monomer to ring-opening polymerization in a molar ratio of 12:88 to 30:70 to obtain a copolymer having a structure represented by the following formula (III), 【Chemistry 15】 3) The copolymer is reacted with a halogen having a structure represented by the following formula (IV): R 3 -Hal (IV) Here, the R3 group is selected from the group consisting of hydrogen (H), C1-24 linear or branched aliphatic hydrocarbyl groups, substituted or unsubstituted C3-12 alicyclic hydrocarbyl groups, substituted or unsubstituted C6-18 aryl groups, and substituted or unsubstituted C7-30 aralkyl groups. Hal represents halogen, A step to obtain antibacterial nylon 6 having a structure represented by the following formula (I), 【Chemistry 16】 A method for preparing an antibacterial nylon 6 material, including, Here, the term "substitution" means that the group is substituted by one or more substituents selected from C1-18 linear or branched alkyl groups in this method.

14. The aforementioned R １ and R ２ The base is C １－１２ Linear or branched aliphatic hydrocarbyl groups, substituted or unsubstituted C ３－６ Alicyclic hydrocarbyl group, substituted or unsubstituted C ６－１０ Aryl groups, and substituted or unsubstituted carbons ７－１６ Independently selected from the group consisting of aralkyl groups, or the R １ and R ２ The group, together with the bonded N atom, forms a 5-6 member saturated or unsaturated heterocycle; and The aforementioned R ３ The base is hydrogen (H), C １－１２ Linear or branched aliphatic hydrocarbyl groups, substituted or unsubstituted C ３－６ Alicyclic hydrocarbyl group, substituted or unsubstituted C ６－１０ Aryl groups, and substituted or unsubstituted C ７－１６ The method according to claim 13, selected from the group consisting of aralkyl groups.

15. The R1 and R2 groups are independently selected from the group consisting of methyl, ethyl, propyl, butyl, hexyl, octyl, dodecyl, allyl, phenyl, and benzyl, or the R1 and R2 groups, together with the bonded N atom, form a tetrahydropyrrolyl group or a hexahydropyridyl group; and The method according to claim 14, wherein the R3 group is selected from the group consisting of hydrogen (H), methyl, ethyl, propyl, butyl, hexyl, octyl, dodecyl, cyclohexyl, phenyl, and benzyl.

16. The method according to any one of claims 12 to 15, wherein the cyclic lysine monomer is provided in step 1) by protecting a primary amine group on an aminocaprolactam represented by formula (V) with a protecting group. 【Chemistry 17】

17. Step 1) above involves the aminocaprolactam being R １ and / or R ２ The method according to claim 16, which is achieved by reacting with an aldehyde and / or halogenated hydrocarbon having a group.

18. The method according to any one of claims 12 to 15, wherein step 2) is carried out in the presence of a catalyst selected from the group consisting of a carbene reagent, a guanidine reagent, an amidine reagent, a phosphazene reagent, an alkali metal, an alkali metal oxide, an alkali metal hydroxide, an alkali metal hydride, an alkali metal alkoxide, an alkaline earth metal, an alkaline earth metal oxide, an alkaline earth metal hydroxide, an alkaline earth metal hydride, an alkaline earth metal alkoxide, or a combination thereof.

19. The method according to claim 18, wherein the molar ratio of the total amount of the cyclic lysine monomer and the caprolactam monomer to the catalyst in step 2) is (10 to 50):

1.

20. The ring-opening polymerization in step 2) is carried out in the presence of an activator having the following structure; [Chemistry 18] Here, R is selected from the group consisting of methyl, ethyl, phenyl, t-butylphenyl, and trifluoromethylphenyl; The method according to any one of claims 12 to 15, wherein the molar ratio of the total amount of the cyclic lysine monomer and the caprolactam monomer to the activator in step 2) is (10-50):

1.

21. The method according to any one of claims 12 to 15, having one or more of the following features: The reaction conditions for step 2) include a polymerization temperature of 140 to 180°C and a reaction time of 3 to 6 hours; The halogenated compound represented by formula (IV) used in step 3) is selected from the group consisting of hydrochloric acid, methyl iodide, ethyl bromide, butyl bromide, bromohexane, bromocyclohexane, benzyl bromide, or combinations thereof; The reaction in step 3) is carried out in a solvent selected from the group consisting of methanol, ethanol, trifluoroethanol, benzyl alcohol, ethylene glycol, cyclohexanol, or a combination thereof, under reaction conditions including a reaction temperature of 40 to 70°C and a reaction time of 10 to 12 hours; and / or Step 3) further includes the step of precipitating the reaction product of the copolymer and the halogen in ethyl acetate, centrifuging it, and drying it to obtain antibacterial nylon 6.

22. An article comprising an antimicrobial nylon 6 material according to any one of claims 1 to 6, a nylon 6 composition according to any one of claims 8 to 11, or an antimicrobial nylon 6 material obtained by the method according to any one of claims 12 to 15.

23. The article according to claim 22, selected from the group consisting of textile products, daily necessities, building materials, packaging materials and panels.

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