Patent Application
20240343863
The present application relates to the technical field of antibacterial high polymer materials, and particularly relates to an antibacterial nylon 6 material, preparation method therefor and application thereof.
Microorganisms in nature are of a wide variety. In daily life, microorganisms are closely and indiscriminately connected with people, and part of bacteria, fungi, viruses and the like as pathogenic bacteria seriously jeopardize the health and even the life of human beings. 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 the outbreaks, people pay more and more attention to the harm of bacteria or microorganisms to the health and living environment of people, and the requirements on the quality and the function of products used are higher and higher. Therefore, the development of new antibacterial materials becomes important. The antibacterial polymer material can inhibit and kill microorganisms such as bacteria, fungi and the like present on the antibacterial polymer material, and is widely used in the fields of sanitation, medical treatment, environmental protection and the like.
Polycaprolactam (commonly called nylon or chinlon) has the excellent properties of light weight, high strength, wear resistance, resistance to weak acid, weak base, and some organic solvents, easy forming and processing and the like, and is widely used in the fields of fibers, engineering plastics, films and the like. However, the molecular chain segment of nylon 6 (PA-6) contains amide groups with strong polarity, so that hydrogen bonds are easily formed with water molecules, and the product easily absorbs moisture in the environment, thereby providing a good breeding place for bacteria and fungi. The nylon 6 material is almost ubiquitous in daily life, so that the development of a nylon 6 material with an antibacterial function can effectively reduce or avoid the infection and the transmission of bacteria, and has important significance for improving the living environment of people and reducing diseases.
Currently, commercial antibacterial nylon 6 materials are mainly prepared by blending polycaprolactam and small molecule antibacterial agents, see, for example, CN107652669, CN107793748 and CN108047709, which have many problems in terms of safety, environmental friendliness, and antibacterial efficiency and durability.
Therefore, the development of a novel antibacterial nylon 6 material which is environment-friendly and has lasting and efficient antibacterial performance is of great significance.
An object of the present application is to provide a novel nylon 6 material with an antibacterial function, preparation method therefor and application thereof, the nylon 6 material can overcome the defects of poor antibacterial durability, low stability and the like of antibacterial nylon 6 materials obtained by blending, and is low in cost, simple in preparation and suitable for large-scale production.
To achieve the above object, in an aspect, the present application provides an antibacterial nylon 6 material having a structure represented by the following formula (I):
In another aspect, the present application provides a nylon 6 composition comprising from 70 wt % to less than 100 wt % of the antibacterial nylon 6 material according to the present application and from 0 wt % to 30 wt % of at least one polymer comprising a recurring unit having a structure of
In another aspect, the present application provides a method for preparing an antibacterial nylon 6 material, comprising the steps of:
R3-Hal (IV),
The antibacterial nylon 6 material according to the present application has a broad-spectrum and high antibacterial effect, has good antibacterial durability and stability, and can be widely used in textiles, daily necessities, building materials, packaging materials, various panels and the like as a public health material; and is low in cost, simple in preparation and easy for large-scale production.
In yet another aspect, the present application provides an article comprising the antibacterial nylon 6 material according to the present application, the nylon 6 composition according to the present application, or an antibacterial nylon 6 material obtained by the method according to the present application.
Preferably, the article is selected from the group consisting of textiles, daily necessities, building materials, packaging materials and panels.
Other characteristics and advantages of the present application will be described in detail in the detailed description hereinbelow.
The drawings, forming a part of the present description, are provided to help the understanding of the present application, and should not be considered to be limiting. The present application can be interpreted with reference to the drawings in combination with the detailed description hereinbelow. In the drawings:
The present application will be further described hereinafter in detail with reference to the drawing and specific embodiments thereof. It should be noted that the specific embodiments of the present application are provided for illustration purpose only, and are not intended to be limiting in any manner.
Any specific numerical value, including the endpoints of a numerical range, described in the context of the present application is not restricted to the exact value thereof, but should be interpreted to further encompass all values close to said exact value, for example all values within ±5% of said exact value. Moreover, regarding any numerical range described herein, arbitrary combinations can be made 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, to provide one or more new numerical range(s), where said new numerical range(s) should also be deemed to have been specifically described in the present application.
Unless otherwise stated, the terms used herein have the same meaning as commonly understood by those skilled in the art; and if the terms are defined herein and their definitions are different from the ordinary understanding in the art, the definition provided herein shall prevail.
In the present application, the term “substituted” means that the group is substituted with one or more substituents selected from C1-18 linear or branched alkyl groups, preferably C1-12 linear or branched alkyl groups, more preferably C1-6 linear or branched alkyl groups.
In the context of the present application, in addition to those matters explicitly stated, any matter or matters not mentioned are considered to be the same as those known in the art without any change. Moreover, any of the embodiments described herein can be freely combined with another one or more embodiments described herein, and the technical solutions or ideas thus obtained are considered as part of the original disclosure or original description of the present application, and should not be considered to be a new matter that has not been disclosed or anticipated herein, unless it is clear to the person skilled in the art that such a combination is obviously unreasonable.
All of the patent and non-patent documents cited herein, including but not limited to textbooks and journal articles, are hereby incorporated by reference in their entirety.
As described above, in a first aspect, the present application provides an antibacterial nylon 6 material having a structure represented by the following formula (I):
In a preferred embodiment, each R1 group and each R2 group are independently selected from the group consisting of C1-12 linear or branched aliphatic hydrocarbyl groups (e.g., C1-8 linear or branched aliphatic hydrocarbyl groups, C1-6 linear or branched aliphatic hydrocarbyl groups, C1-4 linear or branched aliphatic hydrocarbyl groups, such as alkyl or alkenyl groups, preferably alkyl groups), substituted or unsubstituted C3-6 alicyclic hydrocarbyl groups, substituted or unsubstituted C6-10 aryl groups, and substituted or unsubstituted C7-16 aralkyl groups, or the R1 and R2 groups on the same nitrogen atom, together with the attached N atom, form a 5-6 membered saturated or unsaturated heterocyclic ring; and each R3 group is independently selected from the group consisting of hydrogen (H), C1-12 linear or branched aliphatic hydrocarbyl groups (e.g., C1-8 linear or branched aliphatic hydrocarbyl groups, C1-6 linear or branched aliphatic hydrocarbyl groups, C1-4 linear or branched aliphatic hydrocarbyl groups, such as alkyl or alkenyl groups, preferably alkyl groups), substituted or unsubstituted C3-6 alicyclic hydrocarbyl groups, substituted or unsubstituted C6-10 aryl groups, and substituted or unsubstituted C7-16 aralkyl groups.
In a further 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 the R1 and R2 groups on the same nitrogen atom, together with the attached N atom, form a tetrahydropyrrolyl or 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.
In a still further preferred embodiment, all R1 groups and R2 groups are the same and are 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 attached N atom, form a tetrahydropyrrolyl or hexahydropyridyl group; and all R3 groups are the same and are selected from the group consisting of hydrogen (H), methyl, ethyl, propyl, butyl, hexyl, octyl, dodecyl, cyclohexyl, and benzyl.
In a particularly preferred embodiment, all R1 groups and R2 groups are the same and are 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 on the same nitrogen atom, together with the attached N atom, form a hexahydropyridyl group; and all R3 groups are the same and are selected from the group consisting of hydrogen (H), ethyl, cyclohexyl, and benzyl, especially ethyl.
In a preferred embodiment, x in formula (I) is in a range of 0.03 to 0.25, more preferably 0.04 to 0.20, for example in a range of 0.08 to 0.20, 0.12 to 0.20 or 0.16 to 0.20; y is in a range of 0.75 to 0.97, more preferably 0.80 to 0.96, e.g. in a range of 0.80 to 0.92, 0.88 to 0.80 or 0.84 to 0.80, and x+y=1.
In a preferred embodiment, the total number of recurring units in the antibacterial nylon 6 material represented by formula (I) is in a range of 10 to 2500, preferably 20 to 1000, more preferably 20 to 500.
In a preferred embodiment, the antibacterial nylon 6 material has a weight average molecular weight of 2000 to 500000, preferably 5000 to 200000, more preferably 5000 to 100000.
In a second aspect, the present application provides a nylon 6 composition comprising from 70 wt % to less than 100 wt % of the antibacterial nylon 6 material according to the present application and from 0 wt % to 30 wt % of at least one polymer comprising a recurring unit having a structure of
In a preferred embodiment, the nylon 6 composition comprises from 80 wt % to less than 100 wt %, more preferably from 90 wt % to less than 100 wt %, such as 91 wt %, 92 wt %, 93 wt %, 94 wt %, 95 wt %, 96 wt %, 97 wt %, 98 wt %, 99 wt %, of the antibacterial nylon 6 material according to the present application and from more than 0 wt % to 20 wt %, more preferably from more than 0 wt % to 10 wt %, such as 0.1 wt %, 0.2 wt %, 0.3 wt %, 0.4 wt %, 0.5 wt %, 0.6 wt %, 0.7 wt %, 0.8 wt %, 0.9 wt %, 1 wt %, 2 wt %, 3 wt %, 4 wt %, 5 wt %, 6 wt %, 7 wt %, 8 wt %, 9 wt %, of the at least one polymer different from said antibacterial nylon 6 material.
In some particular embodiments, the polymer different from the antibacterial nylon 6 material has a structure similar to formula (I), except that x is outside the range of 0.02-0.30, y is outside the range of 0.70-0.98, and x+y=1.
In a preferred embodiment, the nylon 6 composition according to the present application further comprises from 0 wt % to 30 w t %, preferably from 0 wt % to 20 wt %, more preferably from 0 wt % to 10 wt %, such as 0.1 wt %, 0.2 wt %, 0.3 wt %, 0.4 wt %, 0.5 wt %, 0.6 wt %, 0.7 wt %, 0.8 wt %, 0.9 wt %, 1 wt %, 2 wt %, 3 wt %, 4 wt %, 5 wt %, 6 wt %, 7 wt %, 8 wt %, 9 wt %, of an additive selected from the group consisting of reinforcing agents, fillers, toughening agents, plasticizers, flame retardants, colorants, optical brighteners, light stabilizers, antioxidants, heat stabilizers, lubricants, mold release agents, and combinations thereof.
Suitable additives for use in the composition of the present application may be any additive conventionally used in nylon production and processing, and there is no particular limitation in the present application. For example, fillers suitable for use in the composition of the present application may be those commonly used in the art, including, but not limited to, activated calcium carbonate, talc, wollastonite, mica, and the like; antioxidants suitable for use in the composition of the present application can be those commonly used in the art, including, but not limited to, phenolic antioxidants, phosphite antioxidants, and the like.
In a third aspect, the present application provides a method for preparing an antibacterial nylon 6 material, comprising the steps of:
R3-Hal (IV),
In a preferred embodiment, the R1 and R2 groups are independently selected from the group consisting of C1-12 linear or branched aliphatic hydrocarbyl groups (e.g., C1-8 linear or branched aliphatic hydrocarbyl groups, C1-6 linear or branched aliphatic hydrocarbyl groups, C1-4 linear or branched aliphatic hydrocarbyl groups, such as alkyl or alkenyl groups, preferably alkyl groups), substituted or unsubstituted C3-6 alicyclic hydrocarbyl groups, substituted or unsubstituted C6-10 aryl groups, and substituted or unsubstituted C7-16 aralkyl groups, or the R1 and R2 groups, together with the attached N atom, form a 5-6 membered saturated or unsaturated heterocyclic ring; the R3 group is selected from hydrogen (H), C1-12 linear or branched aliphatic hydrocarbyl groups (e.g., C1-8 linear or branched aliphatic hydrocarbyl groups, C1-6 linear or branched aliphatic hydrocarbyl groups, C1-4 linear or branched aliphatic hydrocarbyl groups, such as alkyl or alkenyl groups, preferably alkyl groups), substituted or unsubstituted C3-6 alicyclic hydrocarbyl groups, substituted or unsubstituted C6-10 aryl groups, and substituted or unsubstituted C7-16 aralkyl groups; and Hal represents chlorine, bromine or iodine.
In a further 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 attached N atom, form a tetrahydropyrrolyl 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.
In a still further preferred embodiment, the R1 and R2 groups are the same and are 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 attached N atom, form a tetrahydropyrrolyl 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; and Hal represents chlorine, bromine or iodine.
In a particularly preferred embodiment, the R1 and R2 groups are the same and are 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 attached 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.
In a preferred embodiment of the method according to the present application, the cyclic lysine monomer is provided in step 1) by protecting the primary amine group of the aminocaprolactam represented by formula (V) with a protecting group,
For example, the protecting groups can be the R1 and R2 groups as defined hereinabove above, and will not be described in detail herein.
In a further preferred embodiment, said step 1) is carried out by reacting said aminocaprolactam with a corresponding aldehyde and/or halogenated hydrocarbon having the R1 and/or R2 group, preferably by reacting said 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.
In certain still further preferred embodiments, the aminocaprolactam used in step 1) can be prepared from L-lysine hydrochloride by: i) carrying out methyl esterification on L-lysine hydrochloride to obtain a methyl esterified L-lysine, preferably taking methanol as a solvent and a methyl esterification reagent and concentrated sulfuric acid as a catalyst, and reacting under reflux conditions for 8-10 h to obtain the methyl esterified L-lysine; and ii) reacting the methyl esterified L-lysine with a basic solution in a methanol solvent to obtain aminocaprolactam, preferably reacting at room temperature for 10 to 12 h, and then concentrating and recrystallizing to obtain aminocaprolactam.
In a preferred embodiment, the molar ratio of cyclic lysine monomer to caprolactam monomer used in step 2) is from 3:97 to 25:75, more preferably from 4:96 to 20:80.
In a preferred embodiment, the step 2) is carried out in the presence of a catalyst, preferably the catalyst is 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. Further 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]undec-7-ene), TBD (1,5,7-triazabicyclo[4,4,0]dec-5-ene), sodium, potassium, or combinations thereof.
In a further preferred embodiment, the molar ratio of the total amount of cyclic lysine monomer and caprolactam monomer to the catalyst used in the step 2) is: (10-50):1, preferably (10-30):1.
In a further preferred embodiment, the ring-opening polymerization of step 2) is carried out in the presence of an activator having the following structure:
Still more preferably, the molar ratio of the total amount of the cyclic lysine monomer and caprolactam monomer to the activator used in step 2) is: (10-50):1, preferably (10-30):1.
In a preferred embodiment, the reaction conditions of step 2) include: a polymerization temperature of 140-180° C., and a reaction time of 3-6 h.
In a preferred embodiment, the halide 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, more preferably selected from hydrochloric acid, ethyl bromide, cyclohexyl bromide, benzyl bromide, or a combination thereof.
In a preferred embodiment, the reaction of 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.
Further preferably, the reaction conditions of step 3) include: a reaction temperature of 40-70° C., and a reaction time of 10-12 h.
In some preferred embodiments, the step 3) further comprises settling the reaction product of the copolymer and the halide in ethyl acetate, centrifuging, and drying to obtain the antibacterial nylon 6 material.
In a fourth aspect, the present application provides an article comprising the antibacterial nylon 6 material according to the present application, the nylon 6 composition according to the present application, or an antibacterial nylon 6 material obtained by the method according to the present application.
In some preferred embodiments, at least a part of the article is made from the antibacterial nylon 6 material.
In a preferred embodiment, the article is selected from the group consisting of textiles, daily necessities, building materials, packaging materials and panels, such as masks, protective clothing, towels, carpets, cling films, bicycle handles, and the like.
According to the present application, the article or a part thereof can be manufactured using the antibacterial nylon 6 material according to the present application or the nylon 6 composition according to the present application in a conventional manner, for example, by injection molding, blow molding, extrusion, calendering, and the like, and the operations and conditions thereof are well known to those skilled in the art and can be selected according to actual needs, and will not be described in detail herein.
The present application will be further illustrated with reference to the following examples, but the present application is not limited thereto.
Unless otherwise specified, the reagents used in the following examples are commercially available products, and have a purity of analytical grade.
In the following examples and comparative examples, nuclear magnetic resonance spectrums of the aminocaprolactam intermediate and nylon 6 material obtained are measured by a Burker AV-300 liquid superconducting nuclear magnetic resonance spectrometer, using a mixed solvent of deuterated dimethyl sulfoxide and trifluoroacetic acid at room temperature; the weight average molecular weight was measured at room temperature using a Waters515 Gel Permeation Chromatograph (Waters Corporation, USA), using hexafluoroisopropanol containing 0.02 mol/L sodium trifluoroacetate as an eluent.
In the following examples and comparative examples, the melting point of the nylon 6 material obtained was measured by Q2000 DSC7 Differential Scanning Calorimeter (DSC) of TA Instruments, USA, as follows: 5 mg of sample was weighed, placed in a sample tank of the DSC7 differential scanning calorimeter, heated from 25° C. to 250° C. under a nitrogen flow of 50 ml/min at a heating rate of 10° C./min, and then the melting point of the sample was detected.
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 mechanically stirred. After the dropping of the concentrated sulfuric acid, the solution was in a clear state and was transferred to a 2 L single-necked flask for reaction under reflux conditions for 8 hours to obtain a methyl esterified lysine.
The methyl esterified lysine was transferred into a 50 L reaction kettle, 28.5 L of methanol was added thereto, further mechanically stirred, a sodium hydroxide solution in methanol (a solution of 480 g sodium hydroxide in 2 L methanol) was added dropwise, and then reacted at room temperature for 10-12 h. The resultant was subjected to concentration and recrystallization to obtain an aminocaprolactam with a yield of 80%, which had a purity of 90% according to nuclear magnetic resonance hydrogen spectrum analysis.
30 g (234 mmol) of the aminocaprolactam obtained in step (1) were weighed and dissolved into 500 ml of methanol, 42 g (514 mmol) of formaldehyde solution (37% by mass) and 3 g of 10% palladium on carbon were added and reacted for 24 hours under a hydrogen atmosphere. The resultant was subjected to suction filtration, concentration and recrystallization to obtain a dimethyl-protected aminocaprolactam with a yield of 92%, which had a purity of 98% according to nuclear magnetic resonance hydrogen spectrum analysis.
0.5 g (3.2 mmol) of the dimethyl-protected aminocaprolactam obtained in step (2), 9.5 g (84 mmol) of caprolactam, 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 min and 70 mg (1.7 mmol) sodium hydride was then added for reaction under the protection of nitrogen in a 180° C. oil bath for 6 h.
100 ml of trifluoroethanol was added for dissolution, and a part of the resulting material was taken out for nuclear magnetic resonance characterization. The results are shown in
The mole percentage of the ε-lysine derived copolymerization units in the resulting copolymer was about 4%, which was calculated as the ratio of the integrated area of the peak at the f-position to that of the peak at the h-position in
2 g (12.8 mmol) of the dimethyl-protected aminocaprolactam obtained in step (2) of Example 1, 18 g (0.16 mol) of caprolactam, 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 min, and 0.14 g (3.5 mmol) of sodium hydride was then added for reaction under the protection of nitrogen in a 180° C. oil bath for 6 h.
180 ml of trifluoroethanol was added for dissolution, and a part of the resulting material was taken out for nuclear magnetic resonance characterization. The results are as follows: 1H NMR (DMSO-d6, 300 MHz) δ 3.70-3.61, 3.13-3.02, 2.76-2.72, 2.51-2.50, 1.81-1.18.
To the remaining solution, 4.2 g (38.4 mmol) of bromoethane was added for reaction in a 40° C. oil bath for 12 h, the reaction solution was settled in ethyl acetate, centrifuged and dried to obtain a cationic poly(ε-lysine)-derived antibacterial nylon 6 material having the general formula (I) with a yield of 95%, which had a weight average molecular weight of 10000, and a melting point of 199.5° C., and its DSC melting point test diagram is shown in
3 g (19.2 mmol) of the dimethyl-protected aminocaprolactam obtained in step (2) of Example 1, 17 g (0.15 mol) of caprolactam, 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 min, and 0.14 g (3.4 mmol) of sodium hydride was then added for reaction under the protection of nitrogen in a 180° C. oil bath for 6 h.
150 ml of trifluoroethanol was added for dissolution, and a part of the resulting material was taken out for nuclear magnetic resonance characterization. The results are as follows: 1H NMR (DMSO-d6, 300 MHz) δ 3.70-3.61, 3.13-3.02, 2.76-2.72, 2.51-2.50, 1.81-1.18.
To the remaining solution, 6.3 g (57.6 mmol) of ethyl bromide was added for reaction in a 40° C. oil bath for 12 h, the reaction solution was settled in ethyl acetate, centrifuged and dried to obtain a cationic poly(ε-lysine)-derived antibacterial nylon 6 material having the general formula (I) with a yield of 90%, which had a weight average molecular weight of 12000, and a melting point of 185.7° C., and its DSC melting point test diagram is shown in
4 g (25.6 mmol) of the dimethyl-protected aminocaprolactam obtained in step (2) of Example 1, 16 g (0.14 mol) of caprolactam, 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 min, and 0.13 g (3.3 mmol) of sodium hydride was then added for reaction under the protection of nitrogen in a 180° C. oil bath for 6 h.
180 ml of trifluoroethanol was added for dissolution, and a part of the resulting material was taken out for nuclear magnetic resonance characterization. The results are as follows: 1H NMR (DMSO-d6, 300 MHz) δ 3.70-3.61, 3.13-3.02, 2.76-2.72, 2.51-2.50, 1.81-1.18.
To the remaining solution, 8.4 g (77.8 mmol) of bromoethane was added for reaction in a 40° C. oil bath for 12 hours, and the reaction solution was settled in ethyl acetate, centrifuged, and dried to obtain a cationic poly(ε-lysine)-derived antibacterial nylon-6 material having the general formula (I) with a yield of 89%, which had a weight average molecular weight of 15000, and a melting point of 176.3° C. and its DSC melting point test diagram is shown in
5 g (32 mmol) of the dimethyl-protected aminocaprolactam obtained in step (2) of Example 1, 15 g (0.13 mol) of caprolactam, 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 min, and 0.13 g (3.3 mmol) of sodium hydride was then added for reaction under the protection of nitrogen in a 180° C. oil bath for 6 h.
160 ml of trifluoroethanol was added for dissolution, and a part of the resulting material was taken out for nuclear magnetic resonance characterization. The results are as follows: 1H NMR (DMSO-d6, 300 MHz) δ 3.70-3.61, 3.13-3.02, 2.76-2.72, 2.51-2.50, 1.81-1.18.
10.5 g (96 mmol) of bromoethane was added to the remaining solution for reaction in a 40° C. oil bath for 12 h, the reaction solution was settled in ethyl acetate, centrifuged and dried to obtain a cationic poly(ε-lysine)-derived antibacterial nylon 6 material having the general formula (I) with a yield of 85%, which had a weight average molecular weight of 18000, and a melting point of 167.5° C., and its DSC melting point test diagram is shown in
0.5 g (3.2 mmol) of the dimethyl-protected aminocaprolactam obtained in step (2) of Example 1, 9.5 g (84 mmol) of caprolactam, 0.48 g (1.7 mmol) of N-trifluoromethylbenzoyl caprolactam activator were weighed into a 25 ml round bottom flask, purged at 40° C. for 30 min and 70 mg (1.7 mmol) of sodium hydride was then added for reaction under the protection of nitrogen in a 180° C. oil bath for 6 h.
100 ml of trifluoroethanol was added for dissolution, and a part of the resulting material was taken out for nuclear magnetic resonance characterization. The results are as follows: 1H NMR (DMSO-d6, 300 MHz) δ 3.70-3.61, 3.13-3.02, 2.76-2.72, 2.51-2.50, 1.81-1.18.
To the remaining solution, 100 ml of hydrochloric acid solution (6M) was added for reaction at room temperature for 12 hours. The reaction solution was settled in ethyl acetate, centrifuged and dried to obtain a cationic poly(ε-lysine)-derived antibacterial nylon 6 material having the general formula (I) with a yield of 85%, which had a weight average molecular weight of 6000, and a melting point of 212.4° C. The mole percentage of the ε-lysine derived copolymerization units in the antibacterial nylon 6 material was about 4%.
0.5 g (3.2 mmol) of dimethyl-protected aminocaprolactam obtained in step (2) of Example 1, 9.5 g (84 mmol) of caprolactam, 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 min, and 70 mg (1.7 mmol) of sodium hydride was then added for reaction under the protection of nitrogen in a 180° C. oil bath for 6 h.
100 ml of trifluoroethanol was added for dissolution, and a part of the resulting material was taken out for nuclear magnetic resonance characterization. The results are as follows: 1H NMR (DMSO-d6, 300 MHz) δ 3.70-3.61, 3.13-3.02, 2.76-2.72, 2.51-2.50, 1.81-1.18.
To the remaining solution, 15.6 g (96 mmol) of bromocyclohexane were added for reaction in a 40° C. oil bath for 12 h. The reaction solution was settled in ethyl acetate, centrifuged and dried to obtain a cationic poly(ε-lysine)-derived antibacterial nylon 6 material having the general formula (I) with a yield of 95%, which had a weight average molecular weight of 20000, and a melting point of 208.6° C. The mole percentage of the ε-lysine derived copolymerization units in the antibacterial nylon 6 material was about 4%.
0.5 g (3.2 mmol) of dimethyl-protected aminocaprolactam obtained in step (2) of Example 1, 9.5 g (84 mmol) of caprolactam, 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 min, and 70 mg (1.7 mmol) of sodium hydride was then added for reaction under the protection of nitrogen in a 180° C. oil bath for 6 h.
100 ml of trifluoroethanol was added for dissolution, and a part of the resulting material was taken out for nuclear magnetic resonance characterization. The results are as follows: 1H NMR (DMSO-d6, 300 MHz) δ 3.70-3.61, 3.13-3.02, 2.76-2.72, 2.51-2.50, 1.81-1.18.
To the remaining solution, 16.4 g (96 mmol) of benzyl bromide were added for reaction in a 40° C. oil bath for 12 h. The reaction solution was settled in ethyl acetate, centrifuged and dried to obtain a cationic poly(ε-lysine)-derived antibacterial nylon 6 material having the general formula (I) with a yield of 98%, which had a weight average molecular weight of 50000, and a melting point of 206.3° C. The mole percentage of the ε-lysine derived copolymerization units in the antibacterial nylon 6 material was about 4%.
30 g (234 mmol) of aminocaprolactam were weighed and dissolved into 500 ml of methanol, 56.6 g (514 mmol) of an acetaldehyde solution (40% by mass) and 3 g of 10% palladium on carbon were added, and the mixture was reacted under hydrogen for 24 hours. The resultant was subjected to suction filtration, concentration and recrystallization to obtain a diethyl-protected aminocaprolactam with a yield of 88%, which had a purity of 95% according to nuclear magnetic resonance hydrogen spectrum analysis.
0.59 g (3.2 mmol) of the diethyl-protected aminocaprolactam obtained in step (1), 9.5 g (84 mmol) of caprolactam, 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 min, and 70 mg (1.7 mmol) of sodium hydride was then added for reaction under the protection of nitrogen in a 180° C. oil bath for 6 h.
100 ml of trifluoroethanol was added for dissolution, and a part of the resulting material was taken out for nuclear magnetic resonance characterization. The results are as follows: 1H NMR (DMSO-d6, 300 MHz) δ 3.75-3.63, 3.34-3.12, 2.78-2.62, 2.50-2.40, 1.61-1.28.
To the remaining solution, 1 g (19.2 mmol) of ethyl bromide was added for reaction in a 40° C. oil bath for 12 h. The reaction solution was settled in ethyl acetate, centrifuged and dried to obtain a cationic poly(ε-lysine)-derived antibacterial nylon 6 material having the general formula (I) with a yield of 82%, which had a weight average molecular weight of 13000, and a melting point of 208.2° C. The mole percentage of the ε-lysine derived copolymerization units in the antibacterial nylon 6 material was about 4%.
30 g (234 mmol) of aminocaprolactam were weighed and dissolved into 500 ml of methanol, 29.9 g (514 mmol) of propionaldehyde and 3 g of 10% palladium on carbon were added and the mixture was reacted under hydrogen for 24 hours. The resultant was subjected to suction filtration, concentration and recrystallization to obtain a dipropyl-protected aminocaprolactam with a yield of 89%, which had a purity of 97% according to the nuclear magnetic resonance hydrogen spectrum analysis.
0.68 g (3.2 mmol) of the dipropyl-protected aminocaprolactam obtained in step (1), 9.5 g (84 mmol) of caprolactam, 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 min, and 70 mg (1.7 mmol) of sodium hydride was then added for reaction under the protection of nitrogen in a 180° C. oil bath for 6 h.
100 ml of trifluoroethanol was added for dissolution, and a part of the resulting material was taken out for nuclear magnetic resonance characterization. The results are as follows: 1H NMR (DMSO-d6, 300 MHz) δ 3.85-3.53, 3.30-3.10, 2.88-2.52, 2.40-2.28, 1.71-1.18.
To the remaining solution, 1 g (19.2 mmol) of ethyl bromide was added for reaction in a 40° C. oil bath for 12 h. The reaction solution was settled in ethyl acetate, centrifuged and dried to obtain a cationic poly(ε-lysine)-derived antibacterial nylon 6 material having the general formula (I) with a yield of 93%, which had a weight average molecular weight of 18000, and a melting point of 201.7° C. The mole percentage of the ε-lysine derived copolymerization units in the antibacterial nylon 6 material was about 4%.
30 g (234 mmol) of aminocaprolactam were dissolved in 500 ml of methanol, and 37.1 g (514 mmol) of butyraldehyde and 3 g of 10% palladium on carbon were added and reacted under hydrogen for 24 hours. The resultant was subjected to suction filtration, concentration and recrystallization to obtain the dibutyl-protected aminocaprolactam with a yield of 86%, which had a purity of 96% according to nuclear magnetic resonance hydrogen spectrum analysis.
0.77 g (3.2 mmol) of dibutyl-protected aminocaprolactam obtained in step (1), 9.5 g (84 mmol) of caprolactam, 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 min, and 70 mg (1.7 mmol) of sodium hydride was then added for reaction under the protection of nitrogen in a 180° C. oil bath for 6 h.
100 ml of trifluoroethanol was added for dissolution, and a part of the resulting material was taken out for nuclear magnetic resonance characterization. The results are as follows: 1H NMR (DMSO-d6, 300 MHz) δ 3.95-3.73, 3.30-3.10, 2.58-2.42, 2.30-2.10, 1.60-1.08.
To the remaining solution, 1 g (19.2 mmol) of ethyl bromide was added for reaction in a 40° C. oil bath for 12 h. The reaction solution was settled in ethyl acetate, centrifuged and dried to obtain a cationic poly(ε-lysine)-derived antibacterial nylon 6 material having the general formula (I) with a yield of 86%, which had a weight average molecular weight of 25000, and a melting point of 201.1° C. The mole percentage of the ε-lysine derived copolymerization units in the antibacterial nylon 6 material was about 4%.
30 g (234 mmol) of aminocaprolactam were weighed into 500 ml of acetonitrile, 56 ml (491 mmol) of benzyl chloride and 46.8 g (351 mmol) of potassium carbonate were added for reaction under stirring at 80° C. for 6 h. The resultant was washed with 1M HCl, extracted with dichloromethane, dried with anhydrous sodium sulfate, and then subjected to suction filtration, concentration and recrystallization to obtain dibenzyl-protected aminocaprolactam with a yield of 85%, which had a purity of 95% according to nuclear magnetic resonance hydrogen spectrum analysis.
0.99 g (3.2 mmol) of the dibenzyl-protected aminocaprolactam obtained in step (1), 9.5 g (84 mmol) of caprolactam, 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 min, and 70 mg (1.7 mmol) of sodium hydride was then added for reaction under the protection of nitrogen in a 180° C. oil bath for 6 h.
100 ml of trifluoroethanol was added for dissolution, and a part of the resulting material was taken out for nuclear magnetic resonance characterization. The results are as follows: 1H NMR (DMSO-d6, 300 MHz) 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.
To the remaining solution, 1 g (19.2 mmol) of ethyl bromide was added for reaction in a 40° C. oil bath for 12 h. The reaction solution was settled in ethyl acetate, centrifuged and dried to obtain a cationic poly(ε-lysine)-derived antibacterial nylon 6 material having the general formula (I) with a yield of 93%, which had a weight average molecular weight of 50000, and a melting point of 196.5° C. The mole percentage of the ε-lysine derived copolymerization units in the antibacterial nylon 6 material was about 4%.
(1) Preparation of N,N-hexahydropyridyl aminocaprolactam
30 g (234 mmol) of aminocaprolactam were weighed into 500 ml of acetonitrile, 80.7 g (351 mmol) of 1,5-dibromopentane and 46.8 g (351 mmol) of potassium carbonate were added for reaction under stirring at 80° C. for 6 h. The resultant was washed with 1M HCl, extracted with dichloromethane, dried with anhydrous sodium sulfate, and then subjected to suction filtration, concentration and recrystallization to obtain N,N-hexahydropyridyl aminocaprolactam with a yield of 75%, which had a purity of 90% according to nuclear magnetic resonance hydrogen spectrum analysis.
0.63 g (3.2 mmol) N,N-hexahydropyridyl aminocaprolactam, 9.5 g (84 mmol) caprolactam, 0.37 g (1.7 mmol) N-benzoylcaprolactam activator were weighed into a 25 ml round bottom flask, purged at 40° C. for 30 min, and 70 mg (1.7 mmol) of sodium hydride was then added for reaction under the protection of nitrogen in a 180° C. oil bath for 6 h.
100 ml of trifluoroethanol was added for dissolution, and a part of the resulting material was taken out for nuclear magnetic resonance characterization. The results are as follows: 1H NMR (DMSO-d6, 300 MHz) δ 5.53-5.31, 3.70-3.53, 3.32-3.12, 2.55-2.40, 1.61-1.18.
To the remaining solution, 1 g (19.2 mmol) of ethyl bromide was added for reaction in a 40° C. oil bath for 12 h. The reaction solution was settled in ethyl acetate, centrifuged and dried to obtain a cationic poly(ε-lysine)-derived antibacterial nylon 6 material having the general formula (I) with a yield of 88%, which had a weight average molecular weight of 20000, and a melting point of 193.8° C. The mole percentage of the ε-lysine derived copolymerization units in the antibacterial nylon 6 material was about 4%.
30 g (234 mmol) of aminocaprolactam were weighed into 500 ml of acetonitrile, 59.4 g (491 mmol) of allyl bromide and 46.8 g (351 mmol) of potassium carbonate were added for reaction under stirring at 80° C. for 6 h. The resultant was washed with 1M HCl, extracted with dichloromethane, dried with anhydrous sodium sulfate, and then subjected to suction filtration, concentration and recrystallization to obtain diallyl-protected aminocaprolactam with a yield of 78%, which had a purity of 97% according to nuclear magnetic resonance hydrogen spectrum analysis.
0.67 g (3.2 mmol) of diallyl-protected aminocaprolactam, 9.5 g (84 mmol) of caprolactam, 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 min, and 70 mg (1.7 mmol) of sodium hydride was then added for reaction under the protection of nitrogen in a 180° C. oil bath for 6 h.
100 ml of trifluoroethanol was added for dissolution, and a part of the resulting material was taken out for nuclear magnetic resonance characterization. The results are as follows: 1H NMR (DMSO-d6, 300 MHz) δ 4.53-4.23, 3.95-3.73, 3.44-3.22, 2.53-2.40, 1.81-1.38.
To the remaining solution, 1 g (19.2 mmol) of ethyl bromide was added for reaction in a 40° C. oil bath for 12 h. The reaction solution was settled in ethyl acetate, centrifuged and dried to obtain a cationic poly(ε-lysine)-derived antibacterial nylon 6 material having the general formula (I) with a yield of 92%, which had a weight average molecular weight of 18000, and a melting point of 200.3° C. The mole percentage of the ε-lysine derived copolymerization units in the antibacterial nylon 6 material was about 4%.
30 g (234 mmol) of aminocaprolactam were weighed into 500 ml of acetonitrile, 122.4 g (491 mmol) of dodecylbromide and 46.8 g (351 mmol) of potassium carbonate were added for reaction under stirring at 80° C. for 6 h. The resultant was washed with 1M HCl, extracted with dichloromethane, dried with anhydrous sodium sulfate, and then subjected to suction filtration, concentration and recrystallization to obtain didodecyl-protected aminocaprolactam with a yield of 70%, which had a purity of 90% according to nuclear magnetic resonance hydrogen spectrum analysis.
1.49 g (3.2 mmol) of the didodecyl-protected aminocaprolactam obtained in step (1), 9.5 g (84 mmol) of caprolactam, 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 min, and 70 mg (1.7 mmol) of sodium hydride was then added for reaction under the protection of nitrogen in a 180° C. oil bath for 6 h.
100 ml of trifluoroethanol was added for dissolution, and a part of the resulting material was taken out for nuclear magnetic resonance characterization. The results are as follows: 1H NMR (DMSO-d6, 300 MHz) δ 3.65-3.43, 3.24-3.02, 2.758-2.32, 2.20-2.06, 1.51-1.18.
To the remaining solution, 1 g (19.2 mmol) of ethyl bromide was added for reaction in a 40° C. oil bath for 12 h. The reaction solution was settled in ethyl acetate, centrifuged and dried to obtain a cationic poly(ε-lysine)-derived antibacterial nylon 6 material having the general formula (I) with a yield of 89%, which had a weight average molecular weight of 80000, and a melting point of 185.6° C. The mole percentage of the ε-lysine derived copolymerization units in the antibacterial nylon 6 material was about 4%.
9.5 g (84 mmol) caprolactam and 0.37 g (1.7 mmol) N-benzoyl caprolactam activator were weighed into a 25 ml round bottom flask, purged at 40° C. for 30 min, and 70 mg (1.7 mmol) of sodium hydride was then added for reaction under the protection of nitrogen in a 180° C. oil bath for 6 h, to obtain a conventional nylon 6 material, which had a melting point of 222.3° C.
0.25 g (1.6 mmol) of dimethyl-protected aminocaprolactam obtained in step (2) of Example 1, 36.2 g (320 mmol) of caprolactam, 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 min, and 260 mg (6.5 mmol) of sodium hydride was then added for reaction under the protection of nitrogen in a 180° C. oil bath for 6 h.
100 ml of trifluoroethanol was added for dissolution, and a part of the resulting material was taken out for nuclear magnetic resonance characterization. The results are as follows: 1H NMR (DMSO-d6, 300 MHz) δ 3.70-3.61, 3.13-3.02, 2.76-2.72, 2.51-2.50, 1.81-1.18.
To the remaining solution, 1 g (19.2 mmol) of ethyl bromide was added for reaction in a 40° C. oil bath for 12 h. The reaction solution was settled in ethyl acetate, centrifuged and dried to obtain a cationic poly(ε-lysine)-derived modified nylon 6 material with a yield of 98%, which had a weight average molecular weight of 50000, and a melting point of 219.5° C. The mole percentage of the ε-lysine derived copolymerization units in the modified nylon 6 material was about 0.5%.
15.6 g (100 mmol) of the dimethyl-protected aminocaprolactam obtained in step (2) of Example 1, 11.3 g (100 mmol) of caprolactam, 0.87 g (4 mmol) of N-benzoylcaprolactam activator were weighed into a 25 ml round bottom flask, purged at 40° C. for 30 min, and 160 mg (4 mmol) of sodium hydride was then added for reaction under the protection of nitrogen in a 180° C. oil bath for 6 h.
100 ml of trifluoroethanol was added for dissolution, and a part of the resulting material was taken out for nuclear magnetic resonance characterization. The results are as follows: 1H NMR (DMSO-d6, 300 MHz) δ 3.70-3.61, 3.13-3.02, 2.76-2.72, 2.51-2.50, 1.81-1.18.
To the remaining solution, 65.3 g (600 mmol) of ethyl bromide were added and reacted in a 40° C. oil bath for 12 h. The reaction solution was settled in ethyl acetate, centrifuged, and dried to obtain a cationic poly(ε-lysine)-derived modified nylon 6 material with a yield of 60%, which had a weight-average molecular weight of 13500, and had no measured melting point as being a amorphous material. The mole percentage of the ε-lysine derived copolymerization units in the modified nylon 6 material was about 40%.
The antibacterial effect of the materials was tested according to the Chinese National Standard GB/T 31402-2015, with the time and temperature for culturing being adjusted according to the actual situation, as follows: the antibacterial nylon 6 materials obtained in Examples 1-15 and the nylon 6 materials obtained in Comparative Examples 1-3 were respectively pressed into square sheets of 0.75 cm×0.75 cm, sterilized by irradiation under an ultraviolet lamp for 30 min, then a pre-made bacterial solution was dropped on the sheets, and the sheets were covered with a PE film, and incubated at 37° C. for 6 h. After thant, the bacterial solution was subjected to ultrasonic treatment for 3 min, diluted by 100 times, and cultured on solid nutrient medium at 37° C. for 20 h. The conventional nylon 6 material obtained in Comparative Example 1 was used as a control. The bacteria used for the test were Staphylococcus aureus (S. aureus) ATCC6538 and Escherichia coli (E. coli) ATCC25922. The test results are shown in Table 2.
The antibacterial rate was calculated using the following equation:
The antibacterial nylon 6 materials obtained in Examples 1 to 15 and the nylon 6 materials obtained in Comparative Examples 1 to 3 were injection-molded into bars of 40 mm×4 mm×2 mm, respectively, and tested for tensile properties. The test results are shown in Table 2.
S. aureus (%)
E. coli (%)
As shown by the data of Table 2, the antibacterial nylon 6 material of the present application has a significant antibacterial effect, and mechanical properties substantially equivalent to those of conventional nylon 6 material. In contrast, the nylon 6 material of Comparative Example 2 has insufficient antibacterial capability, and the nylon 6 material of Comparative Example 3 has inferior mechanical properties.
The present application is illustrated in detail hereinabove with reference to preferred embodiments, but is not intended to be limited to those embodiments. Various modifications may be made following the inventive concept of the present application, and these modifications shall be within the scope of the present application.
It should be noted that the various technical features described in the above embodiments may be combined in any suitable manner without contradiction, and in order to avoid unnecessary repetition, various possible combinations are not described in the present application, but such combinations shall also be within the scope of the present application.
In addition, the various embodiments of the present application can be arbitrarily combined as long as the combination does not depart from the spirit of the present application, and such combined embodiments should be considered as the disclosure of the present application.
| Number | Date | Country | Kind |
|---|---|---|---|
| 202110960422.3 | Aug 2021 | CN | national |
| Filing Document | Filing Date | Country | Kind |
|---|---|---|---|
| PCT/CN2022/113177 | 8/18/2022 | WO |
