Triazine antibacterial agents, methods of making and use thereof

Abstract

The application discloses a triazine antibacterial agent, a preparation method and application thereof. The structure of the antibacterial agent is shown in the following formula (I): wherein R1 and R2 are independently selected from H, substituted or unsubstituted alkyl or halogen. The triazine antibacterial agent provided by the application not only has excellent antibacterial performance, but also has excellent high-temperature resistance and thermal stability, and has good compatibility with polyethylene terephthalate (PET), can be uniformly dispersed in the PET, and is resistant to precipitation and migration, can endow the antibacterial product with long-acting and broad-spectrum antibacterial performance, and can especially significantly improve the mechanical properties such as tensile strength and impact strength of the antibacterial PET product.

Description

Technical Field

[0001] This application relates to an antibacterial agent, and more particularly to a triazine antibacterial agent, its preparation method, and its application. Background Technology

[0002] Antibacterial agents are chemical substances that can keep the growth or reproduction of certain microorganisms (bacteria, fungi, yeasts, algae, and viruses, etc.) below a necessary level for a certain period of time. They have been widely used in many fields such as industry and agriculture.

[0003] Currently, commonly used antibacterial agents mainly include inorganic, organic, and biological antibacterial agents. Typical inorganic antibacterial agents include metals such as silver, copper, and zinc. Typical organic antibacterial agents mainly include vanillin or ethyl vanillin compounds. Typical natural antibacterial agents are mainly extracted from natural plants, such as chitin, mustard, castor oil, and wasabi. However, for plastic products and coated products, while existing inorganic and organic antibacterial agents can impart certain antibacterial properties, they often lead to other problems. For example, inorganic antibacterial agents, represented by silver ion antibacterial agents or nano-silver antibacterial agents, have poor compatibility with the matrix resin in plastic products and the film-forming polymers in coatings, and are prone to agglomeration, which may reduce the mechanical properties of these products and prevent the achievement of uniform antibacterial effects. While organic antibacterial agents, represented by vanillin, have better compatibility with matrix resins and film-forming polymers and are easier to disperse uniformly, they are highly toxic, have poor thermal stability, and are easily decomposed, thus limiting their widespread application in plastic products. Summary of the Invention

[0004] The main objective of this application is to provide a triazine antibacterial agent, its preparation method, and its application, in order to overcome the shortcomings of the prior art.

[0005] To achieve the aforementioned objectives, the technical solution adopted in this application includes:

[0006] One aspect of this application provides a triazine antibacterial agent comprising the compound shown in formula (I):

[0007]

[0008] R1 and R2 are independently selected from H, substituted or unsubstituted alkyl groups, or halogens.

[0009] Another aspect of this application provides a method for preparing a triazine antibacterial agent, comprising: reacting melamine with a compound of formula (II) at 100°C to 140°C in the presence of a solvent to obtain a triazine antibacterial agent having the structure shown in formula (I).

[0010]

[0011] R1 and R2 are independently selected from H, substituted or unsubstituted alkyl groups, or halogens.

[0012] Another aspect of this application provides the use of the triazine antimicrobial agent in the preparation of antimicrobial products. The antimicrobial products include, but are not limited to, antimicrobial PET materials or articles thereof, antimicrobial coatings or antimicrobial coatings formed therefrom.

[0013] Compared to existing technologies, the advantages of this application include:

[0014] (1) The provided triazine antibacterial agent not only has excellent antibacterial properties, but also excellent high temperature resistance and thermal stability. It has good compatibility with polyethylene terephthalate (PET), can be uniformly dispersed in PET, and is resistant to precipitation and migration. It can give antibacterial products long-lasting and broad-spectrum antibacterial properties. In particular, it can significantly improve the tensile strength, impact strength and other mechanical properties of antibacterial PET products.

[0015] (2) The preparation process of the provided triazine antibacterial agent is simple, has a high yield, is safe and environmentally friendly, and has a wide range of raw material sources and low cost. Detailed Implementation

[0016] In view of the shortcomings of existing inorganic and organic antibacterial agents, the technical solution proposed in this application mainly includes: preparing a triazine antibacterial agent by reacting melamine with indole-3-carboxaldehyde or its derivatives, and using it to prepare products with antibacterial functions. The performance of the triazine antibacterial agent and the corresponding antibacterial products can be referred to above and below.

[0017] The technical solution, implementation process, and principles of this application will be further explained below. It should be noted that the following detailed descriptions are exemplary and intended to provide further explanation of this application. Unless otherwise specified, all technical and scientific terms used in this specification have the same meaning as commonly understood by one of ordinary skill in the art to which this application pertains.

[0018] Some embodiments of this application provide a triazine antibacterial agent comprising the compound shown in formula (I):

[0019]

[0020] R1 and R2 are independently selected from H, substituted or unsubstituted alkyl groups, or halogens. The halogens include fluorine, chlorine, or bromine, etc.

[0021] In one embodiment, both R1 and R2 are selected as H.

[0022] In one embodiment, R1 and R2 are independently selected from H, C1-C3 alkyl groups or halogens.

[0023] In one embodiment, one of R1 and R2 is H, and the others are selected from C1-C3 alkyl or halogen.

[0024] In one embodiment, R1 and R2 are independently selected from H or halogens.

[0025] Some embodiments of this application also provide the use of the compound represented by formula (I) in the preparation of antimicrobial agents.

[0026] Some embodiments of this application also provide a method for preparing a triazine antibacterial agent, comprising: reacting melamine with a compound of formula (II) at 100°C to 140°C in the presence of a solvent, thereby obtaining a triazine antibacterial agent having the structure shown in formula (I).

[0027]

[0028] R1 and R2 are independently selected from H, C1-C3 alkyl groups or halogens, preferably from H, -CH3 or halogens.

[0029] In one embodiment, the molar ratio of melamine to the compound represented by formula (II) is 1:1 to 10.

[0030] In one embodiment, the solvent includes any one or more combinations of DMSO, ethanol, DMF, and deionized water, but is not limited thereto.

[0031] In one embodiment, the reaction time is 6 to 12 hours.

[0032] In one embodiment, the compound represented by formula (II) includes any one or more combinations of indole-3-carboxaldehyde, chloroindole-3-carboxaldehyde, bromoindole-3-carboxaldehyde, 8-methyl-indole-tricarboxaldehyde, 8-ethyl-indole-2-carboxaldehyde, and 8-propyl-indole-2-carboxaldehyde, and is not limited thereto.

[0033] In one embodiment, the preparation method specifically includes: dissolving melamine and the compound shown in formula (II) in the solvent, and refluxing the reaction at 100°C to 140°C for 6 to 12 hours under a protective atmosphere, and then performing post-treatment to obtain the triazine antibacterial agent after the reaction is completed.

[0034] Furthermore, the post-processing includes: after the reaction is completed, adding the obtained reaction solution dropwise to toluene or deionized water for recrystallization, allowing it to stand, filtering it, and drying it in a vacuum oven to obtain the triazine antibacterial agent.

[0035] Furthermore, the protective atmosphere includes an inert atmosphere such as nitrogen or argon, or a mixture thereof.

[0036] Some embodiments of this application also provide the use of the compound represented by formula (I) in the preparation of antimicrobial products, which may include, but are not limited to, antimicrobial PET materials or articles thereof, antimicrobial coatings or coatings formed therefrom.

[0037] Some embodiments of this application provide an antibacterial polyethylene terephthalate material, the raw materials of which include: a matrix resin, an antibacterial agent, an antioxidant, and a lubricant. The matrix resin comprises polyethylene terephthalate, preferably composed of polyethylene terephthalate.

[0038] Furthermore, the antioxidant includes, but is not limited to, any one or more combinations of pentaerythritol tetrakis[β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], triethylene glycol bis[triethylene glycol tert-butyl-4-hydroxy-5-methylphenyl)propionate], N,N′-bis-(3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionyl)hexamethylenediamine and 1,3,5-tris(3,5-di-tert-butyl-4-hydroxybenzyl)isocyanuric acid.

[0039] Furthermore, the lubricant may be selected from lubricants commonly used in the art, such as any one or more combinations of linaloate esters or salts, stearates (such as calcium stearate), fatty amides or polyol esters, and is not limited thereto.

[0040] In one embodiment, the raw materials of the antibacterial polyethylene terephthalate material include the following components calculated by weight: 100 parts of matrix resin, 0.5 to 3 parts of antibacterial agent, 0.1 to 0.3 parts of antioxidant, and 0.2 to 1.0 parts of lubricant.

[0041] Some embodiments of this application also provide a method for preparing an antibacterial polyethylene terephthalate material, which includes: thoroughly mixing a matrix resin, an antibacterial agent, an antioxidant, and a lubricant, then adding the mixture to a twin-screw extruder, and then mixing and extruding the mixture, wherein the twin-screw extrusion processing temperature is 260-280°C.

[0042] Some embodiments of this application also provide an antimicrobial coating formed from the aforementioned antimicrobial paint.

[0043] The triazine antibacterial agents provided in the above embodiments of this application have a broad antibacterial spectrum, strong antibacterial ability, and excellent thermal stability. Furthermore, their main raw materials are biologically derived, making them safe, environmentally friendly, and widely available. They can be compounded with matrix resins such as PET through blending and melt extrusion without easily decomposing due to heat. They also exhibit good compatibility with matrix resins such as PET, effectively ensuring and improving the antibacterial and mechanical properties of antibacterial PET products. Moreover, they are safe, reliable, odorless, and have low harm and pollution levels to human health and the environment. In addition, the preparation processes of the triazine antibacterial agents and antibacterial PET materials provided in the above embodiments of this application have advantages such as simple and easy operation, high yield, safety and environmental friendliness, low cost, and suitability for industrial production.

[0044] The technical solutions of this application are further described in detail below with reference to several preferred embodiments. Obviously, the described embodiments are only some embodiments of this application, and not all embodiments. Based on the embodiments in this application, all other embodiments obtained by those skilled in the art without creative effort are within the scope of protection of this application. Unless otherwise stated, the reagents and raw materials used in the following embodiments are commercially available, and the test methods without specific conditions are generally performed under conventional conditions or according to the conditions recommended by the respective manufacturers. Furthermore, unless otherwise stated, the experimental methods, detection methods, and preparation methods disclosed in this application all adopt conventional techniques in this technical field. These techniques have been well described in existing literature.

[0045] The antibacterial agents used in the following examples are mainly prepared by the following method: melamine and indole-3-carboxaldehyde or their derivatives in molar ratios of 1:1, 1:2, 1:3, 1:8, and 1:10 are dissolved in DMSO, ethanol, deionized water, DMF, or a mixture of several of these solvents, and the mixture is stirred at 100℃, 110℃, 120℃, 130℃, and 140℃ for 6h, 8h, and 12h, respectively. After the reaction is completed, the precipitate obtained by filtration from the reaction system is the target product, the triazine antibacterial agent.

[0046] The indole 3-carboxaldehyde derivatives used are selected from bromoindole 3-carboxaldehyde, chloroindole 3-carboxaldehyde, 8-methyl-indole-tricarboxaldehyde, 8-ethyl-indole-2-carboxaldehyde, 8-propyl-indole-2-carboxaldehyde, etc. By controlling the type of indole 3-carboxaldehyde and its derivatives, the reaction temperature and the reaction time, a series of antibacterial agent products are obtained. The general structural formula of these antibacterial agent products is shown in formula (I).

[0047] More specifically:

[0048] The structural formula of one of the triazine antibacterial agents is as follows:

[0049]

[0050] The NMR characterization information of this antibacterial agent is as follows: 1 ¹H-NMR (300MHz, DMSO, ppm): 11.28 (-NH, indole ring, 3H), 7.07 (-CH, indole ring, 3H), 7.19 (-CH, indole ring, 3H), 7.40 (-CH, indole ring, 3H), 7.63 (-CH, indole ring, 3H), 8.43 (-CH, indole ring, 3H), 8.46 (-CH, 1H), 9.32 (-CH, 2H); 13 C-NMR (100MHz, CDCl3, ppm): 137.1, 137.1, 137.1, 130.7, 130.7, 130.7, 126.3, 126.3, 126.3, 110.4, 110.4, 110.4, 166.2, 166.2, 166.2, 111.1, 111.1, 111.1, 121.8, 121.8, 121.8, 121.7, 121.7, 119.8, 119.8, 119.8, 160.0, 160.0, 160.0. It is defined as antibacterial agent 1 in Tables 1 and 4.

[0051] The NMR characterization information of one of the triazine antibacterial agents (R1 is Cl, R2 is H) is as follows: 1 ¹H-NMR (300MHz, DMSO, ppm): 10.85 (-NH, indole ring, 3H), 6.87 (-CH, indole ring, 3H), 7.22 (-CH, indole ring, 3H), 7.63 (-CH, indole ring, 3H), 8.08 (-CH, indole ring, 3H), 8.46 (-CH, 1H), 9.32 (-CH, 2H); 13 C-NMR (100MHz, CDCl3, ppm): 136.8, 136.8, 136.8, 130.7, 130.7, 130.7, 127.7, 127.7, 119.6, 119.6, 119.6, 166.2, 166.2, 166.2, 119.9, 119.9, 119.9, 119.9, 119.9, 120.6, 120.6, 120.6, 120.6, 160.0, 160.0. It is defined as antibacterial agent 2 in Tables 1 and 4.

[0052]

[0053] The NMR characterization information of one of the triazine antibacterial agents (R2 is Br, R1 is H) is as follows: 1¹H-NMR (300MHz, DMSO, ppm): 11.53 (-NH, indole ring, 3H), 7.64 (-CH, indole ring, 3H), 7.00 (-CH, indole ring, 3H), 7.05 (-CH, indole ring, 3H), 8.47 (-CH, indole ring, 3H), 8.46 (-CH, 1H), 9.32 (-CH, 2H); 13 C-NMR (100MHz, CDCl3, ppm): 112.0, 112.0, 112.0, 135.5, 135.5, 135.5, 126.3, 126.3, 126.3, 110.4, 110.4, 110.4, 166.2, 166.2, 166.2, 111.1, 111.1, 111.1, 121.8, 121.8, 121.8, 121.7, 121.7, 119.8, 119.8, 119.8, 160.0, 160.0, 160.0. It is defined as antibacterial agent 3 in Tables 1 and 4.

[0054]

[0055] The NMR characterization information of one of the triazine antibacterial agents (R1 is methyl, R2 is H) is as follows: 1 ¹H-NMR (300MHz, DMSO, ppm): 10.85 (-NH, indole ring, 3H), 7.11 (-CH, indole ring, 3H), 6.88 (-CH, indole ring, 3H), 8.10 (-CH, indole ring, 3H), 7.63 (-CH, indole ring, 3H), 8.46 (-CH, 1H), 9.32 (-CH, 2H), 2.70 (-CH, 9H); 13 C-NMR (100MHz, CDCl3, ppm): 136.5, 136.5, 136.5, 130.7, 130.7, 130.7, 126.2, 126.2, 126.2, 110.4, 110.4, 110.4, 166.2, 166.2, 166.2, 120.5, 120.5, 120.5, 118.8, 118.8, 118.8, 120.1, 120.1, 120.1, 122.2, 122.2, 122.2, 160.0, 160.0, 160.0, 16.6, 16.6. It is defined as antibacterial agent 4 in Tables 1 and 4.

[0056]

[0057] Antibacterial PET products can be prepared using the various triazine antibacterial agents described in this embodiment. The corresponding preparation method includes: adding PET resin, antibacterial agent, antioxidant, and lubricant to a mixer and mixing for 10-15 minutes; then adding the uniformly mixed material to a twin-screw extruder for compounding and extrusion to obtain antibacterial PET material. The twin-screw extrusion processing temperature is 260-280°C. The proportions of PET resin, antibacterial agent, antioxidant, and lubricant, as well as the types of PET resin, antibacterial agent, antioxidant, and lubricant, and the extrusion temperature, can be adjusted according to actual production needs.

[0058] Furthermore, the applicant prepared a series of antibacterial PET products using the aforementioned triazine antibacterial agent products (hereinafter referred to as "antibacterial agents" in Tables 1 and 2) according to the process conditions shown in Table 1. The performance test results of these antibacterial PET products can be found in Table 1. The antibacterial properties, tensile strength, and impact strength of each product were tested according to the methods specified in GB / T 31402-2015, GB / T1040.1-2018, and GB / T 1043.2-2018, respectively.

[0059] Table 1. Raw material composition and performance test results of various antibacterial PET products in the embodiments of this application.

[0060]

[0061]

[0062] Note: The data shown in columns D and G of Table 1 are the average values ​​after testing multiple samples.

[0063] The performance test results of a series of PET products prepared using the process conditions shown in Table 2 without adding any of the aforementioned triazine antibacterial agents can also be found in Table 2.

[0064] Table 2. Raw material composition and performance test results of various PET products in Comparative Example 1 of this application.

[0065]

[0066]

[0067] Note: The data shown in columns D and G of Table 2 are the average values ​​after testing multiple samples.

[0068] When the aforementioned triazine antibacterial agent is replaced with a commercially available inorganic silver ion antibacterial agent, the performance test results of a series of PET products prepared using the process conditions shown in Table 3 can be found in Table 3.

[0069] Table 3. Raw material composition and performance test results of various PET products in Comparative Example 2 of this application.

[0070]

[0071]

[0072] Note: The data shown in columns D and G of Table 3 are the average values ​​after testing multiple samples.

[0073] If other types of matrix resins are used in combination with the aforementioned triazine antibacterial agents, the performance test results of a series of antibacterial plastic products prepared using the process conditions shown in Table 4 can be found in Table 4.

[0074] Table 4. Raw material composition and performance test results of various antibacterial plastic products in Comparative Example 3 of this application.

[0075]

[0076]

[0077] Note: The data shown in columns D and G of Table 4 are the average values ​​after testing multiple samples.

[0078] In addition, the inventors of this case also conducted experiments with other raw materials, process operations, and process conditions described in this specification, referring to the aforementioned embodiments, and obtained relatively ideal results in all cases.

[0079] Although this application has been described with reference to illustrative embodiments, those skilled in the art will understand that various other changes, omissions, and / or additions may be made without departing from the spirit and scope of this application, and that substantially equivalents may be substituted for the materials described in the embodiments. Furthermore, many modifications may be made without departing from the scope of this application to adapt particular situations or materials to the teachings of this application. Therefore, this application is not intended to be limited to the specific embodiments disclosed for carrying out this application, but rather is intended to include all embodiments falling within the scope of the appended claims.

Claims

1. A triazine antibacterial agent, characterized in that, The antibacterial agent includes the compound represented by formula (I): ； Equation (Ⅰ); R1 and R2 are independently selected from H, C1-C3 alkyl groups or halogens.

2. The triazine antibacterial agent according to claim 1, characterized in that, Both R1 and R2 are selected from H.

3. The triazine antibacterial agent according to claim 1, characterized in that, One of R1 and R2 is H, and the others are selected from C1-C3 alkyl, fluorine, chlorine or bromine.

4. The use of the compound shown in formula (Ⅰ) in the preparation of antibacterial agents, wherein the bacteria are one or a combination of two of Escherichia coli and Staphylococcus aureus; ； Equation (Ⅰ); R1 and R2 are independently selected from H, C1-C3 alkyl groups or halogens.

5. A method for preparing a triazine antibacterial agent, characterized in that, include: In the presence of a solvent, melamine is reacted with the compound shown in formula (II) at 100°C to 140°C to obtain a triazine antibacterial agent having the structure shown in formula (I). ； Equation (Ⅰ); ； Equation (II); R1 and R2 are independently selected from H, C1-C3 alkyl groups or halogens.

6. The preparation method according to claim 5, characterized in that, The molar ratio of melamine to the compound shown in formula (II) is 1:1-10.

7. The preparation method according to claim 5, characterized in that, The solvent includes any one or more combinations of DMSO, ethanol, DMF, and deionized water.

8. The preparation method according to claim 5, characterized in that, The reaction time is 6-12 hours.

9. The preparation method according to claim 5, characterized in that, The compound represented by formula (II) includes any one or more combinations of indole-3-carboxaldehyde, chloroindole-3-carboxaldehyde, bromoindole-3-carboxaldehyde, 8-methyl-indole-tricarboxaldehyde, 8-ethyl-indole-2-carboxaldehyde, and 8-propyl-indole-2-carboxaldehyde.

10. The preparation method according to claim 5, characterized in that, Specifically, it includes: Melamine and the compound shown in formula (II) are dissolved in the solvent and refluxed at 100°C to 140°C for 6 to 12 hours under a protective atmosphere. After the reaction is completed, the triazine antibacterial agent is obtained by post-treatment.

11. An antibacterial polyethylene terephthalate material, wherein the raw materials of the antibacterial polyethylene terephthalate material include a matrix resin, an antioxidant, a lubricant, and an antibacterial agent, wherein the matrix resin includes polyethylene terephthalate, characterized in that, The antibacterial agent includes the compound represented by formula (I): ； Equation (Ⅰ); R1 and R2 are independently selected from H, C1-C3 alkyl groups or halogens.

12. The antibacterial polyethylene terephthalate material according to claim 11, characterized in that, The raw materials of the antibacterial polyethylene terephthalate material include the following components calculated by weight: 100 parts of matrix resin, 0.5-3 parts of antibacterial agent, 0.1-0.3 parts of antioxidant, and 0.2-1.0 parts of lubricant.

13. The antibacterial polyethylene terephthalate material according to claim 11, characterized in that, The antioxidants include any one or more combinations of pentaerythritol tetrakis[β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], triethylene glycol bis[triethylene glycol tert-butyl-4-hydroxy-5-methylphenyl)propionate], N,N'-bis-(3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionyl)hexamethylenediamine and 1,3,5-tris(3,5-di-tert-butyl-4-hydroxybenzyl)isocyanuric acid.

14. The antibacterial polyethylene terephthalate material according to claim 11, characterized in that, The lubricant includes any one or more combinations of lignite esters or salts, stearates, fatty amides, or polyol esters.

15. A method for preparing the antibacterial polyethylene terephthalate material according to any one of claims 11-14, characterized in that... include: The matrix resin, antibacterial agent, antioxidant and lubricant are thoroughly mixed and then fed into a twin-screw extruder, and then compounded and extruded. The twin-screw extrusion processing temperature is 260~280℃.

16. An antibacterial polyethylene terephthalate filament, characterized in that, It is formed from the antibacterial polyethylene terephthalate material according to any one of claims 11-14.

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