Antibacterial nylon composite material and application thereof

Abstract

The application relates to an antibacterial nylon composite material and application thereof, and belongs to the technical field of high polymer materials. In the application, silver lactate and 1,3,5 triazine-2,4,6-trichloride are reacted to obtain silver lactate modified 1,3,5 triazine-2,4,6-trichloride, which is then reacted with dodecylmethyl dihydroxyethyl ammonium chloride to form a polymer with quaternary ammonium salt groups and silver ions in the molecular chain. The polymer has quaternary ammonium salt and silver ion antibacterial groups, and the two groups play a synergistic role to improve the antibacterial performance. The nylon material has good mechanical performance in addition to good antibacterial performance, and meets the use requirements of the current automobile field for polymer materials such as nylon.

Description

Technical Field

[0001] This invention relates to an antibacterial nylon composite material and its application, belonging to the field of polymer materials technology. Background Technology

[0002] Nylon possesses excellent mechanical properties, electrical properties, heat resistance, toughness, oil resistance, wear resistance, self-lubrication, and chemical resistance, and has been widely used in various fields. With the rapid development of automobile miniaturization, greening, and the high performance of electronic and electrical equipment, nylon is widely used as a primary structural material in the automotive industry. Furthermore, in recent years, with the rapid development of new energy vehicles, the application of nylon in components such as new energy batteries, connectors, and charging devices has also increased rapidly. For example, PA66 nylon matrix composites are currently used in automotive engine hoods, intake manifolds, fuel tank liners, distributors, and decorative parts.

[0003] To better suit the needs of the automotive industry, scholars and experts have proposed that the future development trend of automotive nylon materials is to increase their fluidity, heat resistance, resistance to high-pressure scratching, and halogen-free flame retardancy. However, for automotive interior parts, in addition to the strength and toughness of the materials, the antibacterial properties of the materials are also receiving increasing attention as people place greater emphasis on health.

[0004] Therefore, there is an urgent need to develop an antibacterial nylon composite material for automobiles. Summary of the Invention

[0005] The purpose of this invention is to provide an antibacterial nylon composite material to meet the requirements of antibacterial performance of nylon materials for automobiles.

[0006] Another objective of this invention is to provide an antibacterial nylon composite material for use as an automotive nylon material, thereby improving the antibacterial properties of automotive nylon materials.

[0007] This invention provides an antibacterial nylon composite material comprising the following components in parts by weight: 50-70 parts nylon, 26-36 parts glass fiber, 7-12 parts toughening agent, 0.2-0.6 parts silane coupling agent, and 1.5-3 parts antibacterial agent; the antibacterial agent is prepared by a method comprising the following steps: mixing and reacting silver lactate and 1,3,5-triazine-2,4,6-triacyl chloride, and then further mixing and reacting the product of the mixture with dodecylmethyldihydroxyethylammonium chloride to obtain the antibacterial agent; the molar ratio of 1,3,5-triazine-2,4,6-triacyl chloride, silver lactate, and dodecylmethyldihydroxyethylammonium chloride is 1:1:1.

[0008] Preferably, the antibacterial agent is prepared as follows: a 5%–10% (w / w) solution of 1,3,5-triazine-2,4,6-triacyl chloride in dichloromethane is added dropwise to a 0.5%–2% (w / w) solution of silver lactate in dichloromethane. The mixture is then reacted at 25–30°C for 2–4 hours. A dodecylmethyldihydroxyethylammonium chloride solution in dichloromethane is then added to the reacted system. The temperature is raised to 30–35°C, and the mixture is reacted for another 15–30 hours. After removing impurities, the antibacterial agent is obtained.

[0009] Preferably, in the dichloromethane solution of dodecylmethyl dihydroxyethyl ammonium chloride, the mass fraction of dodecylmethyl dihydroxyethyl ammonium chloride is 15% to 25%.

[0010] Preferably, the method for removing impurities is as follows: the system after the mixing reaction is filtered, and then the filtrate is evaporated to dryness.

[0011] Preferably, the nylon is PA6.

[0012] Preferably, the toughening agent is maleic anhydride-grafted polyethylene or EPDM rubber compound.

[0013] Preferably, the silane coupling agent is an epoxy silane coupling agent.

[0014] Preferably, the silane coupling agent is γ-(2,3-epoxypropoxy)propyltrimethoxysilane.

[0015] This invention provides an application of the antibacterial nylon composite material described above as a nylon material for automobiles.

[0016] The beneficial effects of this invention are as follows:

[0017] (1) In this invention, silver lactate is reacted with 1,3,5-triazine-2,4,6-triacyl chloride to obtain silver lactate-modified 1,3,5-triazine-2,4,6-triacyl chloride, which is then reacted with dodecylmethyldihydroxyethylammonium chloride to form a polymer with quaternary ammonium salt groups and silver ions in the molecular chain. This polymer has both quaternary ammonium salt and silver ion antibacterial groups, and the two play a synergistic role to improve antibacterial performance.

[0018] (2) The present invention uses a polymer containing a large number of nitrogen atoms in the molecular chain as the carrier polymer of the antibacterial agent, which can improve the affinity between the antibacterial agent and nylon, improve the intermolecular micro-interaction force between the antibacterial agent and nylon, thereby improving the dispersion uniformity of the antibacterial agent in the polymer nylon and improving the antibacterial performance.

[0019] (3) The present invention uses silane coupling agent to improve the bonding strength between antibacterial agent and other additives and nylon molecular chain, improve the dispersion uniformity and stability of additives, and ensure the long-term stability of nylon material performance.

[0020] (4) In addition to having good antibacterial properties, the nylon material of the present invention also has good mechanical properties, which meets the current requirements of the automotive industry for the use of polymer materials such as nylon, and provides a solid foundation for the long-term development of the automotive industry. Attached Figure Description

[0021] Figure 1 This is a schematic diagram showing the tensile strength of the antibacterial nylon composite materials in various embodiments and comparative examples of the present invention;

[0022] Figure 2 This is a schematic diagram showing the elongation at break of the antibacterial nylon composite materials in various embodiments and comparative examples of the present invention.

[0023] Figure 3 This is a schematic diagram of the notched impact strength of a simply supported beam of antibacterial nylon composite material in various embodiments and comparative examples of the present invention;

[0024] Figure 4 This is a schematic diagram showing the antibacterial rate of the antibacterial nylon composite materials against Escherichia coli and Staphylococcus aureus in various embodiments and comparative examples of the present invention. Detailed Implementation

[0025] The following examples are intended to further illustrate the content of the present invention, rather than to limit the scope of protection of the present invention.

[0026] Example 1

[0027] The antibacterial nylon composite material of this embodiment comprises the following components in parts by weight: 50 parts nylon, 26 parts glass fiber, 8 parts toughening agent, 0.2 parts silane coupling agent, and 1.5 parts antibacterial agent. The nylon is commercially available PA6, the toughening agent is maleic anhydride-grafted polyethylene, and the silane coupling agent is γ-(2,3-epoxypropoxy)propyltrimethoxysilane. The antibacterial agent is prepared by a method comprising the following steps: silver lactate is fully dissolved in dichloromethane to obtain a silver lactate solution with a mass fraction of 0.5%; then, a dichloromethane solution of 1,3,5-triazine-2,4,6-triacyl chloride with a mass fraction of 5% is added dropwise to the silver lactate solution at 25°C (the molar ratio of 1,3,5-triazine-2,4,6-triacyl chloride to silver lactate is 1:1); then, triethylamine acid-binding agent is added, and the mixture is stirred for 4 hours; then, a dichloromethane solution of dodecylmethyl dihydroxyethyl ammonium chloride is added (the mass fraction of dodecylmethyl dihydroxyethyl ammonium chloride in the dichloromethane solution of dodecylmethyl dihydroxyethyl ammonium chloride is 25%, and the molar ratio of dodecylmethyl dihydroxyethyl ammonium chloride to 1,3,5-triazine-2,4,6-triacyl chloride is 1:1); the temperature is raised to 35°C, and the mixture is stirred for another 15 hours; the mixture is filtered, and the filtrate is evaporated to dryness to obtain the antibacterial agent. The structural formula of dodecylmethyldihydroxyethylammonium chloride is as follows:

[0028]

[0029] Example 2

[0030] The antibacterial nylon composite material of this embodiment comprises the following components in parts by weight: 70 parts nylon, 36 parts glass fiber, 12 parts toughening agent, 0.6 parts silane coupling agent, and 3 parts antibacterial agent. The nylon is commercially available PA6, the toughening agent is an EPDM rubber compound, and the silane coupling agent is γ-(2,3-epoxypropoxy)propyltrimethoxysilane. The antibacterial agent is prepared by a method comprising the following steps: silver lactate is fully dissolved in dichloromethane to obtain a 2% silver lactate solution; then, a 10% dichloromethane solution of 1,3,5-triazine-2,4,6-triacyl chloride is added dropwise to the silver lactate solution at 30°C (the molar ratio of 1,3,5-triazine-2,4,6-triacyl chloride to silver lactate is 1:1); then, triethylamine acid-binding agent is added, and the mixture is stirred for 2 hours; then, a dichloromethane solution of dodecylmethyl dihydroxyethyl ammonium chloride is added (the dodecylmethyl dihydroxyethyl ammonium chloride in the dichloromethane solution of dodecylmethyl dihydroxyethyl ammonium chloride has a mass fraction of 15%, and the molar ratio of dodecylmethyl dihydroxyethyl ammonium chloride to 1,3,5-triazine-2,4,6-triacyl chloride is 1:1); the temperature is raised to 30°C, and the mixture is stirred for another 30 hours; the mixture is filtered, and the filtrate is evaporated to dryness to obtain the antibacterial agent. The structural formula of dodecylmethyldihydroxyethylammonium chloride is as follows:

[0031]

[0032] Example 3

[0033] The antibacterial nylon composite material of this embodiment comprises the following components in parts by weight: 60 parts nylon, 30 parts glass fiber, 7 parts toughening agent, 0.4 parts silane coupling agent, and 2 parts antibacterial agent. The nylon is commercially available PA6, the toughening agent is maleic anhydride-grafted polyethylene, and the silane coupling agent is γ-(2,3-epoxypropoxy)propyltrimethoxysilane. The antibacterial agent is prepared by a method comprising the following steps: silver lactate is fully dissolved in dichloromethane to obtain a 1% silver lactate solution; then, a 7% dichloromethane solution of 1,3,5-triazine-2,4,6-triacyl chloride is added dropwise to the silver lactate solution at 28°C (the molar ratio of 1,3,5-triazine-2,4,6-triacyl chloride to silver lactate is 1:1); then, triethylamine acid-binding agent is added, and the mixture is stirred for 3 hours; then, a dichloromethane solution of dodecylmethyl dihydroxyethyl ammonium chloride is added (the mass fraction of dodecylmethyl dihydroxyethyl ammonium chloride in the dichloromethane solution of dodecylmethyl dihydroxyethyl ammonium chloride is 18%, and the molar ratio of dodecylmethyl dihydroxyethyl ammonium chloride to 1,3,5-triazine-2,4,6-triacyl chloride is 1:1); the temperature is raised to 32°C, and the mixture is stirred for another 19 hours; the mixture is filtered, and the filtrate is evaporated to dryness to obtain the antibacterial agent. The structural formula of dodecylmethyldihydroxyethylammonium chloride is as follows:

[0034]

[0035] Comparative Example 1

[0036] The only difference between the antibacterial nylon composite material in this comparative example and the antibacterial nylon composite material in Example 1 is that the antibacterial agent used in this comparative example is silver lactate.

[0037] Comparative Example 2

[0038] The difference between the antibacterial nylon composite material of this comparative example and the antibacterial nylon composite material of Example 1 is that the antibacterial agent used in the antibacterial nylon composite material of this comparative example is prepared by a method including the following steps: silver lactate is fully dissolved in dichloromethane to obtain a silver lactate solution with a mass fraction of 0.5%; then, a dichloromethane solution of pyromellitic trimethylol chloride with a mass fraction of 5% is added dropwise to the silver lactate solution at 25°C (the molar ratio of pyromellitic trimethylol chloride to silver lactate is 1:1); then, triethylamine acid binder is added, and the mixture is stirred for 4 hours; then, a dichloromethane solution of dodecylmethyl dihydroxyethyl ammonium chloride is added (the mass fraction of dodecylmethyl dihydroxyethyl ammonium chloride in the dichloromethane solution of dodecylmethyl dihydroxyethyl ammonium chloride is 25%, and the molar ratio of dodecylmethyl dihydroxyethyl ammonium chloride to pyromellitic trimethylol chloride is 1:1); the temperature is raised to 35°C, and the mixture is stirred for 15 hours; the mixture is filtered, and the filtrate is evaporated to dryness to obtain the antibacterial agent. The structural formula of dodecylmethyldihydroxyethylammonium chloride is as follows:

[0039]

[0040] Comparative Example 3

[0041] The difference between the antibacterial nylon composite material of this comparative example and the antibacterial nylon composite material of Example 1 is that the antibacterial agent used in the antibacterial nylon composite material of this comparative example is prepared by a method including the following steps: silver lactate is fully dissolved in dichloromethane to obtain a silver lactate solution with a mass fraction of 0.5%, and then a dichloromethane solution with a mass fraction of 5% 1,3,5-triazine-2,4,6-triacyl chloride is added dropwise to the silver lactate solution at 25°C (the molar ratio of 1,3,5-triazine-2,4,6-triacyl chloride to silver lactate is 1:3). Then, triethylamine acid-binding agent is added, the mixture is stirred and reacted for 4 hours, filtered, and the filtrate is evaporated to dryness to obtain the antibacterial agent.

[0042] Comparative Example 4

[0043] The difference between the antibacterial nylon composite material of this comparative example and the antibacterial nylon composite material of Example 1 is only that the antibacterial agent used in this comparative example is prepared by a method including the following steps: A 5% (w / w) solution of 1,3,5-triazine-2,4,6-triacyl chloride in dichloromethane is added dropwise to a dichloromethane solution of dodecylmethyl dihydroxyethyl ammonium chloride (the dodecylmethyl dihydroxyethyl ammonium chloride in the dichloromethane solution of dodecylmethyl dihydroxyethyl ammonium chloride has a w / w mass fraction of 25%, and the molar ratio of dodecylmethyl dihydroxyethyl ammonium chloride to 1,3,5-triazine-2,4,6-triacyl chloride is 3:2) at 25°C. Then, triethylamine acid-binding agent is added, the mixture is stirred and reacted for 20 hours, filtered, and the filtrate is evaporated to dryness to obtain the antibacterial agent. The structural formula of dodecylmethyl dihydroxyethyl ammonium chloride is as follows:

[0044]

[0045] Application examples

[0046] According to the composition ratios of the antibacterial nylon composite materials in each embodiment and comparative example, the raw materials were added to a twin-screw extruder and melt-extruded at 255°C to obtain the antibacterial nylon composite material. Then, tensile strength, elongation at break, notched impact strength of a simply supported beam, and antibacterial properties were tested. The test results are shown in Table 1 and... Figure 1-4 As shown. Figure 1 This is a schematic diagram showing the tensile strength of the antibacterial nylon composite materials in various embodiments and comparative examples. Figure 2 This is a schematic diagram showing the elongation at break of the antibacterial nylon composite materials in each embodiment and comparative example. Figure 3 This is a schematic diagram showing the notched impact strength of simply supported beams of the antibacterial nylon composite materials in various embodiments and comparative examples. Figure 4This diagram illustrates the antibacterial rates of the antimicrobial nylon composite materials against *Escherichia coli* and *Staphylococcus aureus* in various embodiments and comparative examples. Tensile strength was tested according to standard ISO 527, elongation at break according to standard ISO 527-2, notched impact strength of simply supported beams according to standard ISO 179-1, and antimicrobial rate according to standard QB / T2591-2003. The bacterial species used in the tests were *Escherichia coli* and *Staphylococcus aureus*.

[0047] Table 1. Tensile strength, elongation at break, notched beam impact strength, and antibacterial properties of the antibacterial nylon materials in each embodiment and comparative example.

[0048]

[0049] From Table 1, Figure 1-4 It is understood that the antibacterial nylon composite material of the present invention, by selecting appropriate toughening agents, silane coupling agents and antibacterial agents, can enable nylon materials to simultaneously possess high strength, high elongation at break and high antibacterial ability, which can meet the needs of the automotive field.

Claims

1. An antibacterial nylon composite material, characterized in that, The product comprises the following components in parts by weight: 50-70 parts nylon, 26-36 parts glass fiber, 7-12 parts toughening agent, 0.2-0.6 parts silane coupling agent, and 1.5-3 parts antibacterial agent; the antibacterial agent is prepared by a method comprising the following steps: mixing and reacting silver lactate and 1,3,5-triazine-2,4,6-triacyl chloride, and then further mixing and reacting the product with dodecylmethyldihydroxyethylammonium chloride to obtain the antibacterial agent; the molar ratio of 1,3,5-triazine-2,4,6-triacyl chloride, silver lactate, and dodecylmethyldihydroxyethylammonium chloride is 1:1:

1.

2. The antibacterial nylon composite material as described in claim 1, characterized in that, The preparation method of the antibacterial agent is as follows: a 5%~10% (w / w) solution of 1,3,5-triazine-2,4,6-triacyl chloride in dichloromethane is added dropwise to a 0.5%~2% (w / w) solution of silver lactate in dichloromethane. The mixture is then reacted at 25~30℃ for 2~4 hours. A dodecylmethyldihydroxyethylammonium chloride solution in dichloromethane is then added to the reaction mixture. The temperature is raised to 30~35℃, and the mixture is reacted for another 15~30 hours. After removing impurities, the antibacterial agent is obtained.

3. The antibacterial nylon composite material as described in claim 2, characterized in that, In a dichloromethane solution of dodecylmethyl dihydroxyethyl ammonium chloride, the mass fraction of dodecylmethyl dihydroxyethyl ammonium chloride is 15% to 25%.

4. The antibacterial nylon composite material as described in claim 2, characterized in that, The method for removing impurities is as follows: after the system has been mixed and reacted, it is filtered and the filtrate is then evaporated to dryness.

5. The antibacterial nylon composite material according to any one of claims 1-4, characterized in that, The nylon is PA6.

6. The antibacterial nylon composite material according to any one of claims 1-4, characterized in that, The toughening agent is maleic anhydride-grafted polyethylene or EPDM rubber.

7. The antibacterial nylon composite material according to any one of claims 1-4, characterized in that, The silane coupling agent is an epoxy silane coupling agent.

8. The antibacterial nylon composite material as described in claim 7, characterized in that, The silane coupling agent is γ-(2,3-epoxypropoxy)propyltrimethoxysilane.

9. The application of an antibacterial nylon composite material as described in any one of claims 1-8 as a nylon material for automobiles.

Images