Antibacterial material as well as preparation method and application thereof

Abstract

The invention relates to a bacteriostatic material as well as a preparation method and application thereof. The bacteriostatic material comprises the following components in parts by weight: 70-99.99 parts of a thermoplastic polymer and 0.01-30 parts of a bacteriostatic eutectic composition, and the bacteriostatic eutectic composition comprises a hydrogen bond donor and a hydrogen bond receptor; the hydrogen bond donor comprises plant polyphenol, natural acid or a combination thereof; the hydrogen bond receptor comprises a carrier loaded with plant essential oil. According to the antibacterial material, the injection molding raw material comprising the thermoplastic polymer and the preparation raw material of the antibacterial eutectic composition are subjected to injection molding, the initial antibacterial rate of the antibacterial material reaches 98% or above, and the antibacterial rate reaches 80% or above after the antibacterial material is placed for 9 months. Besides, a large number of natural materials are used in the antibacterial material, so that the antibacterial material has natural plant fragrance, has no toxic or side effect, is environmentally friendly and safe, and improves the user experience of a user.

Description

Technical Field

[0001] The present invention belongs to the field of materials, and in particular relates to an antibacterial material and a preparation method and application thereof. Background Art

[0002] Bacteria permeate every corner of our lives. For example, Staphylococcus aureus is ubiquitous on the skin, in the nose, throat, stomach, carbuncle, festering sores, in the air, in sewage, and in food, causing food poisoning, sepsis, endocarditis, pneumonia, enteritis, osteomyelitis, and toxic shock. Escherichia coli parasitizes the intestines of humans and animals, causing gastrointestinal infections, urinary tract infections, arthritis, meningitis, and septicemic infections.

[0003] Many natural essential oils have good antibacterial effects and are widely used as antibacterial agents. For example, peppermint essential oil has antibacterial activity against Staphylococcus aureus, Escherichia coli, Pseudomonas aeruginosa, Staphylococcus epidermidis, and Klebsiella pneumoniae. Sweet orange essential oil can inhibit the growth of a variety of bacteria, including Staphylococcus aureus, Listeria monocytogenes, Vibrio parahaemolyticus, Salmonella typhimurium, and fungi such as Aspergillus flavus, Aspergillus fumigatus, and Aspergillus terreus. Lemon essential oil has varying antibacterial effects against Escherichia coli, Bacillus subtilis, and Staphylococcus aureus. The antibacterial effects of natural essential oils have been widely verified and applied. However, natural essential oils have problems such as volatility, difficulty in long-term storage, and easy decomposition when heated, which greatly limits their widespread application. Summary of the Invention

[0004] In order to overcome at least one technical problem existing in the above-mentioned prior art, one of the objectives of the present invention is to provide an antibacterial eutectic composition.

[0005] A second object of the present invention is to provide a method for preparing an antibacterial eutectic composition.

[0006] The third object of the present invention is to provide an antibacterial material that can be injection molded and has a sustained antibacterial effect, with an antibacterial rate of more than 80% after being placed for 9 months.

[0007] A fourth object of the present invention is to provide a method for preparing an antibacterial material.

[0008] A fifth object of the present invention is to provide an electronic atomization device.

[0009] A sixth object of the present invention is to provide an antibacterial eutectic composition and / or antibacterial material for use in electronic products.

[0010] In order to achieve the above object, the technical solution adopted by the present invention is:

[0011] The first aspect of the present invention provides an antibacterial eutectic composition, comprising a hydrogen bond donor and a hydrogen bond acceptor; the hydrogen bond donor comprises a plant polyphenol, a natural acid, or a combination thereof; and the hydrogen bond acceptor comprises a carrier loaded with a plant essential oil. In the present invention, the hydrogen bond donor and the carrier loaded with the plant essential oil are heated at low temperatures to form an antibacterial eutectic composition that is liquid at room temperature. The components of the antibacterial eutectic composition are hydrogen-bonded to each other, enhancing the thermal stability of the hydrogen bond donor and the natural acid, thereby preventing substantial volatilization loss or degradation under high heat.

[0012] Preferably, the molar ratio of the carrier loaded with plant essential oil to the hydrogen bond donor is 1:(3-12).

[0013] Preferably, the hydrogen bond donors include plant polyphenols and natural acids.

[0014] Preferably, the molar ratio of the natural acid to the plant polyphenol is (1-6):1; further preferably, the molar ratio of the natural acid to the plant polyphenol is (3-4):1.

[0015] Preferably, the natural acid comprises at least one of citric acid, malic acid, lactic acid, mucic acid and tartaric acid.

[0016] Preferably, the plant polyphenols include at least one of tannic acid, ellagic acid, gallic acid, anthocyanidin, dopamine, and tea polyphenols.

[0017] Preferably, the plant essential oil includes at least one of rose essential oil, verbena essential oil, sweet orange essential oil, lemon essential oil, peppermint essential oil, grapefruit essential oil, jasmine essential oil, yam essential oil, tea tree essential oil, thyme essential oil, and lavender essential oil.

[0018] Preferably, the carrier is a cavity molecular material, which refers to a compound having a cavity.

[0019] Preferably, the carrier is selected from cyclodextrin, pillar aromatics, crown ether, C 60 , cryptand. The carriers in the present invention all have hydrophilic surface and hydrophobic inner cavity properties. The present invention combines plant essential oils with carriers to achieve the embedding of plant essential oils, solving the problem of plant essential oil volatilization or thermal instability during hot injection molding.

[0020] Preferably, in the carrier loaded with plant essential oil, the mass ratio of plant essential oil to carrier is (0.005-4):1; further preferably, the mass ratio of plant essential oil to carrier is (0.1-4):1; even further preferably, the mass ratio of plant essential oil to carrier is (1.5-4):1.

[0021] The second aspect of the present invention provides a method for preparing the antibacterial eutectic composition provided in the first aspect of the present invention, comprising the following steps: heating and mixing a hydrogen bond donor and a carrier loaded with plant essential oil to obtain the antibacterial eutectic composition.

[0022] Preferably, the heating temperature is 60-100°C.

[0023] Preferably, the preparation method of the carrier loaded with plant essential oil is: mixing the plant essential oil and the carrier; further preferably, the preparation method of the carrier loaded with plant essential oil is: mixing the plant essential oil and the carrier for 4 to 20 hours; even more preferably, the preparation method of the carrier loaded with plant essential oil is: mixing the plant essential oil and the carrier for 4 to 20 hours, rotating and centrifuging, and separating to obtain the carrier loaded with plant essential oil.

[0024] A third aspect of the present invention provides an antibacterial material comprising the following raw materials in parts by weight: 70 to 99.99 parts of a thermoplastic polymer injection molding material and 0.01 to 30 parts of the antibacterial eutectic composition provided in the first aspect of the present invention. The antibacterial material is prepared by blending the thermoplastic polymer injection molding material and the raw materials for the antibacterial eutectic composition and then injection molding the resulting material. The material slowly releases the antibacterial active ingredient, achieving a sustained and highly effective antibacterial effect. Specifically, the antibacterial material exhibits an initial antibacterial rate exceeding 98%, and an antibacterial rate exceeding 80% after nine months of storage.

[0025] The injection molding raw material of the thermoplastic polymer refers to the raw material used for injection molding the thermoplastic polymer. The thermoplastic polymers in the present invention are all prepared using the injection molding raw materials and injection molding processes commonly used in the prior art for injection molding such thermoplastic polymers.

[0026] Preferably, the thermoplastic polymer includes at least one of polyethylene terephthalate-1,4-cyclohexanedimethanol, acrylonitrile-butadiene-styrene copolymer, polymethyl methacrylate, nylon polyamide, polycarbonate, polyethylene, polyoxymethylene, polypropylene, polystyrene, and thermoplastic polyurethane.

[0027] Preferably, the antibacterial material is antibacterial plastic.

[0028] The fourth aspect of the present invention provides a method for preparing the antibacterial material provided in the third aspect of the present invention, comprising the following steps:

[0029] The antibacterial material is prepared by mixing an injection molding raw material including a thermoplastic polymer and a preparation raw material of the antibacterial eutectic composition, and then performing injection molding.

[0030] Preferably, the injection molding temperature is 160-260°C; further preferably, the injection molding temperature is 180-240°C; even further preferably, the injection molding temperature is 180-220°C.

[0031] A fifth aspect of the present invention provides an electronic atomization device, comprising an oil storage cup for containing atomized liquid, the oil storage cup being provided with a suction nozzle, the suction nozzle and / or the oil storage cup being made of the antibacterial material provided in the third aspect of the present invention. Preferably, the suction nozzle is provided at one end of the oil storage cup along the longitudinal axis.

[0032] The sixth aspect of the present invention provides use of the antibacterial eutectic composition provided in the first aspect of the present invention and / or the antibacterial material provided in the third aspect of the present invention in electronic products.

[0033] Preferably, the electronic products include electronic cigarettes, medical electronic devices, household appliances, and food production electronic devices.

[0034] The present invention has the following beneficial effects: the antibacterial eutectic composition of the present invention utilizes a hydrogen bond donor combined with a carrier loaded with plant essential oils, forming a large number of hydrogen bonds within the composition, thereby improving the stability and thermal stability of the antibacterial active ingredients (plant polyphenols and / or natural acids and plant essential oils), and preventing volatilization or degradation of the antibacterial active ingredients. The presence of both the carrier and the hydrogen bonds allows for the slow release of the antibacterial active ingredients in the composition, resulting in an excellent and sustained antibacterial effect. Furthermore, the antibacterial eutectic composition of the present invention is liquid, making it more processable than the powdered material before the eutectic.

[0035] The antibacterial material of the present invention is obtained by injection molding an injection molding raw material including a thermoplastic polymer and a raw material for preparing an antibacterial eutectic composition. Its initial antibacterial rate reaches more than 98%, and the antibacterial rate reaches more than 80% after being placed for 9 months. In addition, the antibacterial material of the present invention uses a large amount of natural materials, which makes the antibacterial material have a natural plant fragrance, is non-toxic and has no side effects, is environmentally friendly and safe, and improves the user experience. In addition, the antibacterial eutectic composition is a liquid and has excellent compatibility with thermoplastic polymers. When the two are mixed, the distribution of the antibacterial eutectic composition is more uniform, so that the antibacterial effect of the obtained antibacterial material is better and the composition is more uniform.

[0036] The preparation method of the antibacterial material of the present invention is simple and easy to operate. It only requires mixing the components of the antibacterial eutectic composition and then mixing and injection molding with the injection molding raw materials of the thermoplastic polymer. It does not require complicated equipment and costs, and does not introduce toxic and harmful substances. It is more environmentally friendly and economical. BRIEF DESCRIPTION OF THE DRAWINGS

[0037] Figure 1 This is a bacteriostatic test diagram of the antibacterial plastic in Example 1.

[0038] Figure 2 This is a bacteriostatic test diagram of the antibacterial plastic in Example 2. DETAILED DESCRIPTION

[0039] The specific implementation of the present invention will be further described in detail below in conjunction with the accompanying drawings and examples, but the implementation and protection of the present invention are not limited thereto. It should be noted that if there are any processes that are not particularly described in detail below, they can be implemented or understood by those skilled in the art with reference to the prior art. The reagents or instruments used that do not indicate the manufacturer are all conventional products that can be purchased commercially.

[0040] Example 1

[0041] This example provides an antibacterial plastic, which is formed by injection molding a mixture of a liquid antibacterial eutectic solvent and polypropylene, wherein the mass ratio of the liquid antibacterial eutectic solvent to the polypropylene is 1:4, and the liquid antibacterial eutectic solvent is made from raw materials for preparing cyclodextrin loaded with sweet orange essential oil, citric acid, and tannic acid, and the molar ratio of the cyclodextrin loaded with sweet orange essential oil, citric acid, and tannic acid is 1:3:1.

[0042] The antibacterial plastic in this example is prepared by the following preparation method, the specific steps are:

[0043] (1) 2 kg of cyclodextrin was placed in 4 kg of sweet orange essential oil, stirred for 24 hours, and centrifuged to obtain cyclodextrin loaded with sweet orange essential oil.

[0044] (2) 2 kg of the above-mentioned cyclodextrin loaded with sweet orange essential oil, 1.01 kg of citric acid, and 3 kg of tannic acid were mixed and stirred at 100° C. for 5 hours to obtain a liquid antibacterial eutectic solvent.

[0045] (3) 2 kg of the above-mentioned liquid antibacterial eutectic solvent and 8 kg of polypropylene were mixed and then injection molded at 200° C. to obtain the antibacterial plastic in this example.

[0046] Example 2

[0047] This example provides an antibacterial plastic, which is formed by injection molding a mixture of a liquid antibacterial eutectic solvent and polypropylene, wherein the mass ratio of the liquid antibacterial eutectic solvent to polypropylene is 3:7, and the liquid antibacterial eutectic solvent is made from raw materials for preparing cyclodextrin loaded with sweet orange essential oil, citric acid, and tannic acid, and the molar ratio of the cyclodextrin loaded with sweet orange essential oil, citric acid, and tannic acid is 1:4:1.

[0048] The antibacterial plastic in this example is prepared by the following preparation method, the specific steps are:

[0049] (1) 1 kg of cyclodextrin was placed in 1.5 kg of sweet orange essential oil, stirred for 24 hours, and centrifuged to obtain cyclodextrin loaded with sweet orange essential oil.

[0050] (2) 1 kg of the above-mentioned cyclodextrin loaded with sweet orange essential oil, 0.677 kg of citric acid, and 1.5 kg of tannic acid were mixed and stirred at 100° C. for 5 hours to obtain a liquid antibacterial eutectic solvent.

[0051] (3) 3 kg of the above-mentioned liquid antibacterial eutectic solvent and 7 kg of polypropylene were mixed and injection molded at 200° C. to obtain the antibacterial plastic in this example.

[0052] Example 3

[0053] This example provides an antibacterial plastic, which is formed by injection molding a mixture of a liquid antibacterial eutectic solvent and polypropylene, wherein the mass ratio of the liquid antibacterial eutectic solvent to polypropylene is 0.01:99.99, and the liquid antibacterial eutectic solvent is made from raw materials for preparing cyclodextrin loaded with sweet orange essential oil and citric acid, and the molar ratio of the cyclodextrin loaded with sweet orange essential oil to citric acid is 1:10.

[0054] The antibacterial plastic in this example is prepared by the following preparation method, the specific steps are:

[0055] (1) 1 kg of cyclodextrin was placed in 3 kg of sweet orange essential oil, stirred for 24 hours, and centrifuged to obtain cyclodextrin loaded with sweet orange essential oil.

[0056] (2) 10 kg of the above-mentioned cyclodextrin loaded with sweet orange essential oil and 16.93 kg of citric acid were mixed and stirred at 100° C. for 5 hours to obtain a liquid antibacterial eutectic solvent.

[0057] (3) 0.01 kg of the above-mentioned liquid antibacterial eutectic solvent and 99.99 kg of polypropylene were mixed and injection molded at 200° C. to obtain the antibacterial plastic in this example.

[0058] Example 4

[0059] This example provides an antibacterial plastic, which differs from Example 1 only in that gallic acid is used instead of tannic acid and citric acid in Example 1, and the molar ratio of cyclodextrin loaded with sweet orange essential oil to gallic acid is 1:6.

[0060] Example 5

[0061] This example provides an antibacterial plastic, which differs from Example 1 only in that columnar aromatic hydrocarbons are used instead of cyclodextrin.

[0062] Example 6

[0063] This example provides an antibacterial plastic, which differs from Example 1 only in that crown ether is used instead of cyclodextrin, and polycarbonate is used instead of polypropylene.

[0064] Example 7

[0065] This example provides an antibacterial plastic, which differs from Example 1 only in that: C 60 Instead of cyclodextrin.

[0066] Example 8

[0067] This example provides an antibacterial plastic, which differs from Example 1 only in that cryptand is used instead of cyclodextrin.

[0068] Example 9

[0069] This example provides an antibacterial plastic, which differs from Example 1 only in that malic acid is used instead of citric acid.

[0070] Example 10

[0071] This example provides an antibacterial plastic, which differs from Example 1 only in that lactic acid is used instead of citric acid.

[0072] Example 11

[0073] This example provides an antibacterial plastic, which differs from Example 1 only in that tartaric acid is used instead of citric acid.

[0074] Example 12

[0075] This example provides an antibacterial plastic, which differs from Example 1 only in that ellagic acid is used instead of tannic acid.

[0076] Example 13

[0077] This example provides an antibacterial plastic, which differs from Example 1 only in that gallic acid is used instead of tannic acid.

[0078] Example 14

[0079] This example provides an antibacterial plastic, which differs from Example 1 only in that anthocyanin is used instead of tannic acid.

[0080] Example 15

[0081] This example provides an antibacterial plastic, which differs from Example 1 only in that tea polyphenols are used instead of tannic acid.

[0082] Example 16

[0083] This example provides an antibacterial plastic, which differs from Example 1 only in that dopamine is used instead of tannic acid.

[0084] Example 17

[0085] This example provides an electronic atomization device, which includes an oil storage cup for containing atomized liquid. The oil storage cup has a first end and a second end arranged along the long axis. The first end of the oil storage cup is provided with a suction nozzle. The materials of the suction nozzle and the oil storage cup are both the antibacterial plastic in Example 1.

[0086] Comparative Example 1

[0087] This example provides an antibacterial plastic, which is different from Example 1 in that this example does not contain cyclodextrin loaded with sweet orange essential oil.

[0088] Comparative Example 2

[0089] This example provides an antibacterial plastic, which is different from Example 1 in that it does not contain citric acid and tannic acid.

[0090] Performance testing:

[0091] (1) Antibacterial effect test

[0092] The antibacterial effect test is carried out with reference to the national standard GB / T31402. The specific test method is as follows:

[0093] 1. Test strain: Escherichia coli (CMCC44102)

[0094] 2. Culture medium: nutrient agar culture medium, plate count medium, physiological saline (0.85% NaCl solution)

[0095] 3. Main equipment: autoclave, incubator, clean bench, constant temperature box, pipette, inoculation loop, culture dish

[0096] 4. Experimental steps

[0097] (1) The strains were activated on the slant culture medium for 24 h, and the strains were selected to make different dilution concentrations. The concentrations of the diluted bacterial solution were calculated and the concentration of the prepared bacterial suspension was 10 5 -10 6 CFU / mL.

[0098] (2) Pipette 0.4 mL of the test bacterial suspension and add it to mix. After shaking on a shaker for 4 hours, pipette 1.0 mL of the test bacteria and sample mixture and inoculate the plate.

[0099] (3) Simultaneously, PBS (phosphate buffered saline) was used instead of the sample to conduct a parallel test as a positive control group. The control group was diluted 100-fold and inoculated on a plate. The culture medium from the same batch was used as a negative control (blank control). The culture medium from the same batch was added with the antibacterial plastic in Comparative Example 1 instead of the sample and a parallel test was conducted as a control group; the culture medium from the same batch was added with the antibacterial plastic samples in Example 1 and Example 2 as experimental groups.

[0100] (4) All test samples and control samples were cultured at 36°C ± 1°C for 48 h.

[0101] (5) Count the colonies on a colony counter after 48 hours.

[0102] The antibacterial performance test results of Example 1 and Comparative Example 1 measured according to the above test method are shown in Table 1, wherein the antibacterial test graphs of Example 1 and Example 2 are shown in Table 1. Figure 1 and Figure 2 shown.

[0103] (6) The materials in Examples 1 to 4 and Comparative Examples 1 to 2 were left to stand for 3 months, 6 months, and 9 months, respectively, and then subjected to antibacterial tests using the above-mentioned test method. The specific antibacterial test results are shown in Table 2.

[0104] Table 1 Antibacterial performance test results of Example 1 and Comparative Example 1

[0105]

[0106] Table 2 Continuous antibacterial test results of Examples 1 to 4 and Comparative Examples 1 to 2

[0107]

[0108]

[0109] Depend on Figures 1-2 As can be seen from Tables 1 and 2, the antibacterial plastic of the present invention has an excellent antibacterial effect, with an antibacterial rate exceeding 98%. When the antibacterial plastic of the present invention is placed for 9 months, its antibacterial rate can still exceed 80%, further indicating that the antibacterial plastic of the present invention has an excellent sustained antibacterial effect. However, the antibacterial plastics in Comparative Examples 1 and 2 did not form an antibacterial eutectic composition, and the antibacterial components were all added to the antibacterial plastic in powder form, without a sustained-release effect, and the sustained antibacterial effect was poor, which could not meet the use requirements.

[0110] While the embodiments of the present invention have been described in detail above, the present invention is not limited to the embodiments described above. Various modifications may be made within the scope of knowledge possessed by a person skilled in the art without departing from the spirit of the present invention. Furthermore, the embodiments of the present invention and the features thereof may be combined with one another unless there is a conflict.

Claims

1. An antibacterial eutectic composition, characterized in that: The antibacterial eutectic composition comprises a hydrogen bond donor and a hydrogen bond acceptor; the hydrogen bond donor comprises plant polyphenols, natural acids or a combination thereof; and the hydrogen bond acceptor comprises a carrier loaded with plant essential oil.

2. The antibacterial eutectic composition according to claim 1, characterized in that: The molar ratio of the carrier loaded with plant essential oil to the hydrogen bond donor is 1:(3-12).

3. The antibacterial eutectic composition according to claim 1 or 2, characterized in that: The natural acid includes at least one of citric acid, malic acid, lactic acid, mucic acid, and tartaric acid; And / or, the plant polyphenols include at least one of tannic acid, ellagic acid, gallic acid, anthocyanidin, dopamine, and tea polyphenols; And / or, the plant essential oil includes at least one of rose essential oil, verbena essential oil, sweet orange essential oil, lemon essential oil, peppermint essential oil, grapefruit essential oil, jasmine essential oil, yam essential oil, tea tree essential oil, thyme essential oil, and lavender essential oil; And / or, the carrier is selected from cyclodextrin, pillar aromatics, crown ether, C 60 , cryptand at least one of them.

4. The antibacterial eutectic composition according to claim 1 or 2, characterized in that: In the carrier loaded with plant essential oil, the mass ratio of the plant essential oil to the carrier is (0.005-4):

1.

5. The method for preparing the antibacterial eutectic composition according to any one of claims 1 to 4, characterized in that: The following steps are involved: The hydrogen bond donor and the carrier loaded with plant essential oil are heated and mixed to obtain the antibacterial eutectic composition.

6. An antibacterial material, characterized in that: The antibacterial material comprises the following raw materials in parts by weight: 70 to 99.99 parts of thermoplastic polymer injection molding raw materials and 0.01 to 30 parts of the antibacterial eutectic composition according to any one of claims 1 to 4.

7. The antibacterial material according to claim 6, characterized in that: The thermoplastic polymer includes at least one of polyethylene terephthalate-1,4-cyclohexanedimethanol, acrylonitrile-butadiene-styrene copolymer, polymethyl methacrylate, nylon polyamide, polycarbonate, polyethylene, polyoxymethylene, polypropylene, polystyrene, and thermoplastic polyurethane.

8. The method for preparing the antibacterial material according to claim 6 or 7, characterized in that: The following steps are involved: The antibacterial material is prepared by mixing an injection molding raw material including a thermoplastic polymer and a preparation raw material of the antibacterial eutectic composition, and then performing injection molding.

9. An electronic atomization device, characterized in that: It comprises an oil storage cup for containing atomized liquid, the oil storage cup is provided with a suction nozzle, and the suction nozzle and / or the oil storage cup are made of the antibacterial material according to claim 6 or 7.

10. Use of the antibacterial eutectic composition according to any one of claims 1 to 4 and / or the antibacterial material according to claim 6 or 7 in electronic products.

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