High-temperature-resistant polymerizable quaternary ammonium salt organic antibacterial agent, antibacterial polyolefin resin and preparation method of antibacterial polyolefin resin

Abstract

The invention belongs to the field of polymer synthetic materials, and particularly relates to a high-temperature-resistant polymerizable quaternary ammonium salt organic antibacterial agent, antibacterial polyolefin resin and a preparation method thereof. According to the invention, the cation containing polymerizable double bonds and having a rigid benzene ring structure and the imidazole cation having a long alkyl chain are subjected to anion-cation combination, so that the organic antibacterial agent which is high in heat resistance, polymerizable and excellent in antibacterial effect is obtained. The preparation method comprises the following steps: carrying out free radical polymerization on an organic antibacterial agent, olefin monomers and derivatives thereof to obtain the antibacterial polyolefin resin material which has intrinsic antibacterial characteristics, is not easy to seep, has washing resistance and excellent antibacterial stability and can resist bacteria for a long time. The heat resistance of the high-temperature-resistant polymerizable quaternary ammonium salt organic antibacterial agent can reach up to 300 DEG C, and the high-temperature-resistant polymerizable quaternary ammonium salt organic antibacterial agent can be directly used for free radical polymerization synthesis of antibacterial polyolefin resin. The obtained antibacterial polyolefin resin is high in antibacterial activity, can be directly applied to the antibacterial field, and is good in application prospect.

Description

Technical Field

[0001] The present invention belongs to the field of polymer synthetic materials, and particularly relates to a high-temperature resistant polymerizable quaternary ammonium salt organic antibacterial agent, an antibacterial polyolefin resin and a preparation method thereof. Background Art

[0002] Most polyolefin resins themselves do not have antibacterial properties and need to be modified with antibacterial agents. For example, the antibacterial polystyrene resin used in antibacterial refrigerator linings is prepared by blending a silver ion antibacterial agent with polystyrene. Although inorganic antibacterial agents are easy to process and have good thermal stability, their compatibility with the resin matrix is poor, and they are easily released into the environment, resulting in biological toxicity. Organic antibacterial agents have good compatibility with the resin matrix, have little impact on the mechanical properties of the resin, and can be firmly connected to the polymer main chain through covalent bonds and are not easily released. However, most organic antibacterial agents are easily decomposed at high temperatures, which greatly limits their application in resins that require high-temperature thermal processing.

[0003] In summary, how to solve the problem of easy decomposition of organic antibacterial agents at high temperatures and apply them to the preparation of antibacterial polyolefin resins is a technical problem to be solved urgently. Summary of the Invention

[0004] To solve the problem of easy decomposition of organic antibacterial agents at high temperatures, the present invention provides a high-temperature resistant polymerizable quaternary ammonium salt organic antibacterial agent, an antibacterial polyolefin resin and a preparation method thereof. By designing the quaternary ammonium salt molecule, the present invention obtains an organic antibacterial agent with high heat resistance, polymerizability and excellent antibacterial effect. By carrying out free radical polymerization with olefin monomers, an antibacterial polyolefin resin material with antibacterial properties, not easy to exude, wash-resistant, excellent antibacterial stability and long-term antibacterial effect is obtained.

[0005] In the first aspect, the present invention provides a class of high-temperature resistant polymerizable quaternary ammonium salt organic antibacterial agents, and the structural general formula is selected from one of the following three:

[0006]

[0007] Among them, m, n, h≥0, and m, n, h are natural numbers.

[0008] Further, the performance of the high-temperature resistant polymerizable quaternary ammonium salt organic antibacterial agent is: T d，5％ > 200 °C, the MIC value against Staphylococcus aureus < 50 μg / mL -1 , the MIC value against Escherichia coli < 100 μg / mL -1 .

[0009] Second aspect, the present invention provides a preparation method of a class of heat-resistant polymerizable quaternary ammonium salt organic antibacterial agents, and the heat-resistant polymerizable quaternary ammonium salt organic antibacterial agent is formed by combining a cation containing a polymerizable double bond and having a rigid benzene ring structure and an imidazole cation with a long alkyl chain through anion-cation combination.

[0010] Further, the raw materials of the heat-resistant polymerizable quaternary ammonium salt organic antibacterial agent include: sodium p-styrenesulfonate, metal ion salt, imidazole ionic liquid; the metal salt ion can undergo ion exchange with the sulfonate ion of sodium p-styrenesulfonate to produce a water-insoluble precipitate; in terms of mole fraction, the feeding ratio of sodium p-styrenesulfonate, metal ion salt, and imidazole ionic liquid is 1:1:1.

[0011] Further, the metal ion salt is selected from metal ion salts that can undergo ion exchange with the sulfonate ion of sodium p-styrenesulfonate to produce a water-insoluble precipitate, specifically selected from one of barium sulfate, barium chloride, barium carbonate, calcium carbonate, calcium sulfate, calcium chloride, lead acetate, lead chloride, lead oxide, strontium nitrate, strontium chloride, strontium carbonate, copper sulfate, copper chloride, copper nitrate, zinc sulfate, zinc chloride, zinc oxide, silver nitrate, silver chloride, silver sulfate.

[0012] Further, the imidazole ionic liquid is selected from one of monosubstituted imidazole ionic liquids, disubstituted imidazole ionic liquids, and trisubstituted imidazole ionic liquids;

[0013] The structural general formula is selected from one of the following three:

[0014]

[0015] Among them, X - is selected from chloride ion, borate ion, sulfonate ion, trifluoroacetate ion, p-toluenesulfonate ion, bromide ion, trifluoroacetate ion, nitrate ion, hydrogen sulfate ion, dihydrogen phosphate ion, and m, n, h are all natural numbers, m, n, h≥0.

[0016] Further, a preparation method of a class of heat-resistant polymerizable quaternary ammonium salt organic antibacterial agents specifically includes the following steps:

[0017] S1. Add the first organic phase solution containing sodium p-styrenesulfonate to the first inorganic phase solution containing the metal ion salt, stir and react, and filter to obtain a precipitate;

[0018] S2. Disperse the precipitate obtained in step S1 into a solvent to form a suspension;

[0019] S3. Add the second organic phase solution containing the imidazole ionic liquid to the suspension prepared in step S2, stir, filter, take the filtrate, perform rotary evaporation and drying to obtain the heat-resistant polymerizable quaternary ammonium salt organic antibacterial agent.

[0020] Furthermore, the solvents in the first-phase organic phase solution, the first inorganic phase solution, the second organic phase solution, and the solvent in step S2 are each selected from at least one of water, methanol, and ethanol.

[0021] Furthermore, in terms of molar concentration, the concentrations of the first-phase organic phase solution, the second organic phase solution, and the first inorganic phase solution are 20 - 50 mol / L, 30 - 60 mol / L, and 10 - 50 mol / L, respectively; the feeding ratio of the three solutions is 1:1:1.

[0022] Furthermore, the fumigation temperature in step S3 is 30 - 80 °C, the vacuum drying temperature is 40 - 50 °C, and the drying time is 6 - 8 hours.

[0023] In a third aspect, the present invention provides a method for preparing an antibacterial polyolefin resin. Using a radical polymerization method, the above-mentioned high-temperature resistant polymerizable organic antibacterial agent, olefin monomers and their derivatives, a solvent, and a radical initiator are jointly added to a reaction kettle, heated, and the reaction temperature is controlled at 40 - 150 °C, and the reaction time is 0.5 - 48 h, then the antibacterial polyolefin resin can be prepared.

[0024] The olefin monomers and their derivatives are selected from one or more of styrene, ethylene, isobutene, vinyl chloride, vinyl acetate, acrylic acid, methyl methacrylate, and butadiene.

[0025] Furthermore, in terms of molar parts, the feeding ratio of the high-temperature resistant polymerizable quaternary ammonium salt organic antibacterial agent to the olefin monomers and their derivatives is: 1:20 - 1:50.

[0026] Furthermore, the radical polymerization includes emulsion polymerization, bulk polymerization, suspension polymerization, and anionic polymerization.

[0027] Furthermore, the radical initiator is selected from one of peroxide initiators, azo initiators, photoinitiators, and redox initiators.

[0028] In a fourth aspect, the present invention provides an antibacterial polyolefin resin prepared by using the above method with a high-temperature resistant polymerizable quaternary ammonium salt organic antibacterial agent.

[0029] Beneficial effects:

[0030] Compared with the prior art, the main advantages of the present invention include:

[0031] (1) The class of high-temperature resistant polymerizable quaternary ammonium salt organic antibacterial agents provided by the present invention greatly improves the high-temperature resistance of the organic antibacterial agent, and can still maintain stability and antibacterial activity under high-temperature conditions (such as during processing or use).

[0032] (2) The class of high-temperature resistant polymerizable organic antibacterial agents provided by the present invention can be combined with the polymer matrix through chemical bonds to become a part of the material, avoiding dissolution or migration.

[0033] (3) The class of high-temperature resistant polymerizable organic antibacterial agents provided by the present invention can be chemically bonded with the polymer matrix. The antibacterial agents are not easily lost and can provide a long-lasting antibacterial effect. And because they are not easily dissolved or migrated, the pollution and toxicity risks of the antibacterial agents to the environment are reduced.

[0034] (4) The class of high-temperature resistant polymerizable organic antibacterial agents provided by the present invention can be compatible with a variety of polymer matrices and are suitable for different processing techniques (such as injection molding, extrusion, spinning, etc.).

[0035] (5) Due to the long-lasting and stable properties, the class of high-temperature resistant polymerizable organic antibacterial agents provided by the present invention reduces the addition amount and replacement frequency of the antibacterial agents, thus reducing the cost.

[0036] (6) The present invention synthesizes antibacterial polyolefin resin based on the provided preparation method of antibacterial polyolefin resin. Compared with the traditional physical blending method of silver nanoparticle antibacterial agents, it has a long antibacterial effect, and the antibacterial agent has good compatibility with the resin matrix and does not affect the performance of the material. In addition, the antibacterial agent is not easily released from the resin matrix and has minimal harm to the human body and the environment. Description of the Drawings

[0037] Figure 1 It is the 1H NMR spectrum of Example 2;

[0038] Figure 2 It is the TGA spectrum of Example 2;

[0039] Figure 3 It is the antibacterial activity test effect diagram of Example 2;

[0040] Figure 4 It is the antibacterial activity test diagram of Example 2. Detailed Embodiments

[0041] The following will specifically describe the present invention in combination with the detailed embodiments and examples, and the advantages and various effects of the present invention will be presented more clearly therefrom. Those skilled in the art should understand that these detailed embodiments and examples are used to illustrate the present invention, rather than to limit the present invention.

[0042] Throughout the specification, unless otherwise specifically stated, the terms used herein should be understood as having the meanings commonly used in the art. Therefore, unless otherwise defined, all technical and scientific terms used herein have the same meanings as those generally understood by those skilled in the art to which the present invention belongs. In case of contradiction, this specification shall prevail.

[0043] 1H NMR analysis was carried out using a Bruker Avance II 400 MHz nuclear magnetic resonance spectrometer. Deuterochloroform and deuterated dimethyl sulfoxide were used as the test solvents, and tetramethylsilane (TMS) was used as the internal standard for 1H NMR testing.

[0044] Thermogravimetric analysis (TGA) was performed on a TA-Q500 thermogravimetric analyzer under a nitrogen atmosphere at a heating rate of 10 °C / min. -1 。

[0045] The cantilever beam notched impact test was carried out with reference to the standard of GB / T 1843-2008 / ISO 180:2000. An INSTRONCEAST 9050 instrumented impact tester was used to test the cantilever beam notched impact strength of the polymer. The dimensions of the specimen were 80 mm × 10 mm × 4 mm, the notch depth was 2 mm, the pendulum energy was 5.5 J, and the test temperature was 25 °C.

[0046] Antibacterial test: Staphylococcus aureus and Escherichia coli were screened from solid plates prepared by the streak plate method. The concentrations of Staphylococcus aureus and Escherichia coli in the liquid LB medium were 10 5 ~10 6 CFU / mL.

[0047] In a 96-well plate, the antibacterial agent solution was mixed with the bacterial suspension, and the final concentration of the antibacterial agent was 0.16 to 40 μg / mL. -1 All bacterial suspensions were cultured at 37.5 °C for 24 hours. The MIC was defined as the lowest concentration of the antibacterial agent without visible bacterial growth.

[0048] In the antibacterial performance test of the antibacterial polyolefin resin, the bacterial suspension (10 5 ~10 6 CFU / mL) was smeared on the polystyrene resin and cultured at 37.5 °C for 24 hours. After the culture, the bacterial samples were directly diluted with normal saline (Staphylococcus aureus: 10 2 times; Escherichia coli: 10 4 times). Then, 100 μL of the diluted bacterial suspension was smeared on a solid LB plate and counted after culturing at 37.5 °C for 24 hours.

[0049] Unless otherwise specified, all kinds of raw materials, reagents, instruments, and equipment used in the present invention can be obtained through market purchase or can be prepared by existing methods.

[0050] Example 1

[0051] This example is a method for preparing a high-temperature resistant polymerizable quaternary ammonium salt organic antibacterial agent using a monosubstituted imidazole ionic liquid, which includes the following steps:

[0052] (1) Dissolve 1 mol of sodium p-styrenesulfonate and 1 mol of silver nitrate in 20 mL of water respectively. After fully stirring and dissolving, gradually add 20 mL of silver nitrate solution dropwise to 20 mL of sodium p-styrenesulfonate solution, stir vigorously for 1 h, and filter to obtain a precipitate.

[0053] (2) Disperse all the obtained precipitate into 20 mL of methanol to form a suspension, and dissolve 1 mol of 1-octylimidazole chloride in 20 mL of methanol solution.

[0054] (3) Slowly add 20 mL of 1-octylimidazole chloride solution dropwise to the suspension, stir vigorously for 2 h, filter, rotary evaporate the filtrate at 50 °C to remove methanol, and vacuum dry to obtain a high-temperature resistant polymerizable organic antibacterial agent.

[0055] (4) After testing, the final product T obtained in Example 1 d,5％ > 200 °C, having excellent heat resistance.

[0056] Example 2

[0057] This example is a method for preparing a high-temperature resistant polymerizable quaternary ammonium salt organic antibacterial agent using a disubstituted imidazole ionic liquid, including the following steps:

[0058] (1) Dissolve 1 mol of sodium p-styrenesulfonate and 1 mol of silver nitrate in 20 mL of water respectively. After fully stirring and dissolving, gradually add 20 mL of silver nitrate solution dropwise to 20 mL of sodium p-styrenesulfonate solution, stir vigorously for 1 h, and filter to obtain a precipitate.

[0059] (2) Disperse all the obtained precipitate into 20 mL of methanol to form a suspension, and dissolve 1 mol of 1-hexadecyl-3-methylimidazole bromide in 20 mL of methanol solution.

[0060] (3) Slowly add 20 mL of 1-hexadecyl-3-methylimidazole bromide solution dropwise to the suspension, stir vigorously for 2 h, filter, rotary evaporate the filtrate at 50 °C to remove methanol, and vacuum dry to obtain a high-temperature resistant polymerizable organic antibacterial agent.

[0061] (4) After testing, the final product T obtained in Example 2 d,5％ > 300 °C, having excellent heat resistance.

[0062] Example 3

[0063] This example is a method for preparing a high-temperature resistant polymerizable quaternary ammonium salt organic antibacterial agent using a trisubstituted imidazole ionic liquid, including the following steps:

[0064] (1) Dissolve 1 mol of sodium p-styrenesulfonate and 1 mol of silver nitrate in 20 mL of water respectively. After fully stirring and dissolving, gradually add 20 mL of silver nitrate solution dropwise into 20 mL of sodium p-styrenesulfonate solution, stir vigorously for 1 h, and filter to obtain a precipitate.

[0065] (2) Disperse all the obtained precipitate into 20 mL of methanol to form a suspension, and dissolve 1 mol of 1-hexadecyl-2,3-dimethylimidazolium bromide in 20 mL of methanol solution.

[0066] (3) Slowly add 20 mL of 1-hexadecyl-2,3-dimethylimidazolium bromide solution dropwise into the suspension, stir vigorously for 2 h, filter, and rotary evaporate the filtrate at 50 °C to remove methanol, and then dry it under vacuum to obtain a high-temperature resistant polymerizable organic antibacterial agent.

[0067] (4) After testing, the final product T obtained in Example 3 d,5％ > 250 °C, and has excellent heat resistance.

[0068] Example 4

[0069] This example is a specific method for preparing an antibacterial polyolefin resin, including the following steps:

[0070] (1) Stir and dissolve styrene monomer, high-temperature resistant polymerizable organic antibacterial agent prepared from monosubstituted imidazole ionic liquid, ethylbenzene solvent and free radical initiator according to the molar ratio of feedstock 100:5:20:1 to form an organic phase solution.

[0071] (2) Heat the organic phase solution to the initiation temperature of the free radical initiator for free radical polymerization reaction to obtain a polymer;

[0072] (3) Dissolve the polymer in an organic solvent and then pour it into ethanol to precipitate;

[0073] (4) Filter and wash the precipitate, and dry it under vacuum to obtain an antibacterial polystyrene resin.

[0074] (5) After testing, the molecular weight of the final product obtained in Example 4 is 10 kDa. The antibacterial test shows that the synthesized antibacterial resin has antibacterial performance of more than 95% against Escherichia coli and more than 99% against Staphylococcus aureus.

[0075] Example 5

[0076] This example is a specific method for preparing an antibacterial polyolefin resin, including the following steps:

[0077] (1) Stir and dissolve styrene monomer, high-temperature resistant polymerizable quaternary ammonium salt organic antibacterial agent prepared from disubstituted imidazole ionic liquid, ethylbenzene solvent and free radical initiator according to the molar ratio of feedstock 100:5:20:1 to form an organic phase solution.

[0078] (2) Heat the organic phase solution to the radical initiator initiation temperature for radical polymerization to obtain a polymer.

[0079] (3) Dissolve the polymer in an organic solvent and then pour it into ethanol for precipitation.

[0080] (4) Filter, wash, and vacuum dry the precipitate to obtain the antibacterial polystyrene resin.

[0081] (5) After testing, the molecular weight of the final product obtained in Example 5 is 12 kDa. The antibacterial test shows that the synthesized antibacterial polyolefin resin has nearly 100% antibacterial performance against Escherichia coli and Staphylococcus aureus.

[0082] Example 6

[0083] This example is a specific method for preparing antibacterial polyolefin resin, including the following steps:

[0084] (1) Stir and dissolve styrene monomer, a heat-resistant polymerizable quaternary ammonium salt organic antibacterial agent prepared from a trisubstituted imidazole ionic liquid, ethylbenzene solvent, and radical initiator in a molar ratio of 100:5:20:1 to form an organic phase solution.

[0085] (2) Heat the organic phase solution to the radical initiator initiation temperature for radical polymerization to obtain a polymer.

[0086] (3) Dissolve the polymer in an organic solvent and then pour it into ethanol for precipitation.

[0087] (4) Filter, wash, and vacuum dry the precipitate to obtain the antibacterial polystyrene resin.

[0088] (5) After testing, the molecular weight of the final product obtained in Example 6 is 15 kDa. The antibacterial test shows that the synthesized antibacterial polyolefin resin has nearly 100% antibacterial performance against Escherichia coli and Staphylococcus aureus.

[0089] Examples 7 - 9

[0090] The synthesis process is the same as that in Example 4, except that the styrene monomer is sequentially replaced with vinyl chloride, acrylic acid, and methyl methacrylate monomers.

[0091] After testing, the molecular weight of the final product obtained in Example 7 is 8 kDa. The antibacterial test shows that the synthesized antibacterial polyolefin resin has nearly 100% antibacterial performance against Escherichia coli and Staphylococcus aureus.

[0092] After testing, the molecular weight of the final product obtained in Example 8 was 10 kDa. Antibacterial tests showed that the synthesized antibacterial polyolefin resin had an antibacterial performance of nearly 100% against Escherichia coli and Staphylococcus aureus.

[0093] After testing, the molecular weight of the final product obtained in Example 7 was 12 kDa. Antibacterial tests showed that the synthesized antibacterial polyolefin resin had an antibacterial performance of nearly 100% against Escherichia coli and Staphylococcus aureus.

[0094] Examples 10 - 12

[0095] The synthesis process was the same as that in Example 5, except that the styrene monomer was sequentially replaced with vinyl chloride, acrylic acid, and methyl methacrylate monomers.

[0096] After testing, the molecular weight of the final product obtained in Example 10 was 7 kDa. Antibacterial tests showed that the synthesized antibacterial polyolefin resin had an antibacterial performance of nearly 100% against Escherichia coli and Staphylococcus aureus.

[0097] After testing, the molecular weight of the final product obtained in Example 11 was 11 kDa. Antibacterial tests showed that the synthesized antibacterial polyolefin resin had an antibacterial performance of nearly 100% against Escherichia coli and Staphylococcus aureus.

[0098] After testing, the molecular weight of the final product obtained in Example 12 was 10 kDa. Antibacterial tests showed that the synthesized antibacterial polyolefin resin had an antibacterial performance of nearly 100% against Escherichia coli and Staphylococcus aureus.

[0099] Examples 13 - 15

[0100] The synthesis process was the same as that in Example 6, except that the styrene monomer was sequentially replaced with vinyl chloride, acrylic acid, and methyl methacrylate monomers.

[0101] After testing, the molecular weight of the final product obtained in Example 13 was 13 kDa. Antibacterial tests showed that the synthesized antibacterial polyolefin resin had an antibacterial performance of nearly 100% against Escherichia coli and Staphylococcus aureus.

[0102] After testing, the molecular weight of the final product obtained in Example 14 was 9 kDa. Antibacterial tests showed that the synthesized antibacterial polyolefin resin had an antibacterial performance of nearly 100% against Escherichia coli and Staphylococcus aureus.

[0103] After testing, the molecular weight of the final product obtained in Example 15 was 15 kDa. Antibacterial tests showed that the synthesized antibacterial polyolefin resin had an antibacterial performance of nearly 100% against Escherichia coli and Staphylococcus aureus.

[0104] Analysis of test results

[0105] It can be seen from Figure 1 that the characteristic peaks at 5.27 ppm, 5.84 ppm and 6.73 ppm in the 1 1H NMR spectrum confirm the presence of C═C molecules. In addition, the chemical shifts and integral areas of all proton peaks in the spectrum are consistent with the theoretical values.

[0106] It can be seen from Figure 2 that before the temperature rises to about 326.38 °C, the weight of the antibacterial monomer remains basically unchanged, indicating that the sample is relatively stable within this temperature range and no obvious decomposition or volatilization occurs. The T d，5％ of the antibacterial monomer is 326.38 °C, which indicates that it has an obvious weight loss only at temperatures above 300 °C, indicating that the antibacterial monomer has extremely high thermal stability.

[0107] It can be seen from Figure 3 Figure 4 that the antibacterial experiment shows that the antibacterial rate of the antibacterial polyolefin resin against Staphylococcus aureus and Escherichia coli is close to 100%, proving that the antibacterial polyolefin resin has excellent antibacterial performance.

[0108] Table 1

[0109]

[0110] Table 2

[0111]

[0112] Table 1 shows the cantilever beam notched impact test of Example 5. From the data in the table, it can be seen that after adding an appropriate amount of antibacterial monomer, the mechanical properties of the resin do not decrease significantly, indicating good compatibility between the antibacterial monomer and the resin.

[0113] Table 2 shows the MIC value of Example 2. The minimum inhibitory concentration of the antibacterial monomer against Escherichia coli is only 0.32 μg / ml -1 , and the minimum inhibitory concentration against Staphylococcus aureus is even lower, not exceeding 0.16 μg / ml -1 , proving that the antibacterial effect of the antibacterial monomer is extremely excellent. The reason why this organic antibacterial agent has such an excellent antibacterial effect is that it has a positively charged quaternary ammonium group, which can attract negatively charged bacteria on the cell membrane through electrostatic interaction and disturb the bacterial cell wall. In addition, the hydrophobic effect of the alkyl chain can insert into the phospholipid bilayer of the bacterial cell membrane, causing the bacteria to rupture and the contents to flow out, thus achieving the purpose of efficient antibacterial.

[0114] In summary, for a class of heat-resistant polymerizable organic antibacterial agents described in the present invention, nuclear magnetic resonance hydrogen spectrum analysis, TGA spectrum analysis, and antibacterial tests prove that the organic antibacterial agent has excellent high-temperature stability and antibacterial activity. Using this class of heat-resistant polymerizable organic antibacterial agents, a class of antibacterial polyolefin resins is obtained through free radical polymerization. The cantilever beam notch impact test proves that the mechanical properties of the antibacterial polyolefin resin remain stable after adding the antibacterial agent and have intrinsic antibacterial properties. The antibacterial test proves that the antibacterial rate is close to 100%. Although the specific implementation manners of the present invention are described above in conjunction with the accompanying drawings, it is not a limitation on the protection scope of the present invention. Those skilled in the art should understand that, based on the technical solutions of the present invention, various modifications or deformations that can be made by those skilled in the art without creative labor are still within the protection scope of the present invention.

Claims

1. A class of heat-resistant polymerizable quaternary ammonium salt organic antibacterial agents, characterized in that, The structural general formula is selected from one of the following three: Wherein, m, n, h ≥ 0, and m, n, h are natural numbers.

2. The heat-resistant polymerizable quaternary ammonium salt organic antibacterial agent according to claim 1, wherein The performance parameters are: T d，5％ > 200 °C, the MIC value against Staphylococcus aureus < 50 μg / mL -1 , the MIC value against Escherichia coli < 100 μg / mL -1 .

3. Preparation method of a class of heat-resistant polymerizable quaternary ammonium salt organic antibacterial agents, characterized in that, The high-temperature resistant polymerizable quaternary ammonium salt organic antibacterial agent is formed by the combination of cations containing polymerizable double bonds and having a rigid benzene ring structure and imidazole cations with long alkyl chains through anion-cation combination; The raw materials of the high-temperature resistant polymerizable quaternary ammonium salt organic antibacterial agent include: sodium p-styrenesulfonate, metal ion salt, imidazole ionic liquid; in terms of molar parts, the feeding ratio of sodium p-styrenesulfonate, metal ion salt, and imidazole ionic liquid is 1:1:1; The metal ion salt is selected from one of barium sulfate, barium chloride, barium carbonate, calcium carbonate, calcium sulfate, calcium chloride, lead acetate, lead chloride, lead oxide, strontium nitrate, strontium chloride, strontium carbonate, copper sulfate, copper chloride, copper nitrate, zinc sulfate, zinc chloride, zinc oxide, silver nitrate, silver chloride, silver sulfate. The imidazole ionic liquid is selected from one of monosubstituted imidazole ionic liquids, disubstituted imidazole ionic liquids, and trisubstituted imidazole ionic liquids; The structural general formula is selected from one of the following three: Among them, X - is selected from chloride ion, borate ion, sulfonate ion, trifluoroacetate ion, p-toluenesulfonate ion, bromide ion, trifluoroacetate ion, nitrate ion, bisulfate ion, dihydrogen phosphate ion, and m, n, and h are all natural numbers, where m, n, h ≥ 0.

4. The preparation method according to claim 3 specifically includes the following steps: S1. Add the first organic phase solution containing sodium p-styrenesulfonate to the first inorganic phase solution containing the metal ion salt, stir and react, and filter to obtain a precipitate; S2. Disperse the precipitate obtained in step S1 into a solvent to form a suspension; S3. Add the second organic phase solution containing the imidazole ionic liquid to the suspension prepared in step S2, stir, filter, take the filtrate, perform rotary evaporation and drying to obtain the high-temperature resistant polymerizable quaternary ammonium salt organic antibacterial agent; The solvents in the first organic phase solution, the first inorganic phase solution, the second organic phase solution, and the solvent in step S2 are all selected from at least one of water, methanol, and ethanol.

5. The preparation method according to claim 4, characterized in that, In terms of molar concentration, the concentrations of the first organic phase solution, the second organic phase solution, and the first inorganic phase solution are 20 - 50 mol / L, 30 - 60 mol / L, and 10 - 50 mol / L respectively; the feeding ratio of the three solutions is 1:1:

1.

6. The preparation method according to claim 4, characterized in that, The rotary evaporation temperature in step S3 is 30 - 80 °C, the vacuum drying temperature is 40 - 50 °C, and the drying time is 6 - 8 hours.

7. A method for preparing an antibacterial polyolefin resin using the high-temperature resistant polymerizable quaternary ammonium salt organic antibacterial agent according to any one of claims 1-2, characterized in that, Using the free radical polymerization method, add the high-temperature resistant polymerizable quaternary ammonium salt organic antibacterial agent, olefin monomers and their derivatives, solvent, and free radical initiator into the reaction kettle together, heat and control the reaction temperature at 40 - 150 °C, and the reaction time is 0.5 - 48 h, then the antibacterial polyolefin resin can be prepared; The olefin monomers and their derivatives are selected from one or more of styrene, ethylene, isobutene, vinyl chloride, vinyl acetate, acrylic acid, methyl methacrylate, butadiene.

8. The method according to claim 7, wherein In terms of molar parts, the feeding ratio of the high-temperature resistant polymerizable quaternary ammonium salt organic antibacterial agent to the olefin monomers and their derivatives is: 1:20 - 1:

50.

9. The method according to claim 7, wherein The free radical initiator is selected from one of peroxide initiators, azo initiators, photoinitiators, and redox initiators.

10. The antibacterial polyolefin resin prepared by the method according to any one of claims 8 - 9.

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