Composite antibacterial agents and their preparation methods, antibacterial compositions

Abstract

This invention discloses a composite antibacterial agent, its preparation method, and an antibacterial composition. The composite antibacterial agent is based on mesoporous titanium dioxide and modified with PPG molecules, resulting in excellent antibacterial properties and renewability. This composite antibacterial agent can be used in various polymer materials to obtain antibacterial compositions that meet the requirements for high antibacterial environments and have broad application prospects.

Description

Technical Field

[0001] This invention belongs to the field of polymer modification technology, specifically relating to a composite antibacterial agent and its preparation method, and also to an antibacterial composition containing the composite antibacterial agent. Background Technology

[0002] With the increasing variety of environments in which polymers are used, the demand for their functionality is growing, and antibacterial properties are one of the more common ones. Currently, most common antibacterial polymer materials achieve this by adding certain antibacterial agents to the system; therefore, the performance of the antibacterial agent directly affects the performance of the antibacterial composition.

[0003] Currently, commonly used antibacterial agents are mainly classified into three categories: inorganic antibacterial agents, organic antibacterial agents, and natural antibacterial agents. Among them, inorganic antibacterial agents refer to those that utilize the antibacterial component Ag. + Cu 2+ Zn 2+ Plasma and its compounds, as well as their metals, are combined with inorganic materials to produce antibacterial agents. Among these antibacterial agents, TiO2 antibacterial agents are widely used due to their advantages such as high oxygen activity, good chemical stability, and no toxic side effects on the human body.

[0004] Specifically, TiO2 antibacterial agents achieve their antibacterial effect by decomposing bacteria under photocatalysis. Due to the electronic structure of nano-titanium dioxide (TiO2), which consists of a full valence band and an empty conduction band, in a water-air system, under sunlight, especially ultraviolet radiation, when the electron energy reaches or exceeds its band gap energy, electrons are excited from the valence band to the conduction band, simultaneously generating corresponding holes in the valence band, i.e., generating electron-hole pairs. Under the influence of an electric field, the electrons and holes separate and migrate to different positions on the particle surface, undergoing a series of reactions. Oxygen adsorbed and dissolved on the TiO2 surface captures electrons to form O2, and the generated superoxide anion free radicals react (oxidize) most organic matter. Simultaneously, it can react with organic matter within bacteria to generate CO2 and H2O; while the holes oxidize the -OH and H2O adsorbed on the TiO2 surface into ·OH. ·OH has a strong oxidizing ability, attacking unsaturated bonds in organic matter or extracting H atoms to generate new free radicals, triggering a chain reaction that ultimately leads to bacterial decomposition. It can be seen that its bactericidal effect is mainly due to its quantum size effect. Although ordinary TiO2 also has photocatalytic effect and can generate electron-hole pairs, the time it takes to reach the material surface is on the order of microseconds or more, and it is very easy to recombine, making it difficult to exert an antibacterial effect.

[0005] Furthermore, with the increasing demand for antibacterial materials, TiO2 antibacterial agents alone can no longer meet the actual needs of use. Summary of the Invention

[0006] In view of this, the present invention needs to provide a composite antibacterial agent, which is based on mesoporous titanium dioxide and modified by introducing polypropylene glycol (PPG) to obtain a PPG-NIPA-Cl@TiO2 composite antibacterial agent containing halogen amine functional groups. This composite antibacterial agent has excellent antibacterial properties and renewability.

[0007] To achieve the above objectives, the present invention adopts the following technical solution:

[0008] This invention provides a method for preparing a composite antibacterial agent, comprising the following steps:

[0009] Mesoporous titanium dioxide is available;

[0010] To obtain PPG-NIPA@TiO2 particles: Polypropylene glycol, N-isopropylacrylamide, potassium carbonate, acetone and deionized water are mixed and stirred at room temperature for 6-8 hours to obtain a mixed solution. The mesoporous titanium dioxide is added to the mixed solution and stirred at 40-60℃ for 8-12 hours to obtain PPG-NIPA@TiO2 particles.

[0011] To obtain the PPG-NIPA-Cl@TiO2 composite antibacterial agent: PPG-NIPA@TiO2 particles, hypochlorite and deionized water were mixed and reacted at room temperature for 10-12 hours to obtain the PPG-NIPA-Cl@TiO2 composite antibacterial agent.

[0012] This invention modifies mesoporous TiO2 with PPG molecules to prepare a PPG-NIPA-Cl@TiO2 composite antibacterial agent containing haloamine functional groups. Specifically, potassium carbonate is added to a PPG solution as a catalyst to provide an alkaline environment, allowing the hydroxyl groups on the PPG molecular chain to react with N-isopropylacrylamide (NIPA) to obtain modified PPG-NIPA containing acyclic haloamine precursor functional groups. The amide groups are then chlorinated to finally obtain the PPG-NIPA-Cl@TiO2 composite antibacterial agent containing acyclic haloamine functional groups. This composite antibacterial agent exhibits excellent antibacterial properties and regenerability. It should be noted that the steps of obtaining PPG-NIPA@TiO2 particles and the PPG-NIPA-Cl@TiO2 composite antibacterial agent also include filtering, washing, drying, and grinding the reacted solution. Since these are all conventional methods, they will not be described in detail here.

[0013] Furthermore, the mesoporous titanium dioxide of the present invention can be obtained commercially or by self-preparation, without particular limitation. In some specific embodiments of the present invention, the specific steps for providing mesoporous titanium dioxide are as follows: polyvinylpyrrolidone, dodecyl dimethyl benzyl ammonium chloride, tetrabutyl titanate, acetone, and deionized water are mixed and stirred at 60-80°C for 6-8 hours, filtered, dried, and then calcined at 400-480°C for 10-16 hours to obtain mesoporous titanium dioxide.

[0014] Furthermore, in the step of providing mesoporous titanium dioxide, the raw material ratio is not particularly limited. The particle size and pore size of the mesoporous titanium dioxide can be adjusted by adjusting the ratio between the raw materials. In some specific embodiments of the present invention, the mass ratio of polyvinylpyrrolidone, dodecyl dimethyl benzyl ammonium chloride, tetrabutyl titanate, acetone and deionized water is (18-24):(16-20):(60-80):(80-100):(200-240).

[0015] Furthermore, in the mixed solution, the mass ratio of polyoxypropylene glycol, N-isopropylacrylamide, potassium carbonate, acetone, and deionized water is (20-30):(16-20):(18-22):(60-80):(200-240).

[0016] Furthermore, in order to optimize the performance of the obtained composite antibacterial agent, preferably, the mass ratio of the mesoporous titanium dioxide to the mixed solution is (30-40):(160-200). It can be understood that the above ratio is only for optimizing the performance of the composite antibacterial agent, and there is no particular limitation on the ratio. As long as PPG molecules are used to modify the mesoporous titanium dioxide, a composite antibacterial agent with high antibacterial performance can be obtained.

[0017] Furthermore, in the step of obtaining the PPG-NIPA-Cl@TiO2 composite antibacterial agent, the mass ratio of PPG-NIPA@TiO2 particles, hypochlorite, and deionized water is (20-30):(24-30):(180-200), and the hypochlorite is selected from sodium hypochlorite, potassium hypochlorite, or calcium hypochlorite.

[0018] The present invention also provides a composite antibacterial agent, which is prepared by any of the preparation methods described above.

[0019] The present invention further provides an antibacterial composition comprising a matrix resin and a composite antibacterial agent, wherein the composite antibacterial agent is prepared by any of the preceding methods.

[0020] Furthermore, the mass of the composite antibacterial agent accounts for 2% to 4% of the total mass of the antibacterial composition.

[0021] Furthermore, the matrix resin can be any polymer plastic commonly used in the art, without particular limitation. Specific examples include, but are not limited to, polyethylene, polypropylene, polystyrene, polybutylene terephthalate, and polyamide 6.

[0022] Compared with the prior art, the present invention has the following beneficial effects:

[0023] The antibacterial properties of the composite antibacterial agent in this invention are achieved by releasing the oxidized halogen in the compound structure, which then inhibits or inactivates microbial cells upon contact. During the inhibition or inactivation of microorganisms, the oxidized halogen in the halogen amine antibacterial agent is consumed and loses its activity, and the N-Cl bond in its compound is converted into an NH bond. After antibacterial action, the inactive halogen amine antibacterial agent can be reacted with the material again through a hypohalite solution, which can convert the NH bond into an N-Cl bond, regain the oxidized halogen, and restore its antibacterial properties. Thus, the composite antibacterial agent in this invention possesses excellent antibacterial performance and is regenerable.

[0024] This composite antibacterial agent can meet the requirements of high antibacterial environments and expands the range of antibacterial agents. Detailed Implementation

[0025] To facilitate understanding of the present invention, a more comprehensive description will be given below with reference to specific embodiments. However, the present invention can be implemented in many different forms and is not limited to the embodiments described herein. Rather, these embodiments are provided to provide a more thorough and complete understanding of the disclosure of the present invention.

[0026] Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention pertains. The terminology used herein in the description of the invention is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention.

[0027] The specific information of the raw materials used in the following examples and comparative examples is as follows:

[0028] Polyvinylpyrrolidone, Hubei Jusheng Technology Co., Ltd.;

[0029] n-Butyl titanate, Shanghai Nuotai Chemical Co., Ltd.;

[0030] Dodecyl dimethyl benzyl ammonium chloride, Guangzhou Lili New Materials Co., Ltd.;

[0031] Acetone, Nanjing Shengqinghe Chemical Co., Ltd.

[0032] Polypropylene glycol, Jinan Tengbo Chemical Co., Ltd.;

[0033] N-Isopropylacrylamide, Shanghai Jizhi Biochemical Technology Co., Ltd.;

[0034] Potassium carbonate, Nanjing Guochen Chemical Co., Ltd.

[0035] Sodium hypochlorite, Hubei Baidu Chemical Co., Ltd.;

[0036] Deionized water, Shanghai LianShi Chemical Reagent Co., Ltd.

[0037] PBT (Model 2002U), Polyplastics, Japan;

[0038] PP (model Z30S), Maoming Petrochemical;

[0039] PE (Model 5070), Panjin Ethylene;

[0040] PA6 (model CM1017), Toray Industries, Japan;

[0041] PS (Model 350).

[0042] It should be noted that, unless otherwise specified, the preparation processes in the following embodiments are all conventional methods in the prior art, and therefore will not be described in detail; in addition, unless otherwise specified, the parts mentioned below refer to parts by weight.

[0043] The following antibacterial rate test uses test pieces with dimensions of (50mm±2mm)×(50mm±2mm)×(6mm±0.1mm), and the test is conducted 24 hours after inoculation.

[0044] Example 1

[0045] Mesoporous titanium dioxide is prepared by weighing 180g of polyvinylpyrrolidone, 160g of dodecyl dimethyl benzyl ammonium chloride, 600g of tetrabutyl titanate, 800g of acetone, and 2.0kg of deionized water, adding them to a reactor vessel, stirring and reacting at 60℃ for 6h, filtering and washing, drying in a vacuum drying oven at 40℃ for 1h, and then calcining in a muffle furnace at 400℃ for 10h to obtain mesoporous titanium dioxide.

[0046] To obtain PPG-NIPA@TiO2 particles: Weigh 200g polypropylene glycol (PPG), 160g N-isopropylacrylamide (NIPA), 180g potassium carbonate, 600g acetone, and 2.0kg deionized water, add them to a reactor vessel, and stir at room temperature for 6 hours to obtain a PPG-NIPA mixed solution; add 300g mesoporous titanium dioxide to 1.6kg of the PPG-NIPA mixed solution, stir at 40℃ for 8 hours, filter, wash, dry in a vacuum drying oven at 60℃ for 6 hours, grind through a 1000-mesh sieve to obtain PPG-NIPA@TiO2 particles.

[0047] To obtain the PPG-NIPA-Cl@TiO2 composite antibacterial agent: Weigh 200g of PPG-NIPA@TiO2 particles, 240g of sodium hypochlorite, and 1.8kg of deionized water, add them to a reactor vessel, react at room temperature for 10h, centrifuge, filter, wash, and dry in a vacuum drying oven at 50℃ for 5h to obtain the PPG-NIPA-Cl@TiO2 composite antibacterial agent, denoted as P1.

[0048] Application Example 1

[0049] Four parts of P1 were added to 96 parts of polypropylene (PP), stirred in a high-speed mixer for 10 minutes, and then added to a twin-screw extruder for co-extrusion to obtain a PP composite material, denoted as X1.

[0050] The twin-screw extruder includes six temperature zones arranged in sequence: the first temperature zone has a temperature of 170℃, the second temperature zone has a temperature of 220℃, the third temperature zone has a temperature of 230℃, the fourth temperature zone has a temperature of 240℃, the fifth temperature zone has a temperature of 240℃, the sixth temperature zone has a temperature of 240℃, the die head temperature of the twin-screw extruder is 230℃, and the screw speed is 220 r / min.

[0051] Application Comparative Example 1

[0052] Take 96 parts of PP, stir in a high-speed mixer for 10 minutes, and then add it to a twin-screw extruder for co-extrusion (process parameters are the same as in application example 1) to obtain PP composite material, denoted as D1.

[0053] The antibacterial performance data of the PP composite materials prepared in Application Example 1 and Comparative Example 1 are shown in the table below:

[0054]

[0055] As can be seen from the table above, X1 has better antibacterial properties than D1, which indicates that the antibacterial properties of the PP composite material are better after adding the antibacterial agent of this embodiment.

[0056] Example 2

[0057] Mesoporous titanium dioxide is prepared by weighing 240g of polyvinylpyrrolidone, 200g of dodecyl dimethyl benzyl ammonium chloride, 800g of tetrabutyl titanate, 1.0kg of acetone, and 2.4kg of deionized water, adding them to a reactor vessel, stirring and reacting at 80℃ for 8h, filtering and washing, drying in a vacuum drying oven at 60℃ for 3h, and then calcining in a muffle furnace at 480℃ for 16h to obtain mesoporous titanium dioxide.

[0058] To obtain PPG-NIPA@TiO2 particles: Weigh 300g of polypropylene glycol (PPG), 200g of N-isopropylacrylamide (NIPA), 220g of potassium carbonate, 800g of acetone, and 2.4kg of deionized water, and add them to a reactor vessel. Stir and react at room temperature for 8 hours to obtain a PPG-NIPA mixed solution. Add 400g of mesoporous titanium dioxide to 2.0kg of the PPG-NIPA mixed solution, stir and react at 60℃ for 12 hours, filter, wash, dry in a vacuum drying oven at 80℃ for 8 hours, and grind through a 1000-mesh sieve to obtain PPG-NIPA@TiO2 particles.

[0059] To obtain the PPG-NIPA-Cl@TiO2 composite antibacterial agent: Weigh 300g of PPG-NIPA@TiO2 particles, 300g of sodium hypochlorite, and 2.0kg of deionized water, add them to a reactor vessel, react at room temperature for 12h, centrifuge, filter, wash, and dry in a vacuum drying oven at 70℃ for 7h to obtain the PPG-NIPA-Cl@TiO2 composite antibacterial agent, denoted as P2.

[0060] Application Example 2

[0061] Two parts of P2 were added to 98 parts of polybutylene terephthalate (PBT), stirred in a high-speed mixer for 10 minutes, and then added to a twin-screw extruder for co-extrusion to obtain a PBT composite material, denoted as X2.

[0062] The twin-screw extruder includes six temperature zones arranged in sequence: the first temperature zone has a temperature of 200℃, the second temperature zone has a temperature of 230℃, the third temperature zone has a temperature of 240℃, the fourth temperature zone has a temperature of 240℃, the fifth temperature zone has a temperature of 240℃, the sixth temperature zone has a temperature of 240℃, the die head temperature of the twin-screw extruder is 240℃, and the screw speed is 300 r / min.

[0063] Application Comparative Example 2

[0064] Take 98 parts of PBT, stir it in a high-speed mixer for 10 minutes, and then add it to a twin-screw extruder for co-extrusion (process parameters are the same as in application example 2) to obtain PBT composite material, denoted as D2.

[0065] The antibacterial performance data of the PBT composite materials prepared in Application Example 2 and Comparative Example 2 are shown in the table below:

[0066]

[0067] As can be seen from the table above, X2 has better antibacterial properties than D2, which indicates that the antibacterial properties of the PBT composite material are better after adding the antibacterial agent of this embodiment.

[0068] Example 3

[0069] Mesoporous titanium dioxide is prepared by weighing 210g of polyvinylpyrrolidone, 180g of dodecyl dimethyl benzyl ammonium chloride, 700g of tetrabutyl titanate, 900g of acetone, and 2.2kg of deionized water, adding them to a reactor vessel, stirring and reacting at 70℃ for 7h, filtering and washing, drying in a vacuum drying oven at 50℃ for 2h, and then calcining in a muffle furnace at 440℃ for 13h to obtain mesoporous titanium dioxide.

[0070] To obtain PPG-NIPA@TiO2 particles: Weigh 250g polypropylene glycol (PPG), 180g N-isopropylacrylamide (NIPA), 200g potassium carbonate, 700g acetone, and 2.2kg deionized water, and add them to a reactor vessel. Stir and react at room temperature for 7 hours to obtain a PPG-NIPA mixed solution. Add 350g mesoporous titanium dioxide C and 1.8kg solution D to 1.8kg PPG-NIPA mixed solution, stir and react at 50℃ for 10 hours, filter, wash, dry in a vacuum drying oven at 70℃ for 7 hours, and grind through a 1000-mesh sieve to obtain PPG-NIPA@TiO2 particles.

[0071] To obtain the PPG-NIPA-Cl@TiO2 composite antibacterial agent: Weigh 250g of PPG-NIPA@TiO2 particles, 270g of sodium hypochlorite, and 1.9kg of deionized water, add them to a reactor vessel, react at room temperature for 11h, centrifuge, filter, wash, and dry in a vacuum drying oven at 60℃ for 6h to obtain the PPG-NIPA-Cl@TiO2 composite antibacterial agent, denoted as P3.

[0072] Application Example 3

[0073] Take 3 parts of P3 and add them to 97 parts of polyethylene (PE). Mix them in a high-speed mixer for 10 minutes, and then add them to a twin-screw extruder for co-extrusion to obtain a PE composite material, denoted as X3.

[0074] The twin-screw extruder includes six temperature zones arranged in sequence: the first temperature zone has a temperature of 120℃, the second temperature zone has a temperature of 180℃, the third temperature zone has a temperature of 180℃, the fourth temperature zone has a temperature of 180℃, the fifth temperature zone has a temperature of 180℃, and the sixth temperature zone has a temperature of 180℃. The die temperature of the twin-screw extruder is 180℃, and the screw speed is 300 r / min.

[0075] Application Comparative Example 3

[0076] Take 97 parts of PE, stir it in a high-speed mixer for 10 minutes, and then add it to a twin-screw extruder for co-extrusion (process parameters are the same as in application example 3) to obtain PE composite material, denoted as D3.

[0077] The antibacterial performance data of the PE composite materials prepared in Application Example 3 and Comparative Example 3 are shown in the table below:

[0078]

[0079] As can be seen from the table above, X3 has better antibacterial properties than D3, which indicates that the antibacterial properties of the PE composite material are better after adding the antibacterial agent in this embodiment.

[0080] Example 4

[0081] Mesoporous titanium dioxide is prepared by weighing 220g of polyvinylpyrrolidone, 190g of dodecyl dimethyl benzyl ammonium chloride, 690g of n-butyl titanate, 890g of acetone, and 2.3kg of deionized water, adding them to a reactor vessel, stirring and reacting at 75℃ for 8h, filtering and washing, drying in a vacuum drying oven at 45℃ for 2h, and then calcining in a muffle furnace at 420℃ for 12h to obtain mesoporous titanium dioxide.

[0082] To obtain PPG-NIPA@TiO2 particles: Weigh 280g polypropylene glycol (PPG), 190g N-isopropylacrylamide (NIPA), 210g potassium carbonate, 790g acetone, and 2.3kg deionized water, add them to a reactor vessel, and stir at room temperature for 7 hours to obtain a PPG-NIPA mixed solution; add 390g mesoporous titanium dioxide to 1.8kg of the PPG-NIPA mixed solution, stir at 45℃ for 9 hours, filter, wash, dry in a vacuum drying oven at 65℃ for 6 hours, grind through a 1000-mesh sieve to obtain PPG-NIPA@TiO2 particles.

[0083] To obtain the PPG-NIPA-Cl@TiO2 composite antibacterial agent: Weigh 280g of PPG-NIPA@TiO2 particles, 290g of sodium hypochlorite, and 1.9kg of deionized water, add them to a reactor vessel, react at room temperature for 11h, centrifuge, filter, wash, and dry in a vacuum drying oven at 65℃ for 7h to obtain the PPG-NIPA-Cl@TiO2 type antibacterial agent, denoted as P4.

[0084] Application Example 4

[0085] Take 2.5 parts of P4 and add it to 97.5 parts of polyamide 6 (PA6). Stir the mixture in a high-speed mixer for 10 minutes, and then add it to a twin-screw extruder for co-extrusion to obtain the PA6 composite material, denoted as X4.

[0086] The twin-screw extruder includes six temperature zones arranged in sequence: the first temperature zone has a temperature of 210℃, the second temperature zone has a temperature of 230℃, the third temperature zone has a temperature of 230℃, the fourth temperature zone has a temperature of 230℃, the fifth temperature zone has a temperature of 230℃, the sixth temperature zone has a temperature of 230℃, the die head temperature of the twin-screw extruder is 230℃, and the screw speed is 320r / min.

[0087] Application Comparative Example 4

[0088] Take 97.5 parts of PA6, stir it in a high-speed mixer for 10 minutes, and then add it to a twin-screw extruder for co-extrusion (process parameters are the same as in application example 4) to obtain PA6 composite material, denoted as D4.

[0089] Application Comparative Example 5

[0090] 2.5 parts of antibacterial nano TiO2 were added to 97.5 parts of PA6 and stirred in a high-speed mixer for 10 minutes. Then, the mixture was added to a twin-screw extruder for co-extrusion (process parameters were the same as in application comparative example 5) to obtain PA6 composite material, denoted as D5.

[0091] The antibacterial performance data of the PA6 composite materials prepared in Application Example 4, Application Comparative Example 4, and Application Comparative Example 5 are shown in the table below:

[0092]

[0093]

[0094] As can be seen from the table above, X4 has better antibacterial properties than D4 and D5, which indicates that the antibacterial properties of PA6 composite material are better after adding the antibacterial agent of the present invention.

[0095] Example 5

[0096] Mesoporous titanium dioxide is prepared by weighing 190g of polyvinylpyrrolidone, 170g of dodecyl dimethyl benzyl ammonium chloride, 690g of n-butyl titanate, 960g of acetone, and 2.1kg of deionized water, adding them to a reactor vessel, stirring and reacting at 75℃ for 7h, filtering and washing, drying in a vacuum drying oven at 55℃ for 2h, and then placing it in a muffle furnace and calcining at 400-480℃ for 10-16h to obtain mesoporous titanium dioxide C.

[0097] To obtain PPG-NIPA@TiO2 particles: Weigh 290g of polypropylene glycol (PPG), 190g of N-isopropylacrylamide (NIPA), 210g of potassium carbonate, 770g of acetone, and 2.1kg of deionized water, and add them to a reactor vessel. Stir and react at room temperature for 7 hours to obtain a PPG-NIPA mixed solution. Add 370g of mesoporous titanium dioxide to 1.7kg of the PPG-NIPA mixed solution, stir and react at 55℃ for 11 hours, filter, wash, dry in a vacuum drying oven at 75℃ for 7 hours, and grind through a 1000-mesh sieve to obtain PPG-NIPA@TiO2 particles.

[0098] To obtain the PPG-NIPA-Cl@TiO2 composite antibacterial agent: Weigh 280g of PPG-NIPA@TiO2 granules, 270g of sodium hypochlorite, and 1.95kg of deionized water, add them to a reactor vessel, react at room temperature for 11h, centrifuge, filter, wash, and dry in a vacuum drying oven at 65℃ for 6h to obtain the PPG-NIPA-Cl@TiO2 composite antibacterial agent, denoted as P5.

[0099] Application Example 5

[0100] Take 2.5 parts of P5 and add it to 97.5 parts of styrene (PS). Stir the mixture in a high-speed mixer for 10 minutes, and then add it to a twin-screw extruder for co-extrusion to obtain a PS composite material, denoted as X5.

[0101] The twin-screw extruder includes six temperature zones arranged in sequence: the first temperature zone has a temperature of 160℃, the second temperature zone has a temperature of 200℃, the third temperature zone has a temperature of 200℃, the fourth temperature zone has a temperature of 200℃, the fifth temperature zone has a temperature of 200℃, the sixth temperature zone has a temperature of 200℃, the die head temperature of the twin-screw extruder is 200℃, and the screw speed is 280 r / min.

[0102] Application Comparative Example 6

[0103] Take 97.5 parts of PS, stir it in a high-speed mixer for 10 minutes, and then add it to a twin-screw extruder for co-extrusion (process parameters are the same as in application example 5) to obtain PS composite material, denoted as D6.

[0104] Application Comparative Example 7

[0105] Take 2.5 parts of antibacterial agent chitosan micro powder and add it to 97.5 parts of PS. Stir the mixture in a high-speed mixer for 10 minutes, and then add it to a twin-screw extruder for co-extrusion (process parameters are the same as in application example 5) to obtain PS composite material, denoted as D7.

[0106] The antibacterial performance data of the PS composite materials used in Application Examples 5, 6, and 7 are shown in the table below:

[0107]

[0108] As can be seen from the table above, X5 has better antibacterial properties than D6 and D7, which indicates that the PS composite material has better antibacterial performance after adding the antibacterial agent in this embodiment.

[0109] The technical features of the above embodiments can be combined in any way. For the sake of brevity, not all possible combinations of the technical features in the above embodiments are described. However, as long as there is no contradiction in the combination of these technical features, they should be considered to be within the scope of this specification.

[0110] The embodiments described above are merely illustrative of several implementations of the present invention, and while the descriptions are relatively specific and detailed, they should not be construed as limiting the scope of the invention patent. It should be noted that those skilled in the art can make various modifications and improvements without departing from the concept of the present invention, and these all fall within the protection scope of the present invention. Therefore, the protection scope of this invention patent should be determined by the appended claims.

Claims

1. An antibacterial composition comprising a base resin selected from one of polyethylene, polystyrene, polybutylene terephthalate, polyamide 6 and a complex antibacterial agent, characterized in that, The mass of the composite antibacterial agent accounts for 2-4% of the total mass of the antibacterial composition, and the preparation method of the composite antibacterial agent comprises the following steps: Providing mesoporous titanium dioxide; Obtaining PPG-NIPA@TiO2 particles: mixing polyoxypropylene glycol, N-isopropyl acrylamide, potassium carbonate, acetone and deionized water in a mass ratio of (20-30):(16-20):(18-22):(60-80):(200-240) and stirring at room temperature for 6-8 h to obtain a mixed solution, adding the mesoporous titanium dioxide to the mixed solution, stirring at 40-60℃ for 8-12 h to obtain PPG-NIPA@TiO2 particles, and the mass ratio of the mesoporous titanium dioxide to the mixed solution is (30-40):(160-200). Obtaining PPG-NIPA-Cl@TiO2 composite antibacterial agent: mixing PPG-NIPA@TiO2 particles, hypochlorite and deionized water in a mass ratio of (20-30):(24-30):(180-200) and reacting at room temperature for 10-12 h to obtain PPG-NIPA-Cl@TiO2 composite antibacterial agent.

2. The antimicrobial composition of claim 1, wherein, The specific steps for providing mesoporous titanium dioxide are: mixing polyvinylpyrrolidone, dodecyl dimethyl benzyl ammonium chloride, n-butyl titanate, acetone and deionized water at 60-80℃ and stirring for 6-8 h, filtering, drying, and calcining at 400-480℃ for 10-16 h to obtain mesoporous titanium dioxide.

3. The antimicrobial composition of claim 2, wherein, In the step of providing mesoporous titanium dioxide, the mass ratio of polyvinylpyrrolidone, dodecyl dimethyl benzyl ammonium chloride, n-butyl titanate, acetone and deionized water is (18-24):(16-20):(60-80):(80-100):(200-240).

4. The antimicrobial composition of claim 1, wherein, The hypochlorite is selected from sodium hypochlorite, potassium hypochlorite or calcium hypochlorite.

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