Long-acting antibacterial adsorbent filler and method for preparing the same

Abstract

The application discloses a long-acting antibacterial adsorption filler and a preparation method thereof, and comprises the following steps: S1, preparation of composite activated alumina; S2, preparation of aminated composite alumina; S3, preparation of organically modified composite alumina; and S4, preparation of the long-acting antibacterial adsorption filler. The long-acting antibacterial adsorption filler is prepared by loading cerium and bismuth composite oxides on an activated alumina substrate, and then bridging with a silane coupling agent, and sequentially introducing maleic anhydride, 2,3-epoxypropyl trimethyl ammonium chloride and 2-mercaptothiazoline, so that the finally-prepared filler integrates multiple functions such as physical adsorption, chemical adsorption, contact sterilization and slow-release sterilization. The method effectively solves the technical problems of single function of a traditional adsorbent, inability to sterilize and easy secondary pollution, and achieves omnibearing and long-acting purification of indoor air pollutants.

Description

TECHNICAL FIELD

[0001] The present application belongs to the technical field of air adsorption materials, and particularly relates to a long-acting antibacterial adsorption filler and a preparation method thereof. BACKGROUND

[0002] With the acceleration of industrialization and urbanization, the problem of indoor and outdoor air pollution is becoming increasingly serious. Volatile organic compounds (VOCs, such as formaldehyde, benzene series), nitrogen oxides, sulfur oxides, and microorganisms such as bacteria and viruses suspended in the air jointly pose a serious threat to human health and living environment. Therefore, developing efficient air purification technology and core materials-purification filler has become a research hotspot in the field of environmental science and material science. Air adsorption sterilization and purification filler, as a kind of key functional material that can remove chemical pollutants and biological pollutants at normal temperature and pressure, is widely used in air purifiers, fresh air systems, air conditioner filter screens, and industrial waste gas treatment fields.

[0003] At present, the air purification fillers on the market mainly rely on the principle of physical adsorption, among which activated carbon and molecular sieve are the representatives. Activated carbon has a large specific surface area and developed pore structure, and shows good adsorption capacity for a variety of volatile organic compounds, but its adsorption force is weak and easy to desorb, resulting in secondary pollution caused by the desorption of pollutants. More importantly, the activated carbon pores provide rich nutrients and shelters for bacteria and mold after adsorbing organic matter, which makes them reproduce in large quantities and become a new source of pollution. Although molecular sieve has regular pores and high selectivity for specific small molecules, its adsorption capacity is limited and the cost is high, and it also does not have sterilization capacity. To solve the above problems, the existing technology usually adopts the method of physical blending or loading of adsorption materials and antibacterial agents to endow them with sterilization performance.

[0004] In order to overcome the shortcomings of traditional adsorption materials, the prior art mainly improves in the following ways: 1. loading metal ions or compounds with antibacterial activity on porous carriers (such as activated carbon, alumina, zeolite, etc.), such as silver ions, copper ions, zinc oxide or titanium dioxide, etc. Among them, the technology of loading silver ions is the most common, which uses the slow release of silver ions to kill microorganisms. However, such fillers generally have the problem of easy loss and migration of metal ions under changes in air humidity or long-term use, resulting in poor durability of their antibacterial performance. In addition, photocatalytic antibacterial agents (such as titanium dioxide) are severely dependent on ultraviolet light to function, and are completely ineffective in the absence of light or weak light (such as inside equipment, at night), which limits the application scenarios. 2. loading organic small molecules or polymers with antibacterial function on the surface of porous carriers through physical adsorption or impregnation coating. For example, quaternary ammonium salts, guanidine and other organic antibacterial agents are used. The advantage of this method is that there are many types of antibacterial agents and a wide range of bactericidal spectrum. However, its main technical defect is that the combination between the antibacterial agent and the carrier is mainly weak van der Waals force or physical entanglement, which has poor binding firmness. Under long-term airflow scouring, the antibacterial agent molecules are easy to fall off, which not only reduces the antibacterial time effectiveness of the filler, but also releases the fallen antibacterial agents into the air, which may become new potential chemical pollutants and pose a safety hazard.

[0005] In summary, there is an urgent need in the art to develop a long-acting antibacterial adsorption filler that can stably load antibacterial functional components on the adsorption carrier. SUMMARY

[0006] In view of the shortcomings of the prior art, the purpose of the present application is to provide a long-acting antibacterial adsorption filler and a preparation method thereof.

[0007] To achieve the above-mentioned purpose, the present application provides the following technical solutions:

[0008] A preparation method of a long-acting antibacterial adsorption filler, comprising the following steps:

[0009] S1, adding active alumina to deionized water, ultrasonic treatment and drying to obtain pretreated active alumina; then immersing the pretreated active alumina in a mixed solution, taking out after impregnation, drying, repeating the immersion-drying process, and then calcining to obtain composite active alumina;

[0010] S2, adding the composite active alumina in step S1 to toluene, then adding γ-aminopropyl triethoxysilane, and performing reflux reaction. After the reaction is completed, filtering, washing and drying to obtain aminated composite alumina;

[0011] S3, adding the aminated composite alumina in step S2 into DMF, then adding maleic anhydride, stirring under nitrogen atmosphere, after the reaction is completed, filtering, washing, drying to obtain the organic composite alumina;

[0012] S4, adding the organic composite alumina in step S3 into deionized water, then adding 2-mercaptothiazoline, 2, 3-epoxypropyl trimethyl ammonium chloride, triethylamine, constant temperature reaction, after the reaction is completed, filtering, washing, drying to obtain the long-acting antibacterial adsorption filler.

[0013] Preferably, the frequency of the ultrasonic treatment in step S1 is 20-40 kHz, the power is 300-400 W, and the time is 1-2 h.

[0014] Preferably, the preparation method of the mixed solution in step S1 is as follows: adding cerium nitrate, bismuth nitrate and citric acid into deionized water and stirring uniformly to obtain the mixed solution; the mass ratio of the cerium nitrate, bismuth nitrate, citric acid and deionized water is 7-10:8-12:1-2:1000.

[0015] In the present application, the active alumina is pretreated by ultrasonic, effectively cleaning its surface, and then the cerium (Ce) and bismuth (Bi) precursors are loaded on the active alumina by the impregnation-calcination method. The citric acid is introduced into the impregnation solution as a chelating agent, which can form stable soluble complexes with Ce and Bi ions, ensuring the molecular-level uniform dispersion of metal ions on the surface of the porous carrier, effectively avoiding the premature hydrolysis and agglomeration during the drying process.

[0016] Preferably, in step S1, the ratio of the pretreated alumina to the mixed solution is 1:10-15, the temperature of the immersion is 25-30℃, the time is 2-3 h, the temperature of the drying is 80-90℃, the time is 5-6 h, and the repeating times of the immersion-drying process is 4-6 times; the calcination temperature is 500-600℃, and the time is 3-4 h.

[0017] In the present application, through the multiple immersion-drying processes, the loading capacity of active alumina for cerium and bismuth is improved, and then calcination at high temperature of 500-600℃ not only converts the precursors into CeO2 / Bi2O3 nanocrystals with catalytic activity in situ, but also activates the alumina carrier, forming a composite material with high specific surface area and rich pore structure, which integrates physical adsorption, chemical adsorption and catalytic degradation three potential functions, providing a solid foundation for further reactions.

[0018] Preferably, in step S2, the mass ratio of the composite active alumina to γ-aminopropyl triethoxysilane is 100:3-4, and the reflux reaction time is 12-16 h.

[0019] In the present application, gamma-aminopropyltriethoxysilane is firmly grafted to the composite active alumina in the form of covalent bond, so that the composite active alumina is changed from inorganic and hydrophilic hydroxyl surface to organic surface with high reactive amino group, thereby providing reaction conditions for the next step.

[0020] Preferably, in step S3, the mass ratio of the aminated composite alumina and maleic anhydride is 100:2-2.5.

[0021] Preferably, in step S3, the temperature of the stirring reaction is 25-35℃, and the time is 7-9h.

[0022] In the present application, the nucleophilic ring-opening reaction of amino group to maleic anhydride introduces carboxyl and carbon-carbon double bond on the surface of the composite active alumina at the same time, and the chemical reactivity and reaction mechanism of the two functional groups are completely different, thereby providing a basis for the subsequent parallel bonding of two different functional molecules in the same reaction system through different mechanisms such as ring-opening and Michael addition.

[0023] Preferably, in step S4, the mass ratio of the organic composite alumina, 2-mercaptothiazoline, 2,3-epoxypropyltrimethylammonium chloride and triethylamine is 100:1.8-2.3:2-2.7:2.5-3.

[0024] Preferably, in step S4, the temperature of the constant temperature reaction is 60-70℃, and the time is 2-3h.

[0025] In the present application, the organic composite alumina is placed in an aqueous environment, and triethylamine is used as a catalyst. The triethylamine converts the carboxyl group into carboxylate ion with stronger nucleophilicity, and then reacts with the epoxy group of 2,3-epoxypropyltrimethylammonium chloride to covalently graft the 2,3-epoxypropyltrimethylammonium chloride with contact sterilization ability to the filler; at the same time, the triethylamine can also catalyze the Michael addition reaction of the mercapto group of 2-mercaptothiazoline to the carbon-carbon double bond on the filler, thereby firmly anchoring the 2-mercaptothiazoline with slow-release antibacterial function to the filler through stable thioether bond. The synergistic effect of the two molecules improves the long-acting antibacterial property of the filler.

[0026] The present application also protects a long-acting antibacterial adsorption filler prepared by the above method.

[0027] Compared with the prior art, the present application has the following beneficial effects:

[0028] (1) The long-acting antibacterial adsorption filler provided by the present application is prepared by first loading Ce / Bi composite oxides with excellent adsorption performance on volatile organic compounds and acidic gases on an activated alumina substrate, and then introducing maleic anhydride, 2,3-epoxypropyltrimethylammonium chloride and 2-mercaptothiazoline as intermediates of a functional platform in sequence through the bridging of a silane coupling agent, so that the filler integrates physical adsorption, chemical adsorption, contact sterilization and slow-release sterilization functions; the method successfully couples the high-efficiency adsorption of volatile organic compounds, the electrostatic capture of dust particles and the contact killing and long-acting inhibition of microorganisms into a single filler, effectively solves the technical problems of single function and secondary pollution caused by the inability to kill bacteria of traditional adsorbents, and realizes the comprehensive and long-acting purification of indoor air pollutants.

[0029] (2) The long-acting antibacterial adsorption filler provided by the present application is prepared by modifying the activated alumina with Ce / Bi bimetallic oxides to obtain composite activated alumina with adsorption and catalytic functions; the large specific surface area of the composite activated alumina provides a basis for physical adsorption, and the uniformly loaded CeO 2 / Bi2O3 nanocrystals exhibit excellent chemical adsorption activity on formaldehyde, especially the oxygen storage / release characteristics of CeO2, which enables it to catalytically oxidize a variety of organic pollutants at room temperature or low temperature; the synergistic effect of adsorption and catalytic degradation not only improves the removal efficiency and capacity of the filler for chemical pollutants, but also enables in-situ degradation of some adsorbed pollutants, thereby prolonging the service life of the filler; then, the composite activated alumina is reacted with γ-aminopropyltriethoxysilane to convert the inorganic and hydrophilic hydroxyl surface of the composite activated alumina to an organic surface with high-reactivity amino groups; subsequently, the amino-functionalized composite alumina is reacted with maleic anhydride to introduce carboxyl groups and carbon-carbon double bonds, which facilitates subsequent reactions.

[0030] (3) The long-acting antibacterial adsorption filler provided by the present application introduces two antibacterial small molecules, 2,3-epoxypropyltrimethylammonium chloride and 2-mercaptothiazoline, onto the filler through covalent bonding; the fixed 2,3-epoxypropyltrimethylammonium chloride imparts permanent positive charges to the surface of the filler, which can efficiently adsorb bacteria, viruses and other microorganisms in the air through electrostatic attraction, and destroy the cell membrane through its quaternary ammonium salt structure to achieve non-migratory contact sterilization; the 2-mercaptothiazoline anchored through a thioether bond can be slowly released in the use environment to continuously inhibit the activity and reproduction of microorganisms on the surface of the filler and in the surrounding air; the synergistic effect of the two antibacterial agents ensures the cleanliness of the adsorption filler during long-term use and avoids the biological pollution risk of traditional fillers. BRIEF DESCRIPTION OF DRAWINGS

[0031] Figure 1 is the product diagram prepared by the embodiment 1 of the present application. DETAILED DESCRIPTION

[0032] The technical solutions in the embodiments of the present application will be clearly and completely described below with reference to the drawings in the embodiments of the present application. Obviously, the described embodiments are only a part of the embodiments of the present application, rather than all the embodiments of the present application. Based on the embodiments in the present application, all the other embodiments obtained by those skilled in the art without creative work fall within the protection scope of the present application.

[0033] Unless otherwise specified, the chemical reagents and materials in the present application are purchased through market channels or synthesized by raw materials purchased through market channels.

[0034] The particle size of the active alumina is 3-5mm, the specific surface area is 280-360m 2 / g, and the pore volume is 0.4-0.5cm 3 / g.

[0035] Embodiment 1

[0036] A preparation method of a long-acting antibacterial adsorption filler, comprising the following steps:

[0037] S1, active alumina is added to deionized water, and after ultrasonic treatment under the condition of a frequency of 20 kHz and a power of 350 W for 1.5 h, the active alumina is dried to obtain pretreated active alumina; then 100 g of the pretreated active alumina is immersed in 1.3 kg of a mixed solution, taken out after immersion at 27℃ for 2.5 h, and dried at 85℃ for 5.5 h; the immersion-drying process is repeated 5 times, and then the composite active alumina is obtained by calcining at 550℃ for 3.5 h;

[0038] S2, 100 g of the composite active alumina in step S1 is added to 1 L of toluene, followed by adding 3.5 g of γ-aminopropyltriethoxysilane, and refluxing at 110℃ for 14 h; after the reaction is completed, the product is filtered, washed, and dried to obtain aminated composite alumina;

[0039] S3, 100 g of the aminated composite alumina in step S2 is added to 1 L of DMF, followed by adding 2.3 g of maleic anhydride, and stirring at 30℃ for 8 h under a nitrogen atmosphere; after the reaction is completed, the product is filtered, washed, and dried to obtain organic composite alumina;

[0040] S4, 100g of the organically modified composite alumina in step S3 is added into 1.5L of deionized water, then 2g of 2-mercaptothiazoline, 2.4g of 2,3-epoxypropyl trimethyl ammonium chloride, 2.7g of triethylamine are added, and the reaction is carried out at 65℃ for 2.5h. After the reaction is completed, the product is filtered, washed and dried to obtain the long-acting antibacterial adsorption filler.

[0041] In step S1, the mixed solution is prepared by adding 9g of cerium nitrate, 10g of bismuth nitrate and 1.5g of citric acid into 1000g of deionized water and stirring uniformly.

[0042] Example 2

[0043] A method for preparing a long-acting antibacterial adsorption filler comprises the following steps:

[0044] S1, active alumina is added into deionized water, and then ultrasonic treatment is carried out under the condition of 30kHz frequency and 300W power for 2h, and then the product is dried to obtain pretreated active alumina; then 100g of the pretreated active alumina is immersed into 1kg of a mixed solution, and then the product is taken out after being immersed at 25℃ for 3h and dried at 80℃ for 6h, and the immersion-drying process is repeated for 4 times, and then the product is calcined at 500℃ for 4h to obtain composite active alumina;

[0045] S2, 100g of the composite active alumina in step S1 is added into 1L of toluene, then 3g of γ-aminopropyl triethoxysilane is added, and the reaction is carried out at 110℃ for 12h. After the reaction is completed, the product is filtered, washed and dried to obtain aminated composite alumina;

[0046] S3, 100g of the aminated composite alumina in step S2 is added into 1L of DMF, then 2g of maleic anhydride is added, and the reaction is carried out at 25℃ under nitrogen atmosphere for 9h. After the reaction is completed, the product is filtered, washed and dried to obtain organically modified composite alumina;

[0047] S4, 100g of the organically modified composite alumina in step S3 is added into 1.5L of deionized water, then 1.8g of 2-mercaptothiazoline, 2g of 2,3-epoxypropyl trimethyl ammonium chloride, 2.5g of triethylamine are added, and the reaction is carried out at 60℃ for 3h. After the reaction is completed, the product is filtered, washed and dried to obtain the long-acting antibacterial adsorption filler.

[0048] In step S1, the mixed solution is prepared by adding 7g of cerium nitrate, 8g of bismuth nitrate and 1g of citric acid into 1000g of deionized water and stirring uniformly.

[0049] Example 3

[0050] A method for preparing a long-acting antibacterial adsorption filler comprises the following steps:

[0051] S1, active alumina was added into deionized water, and then was treated by ultrasonic under the condition of 40 kHz frequency and 400 W power for 1 h, and then was dried to obtain pretreated active alumina; then 100 g of the pretreated active alumina was immersed into 1.5 kg of mixed solution, and then was taken out after being immersed at 30℃ for 2 h, and then was dried at 90℃ for 5 h, and then the immersion-drying process was repeated for 6 times, and then was calcined at 600℃ for 3 h to obtain composite active alumina;

[0052] S2, 100 g of the composite active alumina in step S1 was added into 1 L of toluene, and then 4 g of γ-aminopropyl triethoxysilane was added, and then was reacted by refluxing at 110℃ for 16 h, and then was filtered, washed and dried after the reaction was completed to obtain aminated composite alumina;

[0053] S3, 100 g of the aminated composite alumina in step S2 was added into 1 L of DMF, and then 2.5 g of maleic anhydride was added, and then was stirred at 35℃ under nitrogen atmosphere for 7 h, and then was filtered, washed and dried after the reaction was completed to obtain organic composite alumina;

[0054] S4, 100 g of the organic composite alumina in step S3 was added into 1.5 L of deionized water, and then 2.3 g of 2-mercaptothiazoline, 2.7 g of 2,3-epoxypropyl trimethyl ammonium chloride and 3 g of triethylamine were added, and then was reacted at 70℃ for 2 h, and then was filtered, washed and dried after the reaction was completed to obtain the long-acting antibacterial adsorption filler.

[0055] In step S1, the mixed solution was prepared by adding 10 g of cerium nitrate, 12 g of bismuth nitrate and 2 g of citric acid into 1000 g of deionized water and stirring uniformly.

[0056] Comparative Example 1

[0057] A preparation method of a long-acting antibacterial adsorption filler, comprising the following steps:

[0058] S1, active alumina was added into deionized water, and then was treated by ultrasonic under the condition of 20 kHz frequency and 350 W power for 1.5 h, and then was dried to obtain pretreated active alumina; then 100 g of the pretreated active alumina was immersed into 1.3 kg of mixed solution, and then was taken out after being immersed at 27℃ for 2.5 h, and then was dried at 85℃ for 5.5 h, and then the immersion-drying process was repeated for 5 times, and then was calcined at 550℃ for 3.5 h to obtain composite active alumina;

[0059] S2, 100 g of the composite active alumina in step S1 was added into 1 L of toluene, and then 3.5 g of γ-aminopropyl triethoxysilane was added, and then was reacted by refluxing at 110℃ for 14 h, and then was filtered, washed and dried after the reaction was completed to obtain aminated composite alumina;

[0060] S3, 100 g of the aminated composite alumina in step S2 was added into 1 L of DMF, then 2.3 g of maleic anhydride was added, and the reaction was stirred at 30°C for 8 h under a nitrogen atmosphere. After the reaction was completed, the product was filtered, washed, and dried to obtain the organically modified composite alumina;

[0061] S4, 100 g of the organically modified composite alumina in step S3 was added into 1.5 L of deionized water, then 2 g of 2-mercaptothiazoline, 2.4 g of 2,3-epoxypropyl trimethyl ammonium chloride, and 2.7 g of triethylamine were added, and the reaction was carried out at 65°C for 2.5 h. After the reaction was completed, the product was filtered, washed, and dried to obtain the long-acting antibacterial adsorption filler.

[0062] The preparation method of the mixed solution in step S1 is as follows: 9 g of cerium nitrate and 1.5 g of citric acid were added into 1000 g of deionized water, and the mixture was stirred to obtain the mixed solution.

[0063] Compared with Example 1, bismuth oxide was not introduced on the activated alumina in the present comparative example.

[0064] Comparative Example 2

[0065] A method for preparing a long-acting antibacterial adsorption filler, comprising the following steps:

[0066] S1, activated alumina was added into deionized water, and the mixture was ultrasonically treated at a frequency of 20 kHz and a power of 350 W for 1.5 h, and then dried to obtain pretreated activated alumina. Then, 100 g of the pretreated activated alumina was immersed in 1.3 kg of a mixed solution, and the mixture was immersed at 27°C for 2.5 h, and then taken out and dried at 85°C for 5.5 h. The immersion-drying process was repeated 5 times, and then the mixture was calcined at 550°C for 3.5 h to obtain composite activated alumina.

[0067] S2, 100 g of the composite activated alumina in step S1 was added into 1 L of toluene, then 3.5 g of γ-aminopropyl triethoxysilane was added, and the reaction was refluxed at 110°C for 14 h. After the reaction was completed, the product was filtered, washed, and dried to obtain aminated composite alumina.

[0068] S3, 100 g of the aminated composite alumina in step S2 was added into 1 L of DMF, then 2.3 g of maleic anhydride was added, and the reaction was stirred at 30°C for 8 h under a nitrogen atmosphere. After the reaction was completed, the product was filtered, washed, and dried to obtain the organically modified composite alumina;

[0069] S4, 100 g of the organic compound composite alumina in step S3 is added into 1.5 L of deionized water, then 2 g of 2-mercaptothiazoline, 2.4 g of 2,3-epoxypropyl trimethyl ammonium chloride, and 2.7 g of triethylamine are added, and the mixture is reacted at 65°C for 2.5 h. After the reaction is completed, the mixture is filtered, washed, and dried to obtain the long-acting antibacterial adsorption filler.

[0070] The preparation method of the mixed solution in step S1 is as follows: 10 g of bismuth nitrate and 1.5 g of citric acid are added into 1000 g of deionized water, and the mixture is stirred uniformly to obtain the mixed solution.

[0071] Compared with Example 1, the cerium oxide is not introduced onto the active alumina in the present comparative example.

[0072] Comparative Example 3

[0073] A preparation method of a long-acting antibacterial adsorption filler includes the following steps:

[0074] S1, active alumina is added into deionized water, and the mixture is ultrasonically treated under the condition of a frequency of 20 kHz and a power of 350 W for 1.5 h, and then dried to obtain pretreated active alumina;

[0075] S2, 100 g of the pretreated active alumina in step S1 is added into 1 L of toluene, then 3.5 g of γ-aminopropyl triethoxysilane is added, and the mixture is refluxed at 110°C for 14 h. After the reaction is completed, the mixture is filtered, washed, and dried to obtain aminated composite alumina;

[0076] S3, 100 g of the aminated composite alumina in step S2 is added into 1 L of DMF, then 2.3 g of maleic anhydride is added, and the mixture is stirred at 30°C for 8 h under a nitrogen atmosphere. After the reaction is completed, the mixture is filtered, washed, and dried to obtain organic compound composite alumina;

[0077] S4, 100 g of the organic compound composite alumina in step S3 is added into 1.5 L of deionized water, then 2 g of 2-mercaptothiazoline, 2.4 g of 2,3-epoxypropyl trimethyl ammonium chloride, and 2.7 g of triethylamine are added, and the mixture is reacted at 65°C for 2.5 h. After the reaction is completed, the mixture is filtered, washed, and dried to obtain the long-acting antibacterial adsorption filler.

[0078] Compared with Example 1, the bismuth cerium oxide is not introduced onto the active alumina in the present comparative example.

[0079] Comparative Example 4

[0080] A preparation method of a long-acting antibacterial adsorption filler includes the following steps:

[0081] S1, the active alumina is added into deionized water, and is treated by ultrasonic under the condition that the frequency is 20 kHz and the power is 350 W for 1.5 h, and then is dried to obtain pretreated active alumina; then 100 g of the pretreated active alumina is immersed into 1.3 kg of a mixed solution, taken out after being immersed at 27 ℃ for 2.5 h, and dried at 85 ℃ for 5.5 h; the immersion-drying process is repeated for 5 times, and then is calcined at 550 ℃ for 3.5 h to obtain composite active alumina;

[0082] S2, 100 g of the composite active alumina in step S1 is added into 1 L of toluene, and then 3.5 g of γ-aminopropyltriethoxysilane is added, and the reaction is carried out under reflux at 110 ℃ for 14 h; after the reaction is completed, filtration, washing and drying are carried out to obtain aminated composite alumina;

[0083] S3, 100 g of the aminated composite alumina in step S2 is added into 1 L of DMF, and then 2.3 g of maleic anhydride is added, and the reaction is carried out under stirring at 30 ℃ for 8 h under nitrogen atmosphere; after the reaction is completed, filtration, washing and drying are carried out to obtain organic composite alumina;

[0084] S4, 100 g of the organic composite alumina in step S3 is added into 1.5 L of deionized water, and then 2 g of 2-mercaptothiazoline and 2.7 g of triethylamine are added, and the reaction is carried out at constant temperature at 65 ℃ for 2.5 h; after the reaction is completed, filtration, washing and drying are carried out to obtain the long-acting antibacterial adsorption filler.

[0085] In step S1, the mixed solution is prepared by the following method: 9 g of cerium nitrate, 10 g of bismuth nitrate and 1.5 g of citric acid are added into 1000 g of deionized water, and then are stirred uniformly to obtain the mixed solution.

[0086] Compared with example 1, the 2,3-epoxypropyltrimethylammonium chloride is not introduced into the adsorption filler in the present comparative example.

[0087] Comparative example 5

[0088] A preparation method of a long-acting antibacterial adsorption filler, comprising the following steps:

[0089] S1, the active alumina is added into deionized water, and is treated by ultrasonic under the condition that the frequency is 20 kHz and the power is 350 W for 1.5 h, and then is dried to obtain pretreated active alumina; then 100 g of the pretreated active alumina is immersed into 1.3 kg of a mixed solution, taken out after being immersed at 27 ℃ for 2.5 h, and dried at 85 ℃ for 5.5 h; the immersion-drying process is repeated for 5 times, and then is calcined at 550 ℃ for 3.5 h to obtain composite active alumina;

[0090] S2, 100 g of the composite activated alumina in step S1 was added into 1 L of toluene, then 3.5 g of γ-aminopropyltriethoxysilane was added, and the reaction was carried out at 110°C for 14 h. After the reaction was completed, filtration, washing and drying were carried out to obtain aminated composite alumina;

[0091] S3, 100 g of the aminated composite alumina in step S2 was added into 1 L of DMF, then 2.3 g of maleic anhydride was added, and the reaction was carried out at 30°C for 8 h under nitrogen atmosphere. After the reaction was completed, filtration, washing and drying were carried out to obtain organic composite alumina;

[0092] S4, 100 g of the organic composite alumina in step S3 was added into 1.5 L of deionized water, then 2.4 g of 2,3-epoxypropyltrimethylammonium chloride and 2.7 g of triethylamine were added, and the reaction was carried out at 65°C for 2.5 h. After the reaction was completed, filtration, washing and drying were carried out to obtain the long-acting antibacterial adsorption filler.

[0093] In step S1, the mixed solution was prepared as follows: 9 g of cerium nitrate, 10 g of bismuth nitrate and 1.5 g of citric acid were added into 1000 g of deionized water, and stirring was carried out to obtain the mixed solution.

[0094] Compared with Example 1, the 2-mercaptothiazoline was not introduced on the adsorption filler in the present comparative example.

[0095] Comparative Example 6

[0096] A method for preparing a long-acting antibacterial adsorption filler, comprising the following steps:

[0097] S1, activated alumina was added into deionized water, and ultrasonic treatment was carried out under the condition of a frequency of 20 kHz and a power of 350 W for 1.5 h, and then drying was carried out to obtain pretreated activated alumina. Then 100 g of the pretreated activated alumina was immersed into 1.3 kg of a mixed solution, and the immersion-drying process was repeated 5 times after the immersion was carried out at 27°C for 2.5 h and the drying was carried out at 85°C for 5.5 h. Then calcination was carried out at 550°C for 3.5 h to obtain composite activated alumina.

[0098] S2, 100 g of the composite activated alumina in step S1 was added into 250 mL of anhydrous ethanol, then 2 g of 2-mercaptothiazoline and 2.4 g of 2,3-epoxypropyltrimethylammonium chloride were added, and stirring was carried out. After the immersion was carried out at room temperature for 2 h, the ethanol was removed by rotary evaporation under reduced pressure to obtain the long-acting antibacterial adsorption filler.

[0099] In step S1, the mixed solution was prepared as follows: 9 g of cerium nitrate, 10 g of bismuth nitrate and 1.5 g of citric acid were added into 1000 g of deionized water, and stirring was carried out to obtain the mixed solution.

[0100] Compared with Example 1, the adsorption filler of the present comparative example is prepared by physical blending of composite activated alumina with 2-mercaptothiazoline and 2,3-epoxypropyl trimethyl ammonium chloride.

[0101] The long-acting antibacterial adsorption filler prepared from Examples 1-3 and Comparative Examples 1-6 is subjected to performance testing, specifically as follows: formaldehyde removal rate and toluene removal rate testing is tested according to the standard QB / T 2761-2024 "Method for testing the purification effect of indoor air purification products", and the formaldehyde initial concentration is 1.2 mg / m 3 In an environmental test chamber, 10.0 g of the adsorbent material to be tested is evenly spread on a sample tray, the test temperature is (23±2)℃, and the relative humidity is 50±15) %RH. For formaldehyde testing, the initial concentration of formaldehyde is 1.2 mg / m 3 For toluene testing, the initial concentration of toluene is 4 mg / m 3 The circulating fan in the chamber is turned on to allow the air to mix thoroughly, and the timing starts from this time. After 8 h, sampling is performed, the residual concentration of pollutants in the chamber is analyzed, and the removal rate of adsorption is calculated; the antibacterial rate is tested according to GB / T 21510-2024 "Method for testing the antibacterial performance of nano inorganic materials", and the test strain is Escherichia coli; the circulation test is as follows: 5 g of the material is placed in a sealed container, and the experimental gas containing 0.5 mg / m 3 PM2.5 particles and air with a humidity of 90%RH are introduced, adsorbed for 1 h, then soaked in sterile saline containing 10 7 CFU / mL of Escherichia coli, and shaken for 2 h. After filtration, the material is washed with sterile water and then with anhydrous ethanol twice, and vacuum dried at 60℃. The regenerated adsorbent material is obtained, and this is one complete "adsorption-regeneration" cycle. The antibacterial rate after 20 cycles is tested; the test results are shown in Table 1.

[0102] Table 1

[0103]

[0104] As can be seen from Table 1, the long-acting antibacterial adsorption filler prepared by the present application has the functions of efficiently removing formaldehyde and toluene, and also has excellent antibacterial properties and long-acting antibacterial properties, and has good application prospects.

[0105] The above content is a further detailed description of the present application in combination with specific implementation examples, and cannot be considered as limiting the specific implementation of the present application to these descriptions. For ordinary skilled persons in the technical field to which the present application belongs, a number of simple deductions or substitutions can be made without departing from the concept of the present application, and all of these should be considered as falling within the protection scope of the present application.

[0106] Those skilled in the art can easily understand that the above description is only the preferred embodiment of the present application, and is not intended to limit the present application. Any modification, equivalent replacement and improvement made within the spirit and principle of the present application shall be included in the protection scope of the present application.

Claims

1. A method for preparing a long-lasting antibacterial adsorbent packing, characterized in that, Includes the following steps: S1. Add activated alumina to deionized water, sonicate and then dry to obtain pretreated activated alumina. The pretreated activated alumina was then immersed in the mixed solution, removed after immersion, dried, and this immersion-drying process was repeated. Subsequently, it was calcined to obtain composite activated alumina. S2. Add the composite activated alumina to toluene, then add γ-aminopropyltriethoxysilane and reflux the reaction. After the reaction is complete, the aminated composite alumina is obtained. S3. Add the aminated composite alumina to DMF, then add maleic anhydride, and stir the reaction under a nitrogen atmosphere. After the reaction is complete, the organic composite alumina is obtained. S4. Add organic composite alumina to deionized water, then add 2-mercaptothiazoline, 2,3-epoxypropyltrimethylammonium chloride and triethylamine, and carry out a constant temperature reaction. After the reaction is completed, the long-lasting antibacterial adsorption filler is obtained. The preparation method of the mixed solution in step S1 is as follows: add cerium nitrate, bismuth nitrate, and citric acid to deionized water and stir evenly to obtain the solution; the mass ratio of cerium nitrate, bismuth nitrate, citric acid, and deionized water is 7-10:8-12:1-2:1000.

2. The preparation method according to claim 1, characterized in that, The ultrasonic treatment in step S1 has a frequency of 20-40kHz, a power of 300-400W, and a duration of 1-2h.

3. The preparation method according to claim 1, characterized in that, In step S1, the mass ratio of the pretreated activated alumina to the mixed solution is 1:10-15; the immersion temperature is 25-30℃ and the time is 2-3 hours; the drying temperature is 80-90℃ and the time is 5-6 hours; the immersion-drying process is repeated 4-6 times; and the calcination temperature is 500-600℃ and the time is 3-4 hours.

4. The preparation method according to claim 1, characterized in that, In step S2, the mass ratio of the composite activated alumina to γ-aminopropyltriethoxysilane is 100:3-4, and the reflux reaction time is 12-16 h.

5. The preparation method according to claim 1, characterized in that, In step S3, the mass ratio of the aminated composite alumina to maleic anhydride is 100:2-2.

5.

6. The preparation method according to claim 1, characterized in that, The stirring reaction in step S3 is carried out at a temperature of 25-35°C for 7-9 hours.

7. The preparation method according to claim 1, characterized in that, The mass ratio of the organic composite alumina, 2-mercaptothiazoline, 2,3-epoxypropyltrimethylammonium chloride, and triethylamine in step S4 is 100:1.8-2.3:2-2.7:2.5-3.

8. The preparation method according to claim 1, characterized in that, The isothermal reaction in step S4 is carried out at a temperature of 60-70°C for 2-3 hours.

9. A long-lasting antibacterial adsorbent packing material prepared by the method according to any one of claims 1-8.

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