Multi-effect antibacterial automobile air conditioner filter element material and preparation process thereof
By preparing pyridine derivative modifiers in automotive air conditioning filter materials and loading them onto the surface of tourmaline powder, combined with modified activated carbon, the problem of antibacterial agent failure under high humidity and high airflow velocity was solved, achieving multi-effect antibacterial effects against bacteria and fungi and improving the purification capacity of the air conditioning filter.
Patent Information
- Authority / Receiving Office
- CN · China
- Patent Type
- Patents(China)
- Current Assignee / Owner
- GUANGZHOU SANTAI AUTOMOTIVE TRIM MATERIALS
- Filing Date
- 2025-12-26
- Publication Date
- 2026-07-31
AI Technical Summary
In existing automotive air conditioning filters, the antibacterial agents are prone to failure and the nanoparticles are easily peeled off under high humidity and high airflow conditions. Furthermore, the filters lack the ability to inhibit fungi, resulting in decreased antibacterial performance and health threats.
A mildew inhibitor was prepared using pyridine derivatives, and the modifier was loaded onto the surface of tourmaline powder via a quaternary ammonium salt reaction. Combined with modified activated carbon, a multi-effect antibacterial filter material was prepared. The trifluoromethyl and pyridinethione structures of the modifier were used to enhance the antibacterial effect, and the tourmaline powder was used to purify the air.
It maintains good antibacterial performance under high humidity and high airflow, improves the ability to inhibit bacteria and fungi, reduces the impact of particulate pollutants on purification efficiency, and enhances the multi-effect antibacterial effect of air conditioning filter.
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Abstract
Description
Technical Field
[0001] This invention belongs to the field of air conditioning filter technology, specifically, it relates to an automotive air conditioning filter material that achieves multi-effect antibacterial properties and its preparation process. Background Technology
[0002] Air conditioning filters are core components of air purification systems, requiring them to simultaneously filter particulate matter and inhibit microbial growth. However, in harsh environments with high humidity and high airflow velocity, the antibacterial agents loaded in the filter material are prone to failure. On one hand, high humidity causes a water film to form on the surface of the filter material, leading to the rapid dissolution and washout of water-soluble antibacterial agents. On the other hand, the strong airflow shear force generated by high airflow velocity easily causes nano-sized antibacterial particles (such as nano-silver) to peel off from the surface of the filter material. This not only significantly reduces or even completely eliminates antibacterial performance, but the detached nanoparticles may also be released with the airflow, posing a threat to the health of occupants. Furthermore, most widely used antibacterial agents are primarily effective against bacteria and often lack the ability to inhibit common fungi, resulting in insufficient protection of the filter against fungal contamination. To address these technical deficiencies, this invention provides a multi-effect antibacterial automotive air conditioning filter material and its preparation process. Summary of the Invention
[0003] The purpose of this invention is to provide an automotive air conditioning filter material with multi-effect antibacterial properties and its preparation process, in order to solve the problems mentioned in the background art.
[0004] The objective of this invention can be achieved through the following technical solutions:
[0005] A preparation process for an automotive air conditioning filter material that achieves multi-effect antibacterial properties includes the following steps:
[0006] Step 1: Oxidize the pyridine derivative to obtain the precursor of the antifungal agent;
[0007] The second step is to thiolize the precursor of the antifungal agent to obtain the antifungal agent.
[0008] The third step is to trifluoromethylate the antifungal agent to obtain a modifier;
[0009] Step 4: After crushing, cleaning and drying the tourmaline, graft a silane coupling agent onto the surface, and then load the modifier onto the surface of the tourmaline powder through a quaternary ammonium salt reaction to obtain modified tourmaline powder.
[0010] Step 5: Pulverize the activated carbon and activate it through high-temperature heat treatment to obtain modified activated carbon. Then, mix the modified activated carbon, modified tourmaline powder, and binder, and mold them to obtain automotive air conditioning filter material.
[0011] Further, the pyridine derivative includes at least one of 6-chloro-N,N-dimethylpyridine-3-amine and 6-bromo-N,N-dimethylpyridine-3-amine.
[0012] Furthermore, the silane coupling agent is at least one of 3-chloropropyltriethoxysilane and 3-chloromethyltriethoxysilane.
[0013] Furthermore, the adhesive is at least one of waterborne polyurethane and sodium alginate.
[0014] Furthermore, the mass ratio of tourmaline powder, silane coupling agent, and modifier is 8–10:4–6:3–4, based on mass parts.
[0015] Furthermore, by mass parts, the mass ratio of modified activated carbon, modified tourmaline powder, and binder is 82-86:8-10:6-8.
[0016] Furthermore, the conditions for activation by high-temperature heat treatment are calcination at 750–850°C for 2–3 hours under nitrogen protection.
[0017] Furthermore, the compression molding conditions are as follows: press for 25-35 seconds under a pressure of 2-3 MPa, and after degassing, press for 110-130 seconds under a pressure of 7.5-8.5 MPa.
[0018] The present invention also provides automotive air conditioning filter material obtained by the above preparation method.
[0019] This invention has at least one of the following beneficial effects:
[0020] 1) The modifier prepared by this invention has a trifluoromethyl structure and a pyridinethione structure with good lipophilicity, which can effectively penetrate the cell membrane of bacteria and fungi, increase the permeability of the cell membrane, and thus cause leakage of substances inside the cell. After entering the cell membrane, the pyridinethione structure can also use its own coordination ability to chelate metal ions to inhibit the activity of various enzymes inside bacteria and fungi and interfere with the energy metabolism of bacteria and fungi, thus having a good inhibitory effect on bacteria and fungi.
[0021] 2) The modifier of this invention has a trifluoromethyl structure. The electron-withdrawing inductive effect of the trifluoromethyl structure can effectively reduce the electron density in the pyridine ring, enhance the metal chelating ability of the pyridinethione structure, and improve the inhibitory effect of the modifier on bacteria and fungi.
[0022] 3) The thiol group in the pyridine thione structure is easily oxidized by air to form a dimer and lose its antibacterial activity. This invention loads the modifier onto the surface of tourmaline powder through chemical bonding to avoid contact between the modifier molecules. This not only effectively inhibits the oxidative deactivation of the pyridine thione structure and solves the problem of scouring loss of antibacterial components in high-speed airflow and high-humidity environments, but the quaternary ammonium salt structure produced by the reaction can also use its own positive charge to adsorb the cell membranes of bacteria and fungi (cell membranes are usually negatively charged), increasing the probability of contact between bacteria and fungi and antibacterial components, thereby improving the antibacterial ability of the air conditioning filter.
[0023] 4) Tourmaline powder is added to the air conditioning filter material of the present invention. Tourmaline powder can generate negative ions through self-polarization to neutralize and settle positively charged particulate pollutants such as dust and smoke in the air, purify the air and reduce the occupation of activated carbon adsorption sites by particulate pollutants or the obstruction of antibacterial components from contacting microorganisms, thereby improving the antibacterial and purification efficiency of the air conditioning filter. Detailed Implementation
[0024] The technical solutions of the embodiments of this application will be clearly and completely described below. Obviously, the described embodiments are only some, not all, of the embodiments of this application. Based on the embodiments in this application specification, all other embodiments obtained by those skilled in the art without creative effort are within the scope of protection claimed in this application.
[0025] The raw materials used in this invention are not particularly restricted in terms of their source; they can be purchased from the market or prepared using conventional methods known to those skilled in the art, at a room temperature of 25±5℃.
[0026] Example 1
[0027] A preparation process for an automotive air conditioning filter material that achieves multi-effect antibacterial properties includes the following steps:
[0028] Step 1: Oxidize 6-chloro-N,N-dimethylpyridine-3-amine to obtain the precursor of the antifungal agent;
[0029] The oxidation conditions were as follows: 40 mmol of 6-chloro-N,N-dimethylpyridin-3-amine and 20 g of glacial acetic acid were mixed in a three-necked flask equipped with a thermometer and a reflux condenser. The system temperature was raised to 80 °C, and 10 g of 30% hydrogen peroxide aqueous solution was added dropwise. The reaction was continued at 80 °C for 4 h. After the reaction was completed, the mixture was cooled to room temperature and some of the glacial acetic acid was removed by rotary evaporation. The remaining mixture was dissolved in 10% sodium hydroxide solution and then extracted with dichloromethane. The organic phase was dried and the solvent was removed by rotary evaporation to obtain the precursor of the antifungal agent.
[0030]
[0031] The second step is to thiolize the precursor of the antifungal agent to obtain the antifungal agent.
[0032] The conditions for thiolization were as follows: 32 mmol of the antifungal agent precursor, 2.8 g of sodium hydrosulfide, and 30 mmol of 10% sodium hydroxide aqueous solution were mixed in a three-necked flask equipped with a thermometer, a reflux condenser, and a tail gas absorption device under nitrogen protection. The reaction was carried out at 85 °C for 3.5 h. The reaction apparatus was then cooled in an ice-water bath, and 10% hydrochloric acid was added to the system to adjust the pH to 5. The mixture was then extracted with dichloromethane, and the organic phase was separated by a separatory funnel. The organic phase was dried and rotary evaporated to obtain the antifungal agent.
[0033]
[0034] The third step is to trifluoromethylate the antifungal agent to obtain a modifier;
[0035] The conditions for trifluoromethylation were as follows: 24 mmol of antifungal agent, 24 mmol of S-(trifluoromethyl)dibenzothiophenonium trifluoromethanesulfonate, 2 mmol of 1,8-diazabicycloundec-7-ene, and 30 mL of dimethyl sulfoxide were mixed in a three-necked flask equipped with a thermometer and a reflux condenser under nitrogen protection. The mixture was reacted at room temperature for 4 h. After the reaction was completed, the reaction solution was poured into ice water and extracted with dichloromethane. The organic phase was collected, dried, and the solvent was removed by rotary evaporation. The modified agent was then obtained by silica gel column chromatography.
[0036]
[0037] Step 4: After crushing, cleaning and drying the tourmaline, graft a silane coupling agent onto the surface, and then load the modifier onto the surface of the tourmaline powder through a quaternary ammonium salt reaction to obtain modified tourmaline powder.
[0038] The conditions for grafting silane coupling agent are as follows: 8g of dried tourmaline powder, 4g of 3-chloromethyltriethoxysilane, and 40mL of 80% (v / v) ethanol aqueous solution are mixed in a three-necked flask equipped with a thermometer and a reflux condenser. The mixture is reacted at 40℃ for 10h. After the reaction is completed, the mixture is cooled to room temperature and the solid is filtered out. The obtained solid is washed with anhydrous ethanol and deionized water in sequence and then dried to obtain tourmaline powder of grafted silane coupling agent.
[0039] The conditions for loading the modifier were as follows: Under nitrogen protection, 8g of tourmaline powder grafted with silane coupling agent, 3g of modifier, and 40mL of acetonitrile were mixed in a three-necked flask equipped with a thermometer and a reflux condenser. The mixture was reacted at 40℃ for 36h. After the reaction was completed, the solid was filtered out and washed with anhydrous ethanol and deionized water in sequence and then dried to obtain modified tourmaline powder.
[0040] Step 5: Pulverize the activated carbon and calcine it at 750℃ for 3 hours under nitrogen protection to obtain modified activated carbon. Then, mix 86g of modified activated carbon, 8g of modified tourmaline powder, and 6g of waterborne polyurethane and press it at 3MPa for 35s. After exhausting the gas, press it at 8.5MPa for 130s to obtain the automotive air conditioning filter material.
[0041] An automotive air conditioning filter material, which is prepared by the above method.
[0042] Example 2
[0043] A preparation process for an automotive air conditioning filter material that achieves multi-effect antibacterial properties includes the following steps:
[0044] Step 1: Oxidize 6-chloro-N,N-dimethylpyridine-3-amine to obtain the precursor of the antifungal agent;
[0045] The oxidation conditions were as follows: 45 mmol of 6-chloro-N,N-dimethylpyridin-3-amine and 25 g of glacial acetic acid were mixed in a three-necked flask equipped with a thermometer and a reflux condenser. The system temperature was raised to 85 °C, and then 14 g of 30% hydrogen peroxide aqueous solution was added dropwise. The reaction was continued at 85 °C for 3.5 h. After the reaction was completed, the mixture was cooled to room temperature and some of the glacial acetic acid was removed by rotary evaporation. The remaining mixture was dissolved in 10% sodium hydroxide solution and then extracted with dichloromethane. The organic phase was dried and the solvent was removed by rotary evaporation to obtain the precursor of the antifungal agent.
[0046] The second step is to thiolize the precursor of the antifungal agent to obtain the antifungal agent.
[0047] The conditions for thiolization were as follows: 35 mmol of the antifungal agent precursor, 3.1 g of sodium hydrosulfide, and 35 mmol of 10% sodium hydroxide aqueous solution were mixed in a three-necked flask equipped with a thermometer, a reflux condenser, and a tail gas absorption device under nitrogen protection. After reacting at 90°C for 3 h, the reaction apparatus was cooled in an ice-water bath, and 10% hydrochloric acid was added to the system to adjust the pH to 4.5. Then, the mixture was extracted with dichloromethane, and the organic phase was separated by a separatory funnel. The organic phase was dried and rotary evaporated to obtain the antifungal agent.
[0048] The third step is to trifluoromethylate the antifungal agent to obtain a modifier;
[0049] The conditions for trifluoromethylation were as follows: 27 mmol of antifungal agent, 27 mmol of S-(trifluoromethyl)dibenzothiophenonium trifluoromethanesulfonate, 2.5 mmol of 1,8-diazabicycloundec-7-ene, and 35 mL of dimethyl sulfoxide were mixed in a three-necked flask equipped with a thermometer and a reflux condenser under nitrogen protection. The mixture was reacted at room temperature for 5 h. After the reaction was completed, the reaction solution was poured into ice water and extracted with dichloromethane. The organic phase was collected, dried, and the solvent was removed by rotary evaporation. The modified agent was then obtained by silica gel column chromatography.
[0050] Step 4: After crushing, cleaning and drying the tourmaline, graft a silane coupling agent onto the surface, and then load the modifier onto the surface of the tourmaline powder through a quaternary ammonium salt reaction to obtain modified tourmaline powder.
[0051] The conditions for grafting silane coupling agent are as follows: 9g of dried tourmaline powder, 4.5g of 3-chloromethyltriethoxysilane, and 50mL of 70% (v / v) ethanol aqueous solution are mixed in a three-necked flask equipped with a thermometer and a reflux condenser. The mixture is reacted at 50℃ for 7h. After the reaction is completed, the mixture is cooled to room temperature and the solid is filtered out. The obtained solid is washed with anhydrous ethanol and deionized water in sequence and then dried to obtain tourmaline powder with grafted silane coupling agent.
[0052] The conditions for loading the modifier were as follows: 9g of tourmaline powder grafted with silane coupling agent, 3.5g of modifier, and 45mL of acetonitrile were mixed in a three-necked flask equipped with a thermometer and a reflux condenser under nitrogen protection. The mixture was reacted at 50℃ for 30h. After the reaction was completed, the solid was filtered out and washed with anhydrous ethanol and deionized water in sequence and then dried to obtain modified tourmaline powder.
[0053] Step 5: Pulverize the activated carbon and calcine it at 800℃ for 2.5 hours under nitrogen protection to obtain modified activated carbon. Then, mix 84g of modified activated carbon, 9g of modified tourmaline powder, and 7g of waterborne polyurethane and press it at 2.5MPa for 30 seconds. After exhausting the gas, press it at 8MPa for 120 seconds to obtain the automotive air conditioning filter material.
[0054] An automotive air conditioning filter material, which is prepared by the above method.
[0055] Example 3
[0056] A preparation process for an automotive air conditioning filter material that achieves multi-effect antibacterial properties includes the following steps:
[0057] Step 1: Oxidize 6-chloro-N,N-dimethylpyridine-3-amine to obtain the precursor of the antifungal agent;
[0058] The oxidation conditions were as follows: 50 mmol of 6-bromo-N,N-dimethylpyridin-3-amine and 30 g of glacial acetic acid were mixed in a three-necked flask equipped with a thermometer and a reflux condenser. The system temperature was raised to 90 °C, and 18 g of 30% hydrogen peroxide aqueous solution was added dropwise. The reaction was continued at 90 °C for 3 h. After the reaction was completed, the mixture was cooled to room temperature and some of the glacial acetic acid was removed by rotary evaporation. The remaining mixture was dissolved in 10% sodium hydroxide solution and then extracted with dichloromethane. The organic phase was dried and the solvent was removed by rotary evaporation to obtain the precursor of the antifungal agent.
[0059] The second step is to thiolize the precursor of the antifungal agent to obtain the antifungal agent.
[0060] The conditions for thiolization were as follows: 38 mmol of the antifungal agent precursor, 3.4 g of sodium hydrosulfide, and 40 mmol of 10% sodium hydroxide aqueous solution were mixed in a three-necked flask equipped with a thermometer, a reflux condenser, and a tail gas absorption device under nitrogen protection. The reaction was carried out at 95 °C for 2.5 h. The reaction apparatus was then cooled in an ice-water bath, and 10% hydrochloric acid was added to the system to adjust the pH to 4. The mixture was then extracted with dichloromethane, and the organic phase was separated by a separatory funnel. The organic phase was dried and rotary evaporated to obtain the antifungal agent.
[0061] The third step is to trifluoromethylate the antifungal agent to obtain a modifier;
[0062] The conditions for trifluoromethylation were as follows: 30 mmol of antifungal agent, 30 mmol of S-(trifluoromethyl)dibenzothiophenonium trifluoromethanesulfonate, 3 mmol of 1,8-diazabicycloundec-7-ene, and 40 mL of dimethyl sulfoxide were mixed in a three-necked flask equipped with a thermometer and a reflux condenser under nitrogen protection. The mixture was reacted at room temperature for 6 h. After the reaction was completed, the reaction solution was poured into ice water and extracted with dichloromethane. The organic phase was collected, dried, and the solvent was removed by rotary evaporation. The modified agent was then obtained by silica gel column chromatography.
[0063] Step 4: After crushing, cleaning and drying the tourmaline, graft a silane coupling agent onto the surface, and then load the modifier onto the surface of the tourmaline powder through a quaternary ammonium salt reaction to obtain modified tourmaline powder.
[0064] The conditions for grafting silane coupling agent are as follows: 10g of dried tourmaline powder, 6g of 3-chloropropyltriethoxysilane, and 60mL of 60% (v / v) ethanol aqueous solution are mixed in a three-necked flask equipped with a thermometer and a reflux condenser. The mixture is reacted at 60℃ for 4h. After the reaction is completed, the mixture is cooled to room temperature and the solid is filtered out. The obtained solid is washed with anhydrous ethanol and deionized water in sequence and then dried to obtain tourmaline powder of grafted silane coupling agent.
[0065] The conditions for loading the modifier were as follows: 10g of tourmaline powder grafted with silane coupling agent, 4g of modifier, and 50mL of acetonitrile were mixed in a three-necked flask equipped with a thermometer and a reflux condenser under nitrogen protection. The mixture was reacted at 60℃ for 24h. After the reaction was completed, the solid was filtered out and washed with anhydrous ethanol and deionized water in sequence and then dried to obtain modified tourmaline powder.
[0066] Step 5: Pulverize the activated carbon and calcine it at 850℃ for 2 hours under nitrogen protection to obtain modified activated carbon. Then, mix 82g of modified activated carbon, 10g of modified tourmaline powder, and 8g of sodium alginate and press it at 2MPa for 25s. After exhausting the gas, press it at 7.5MPa for 110s to obtain the automotive air conditioning filter material.
[0067] An automotive air conditioning filter material, which is prepared by the above method.
[0068] Comparative Example 1
[0069] The difference between this comparative example and Example 1 is that the modifier is not prepared separately, but the conventional antifungal and antibacterial agent zinc pyrithione is used, and the loading method is physical adsorption on activated carbon.
[0070] Step 1: Pulverize the activated carbon and calcine it at 800℃ for 2.5h under nitrogen protection. Then, mix 84g of calcined activated carbon, 3g of zinc pyrithione, and 200mL of anhydrous ethanol in a three-necked flask equipped with a thermometer and a reflux condenser. Stir at 40℃ for 6h, filter out the activated carbon, wash it with anhydrous ethanol, and dry it to obtain modified activated carbon.
[0071] Step 2: After crushing, washing and drying the tourmaline, take 8g of tourmaline powder, 86g of modified activated carbon and 6g of water-based polyurethane, mix them and press them under a pressure of 3MPa for 35s. After degassing, press them under a pressure of 8.5MPa for 130s to obtain the automotive air conditioning filter material.
[0072] Experimental Example 1
[0073] The air conditioning filter materials obtained in Examples 1-3 and Comparative Example 1 were subjected to antibacterial and antifungal performance tests. The antibacterial rate of each component filter material against *Escherichia coli* and *Staphylococcus aureus* was tested according to the national standard GB 21551.2-2010 "Special Requirements for Antibacterial Materials with Antibacterial, Sterilizing, and Purifying Functions for Household and Similar Electrical Appliances". The antifungal rating of each component filter material was tested according to the national standard GB / T2423.16-2022 "Environmental Testing Part 2: Test Methods Test J and Guidelines: Mold Growth". After rinsing each component air conditioning filter material for 100 hours at an airflow velocity of 5 m / s and a humidity of 90%, the antibacterial rate and antifungal rating were repeatedly tested. The test results are shown in Table 1.
[0074] Table 1
[0075]
[0076] As can be seen from Table 1, the air conditioning filter materials of the present invention in Examples 1 to 3 have good antibacterial and anti-mildew properties, and the antibacterial components are not easily lost in the high humidity and high airflow environment inside the car air conditioner.
[0077] The descriptions of the above embodiments are merely illustrative of the methods and core ideas of the present invention. Various modifications to these embodiments will be readily apparent to those skilled in the art, and the general principles defined herein may be implemented in other embodiments without departing from the spirit or scope of the invention. Therefore, the present invention is not to be limited to the embodiments shown herein, but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.
Claims
1. A process for preparing a multi-effect antibacterial automobile air conditioner filter element material, characterized by, Includes the following steps: Step 1: Oxidize the pyridine derivative to obtain the precursor of the antifungal agent; The second step is to thiolize the precursor of the antifungal agent to obtain the antifungal agent. The third step is to trifluoromethylate the antifungal agent to obtain a modifier; Step 4: After crushing, cleaning and drying the tourmaline, graft a silane coupling agent onto the surface, and then load the modifier onto the surface of the tourmaline powder through a quaternary ammonium salt reaction to obtain modified tourmaline powder. Step 5: Pulverize the activated carbon and activate it through high-temperature heat treatment to obtain modified activated carbon. Then, mix the modified activated carbon, modified tourmaline powder, and binder, and mold them to obtain automotive air conditioning filter material. The pyridine derivative includes at least one of 6-chloro-N,N-dimethylpyridine-3-amine and 6-bromo-N,N-dimethylpyridine-3-amine; The silane coupling agent is at least one of 3-chloropropyltriethoxysilane and 3-chloromethyltriethoxysilane; The mass ratio of tourmaline powder, silane coupling agent, and modifier is 8-10:4-6:3-4, based on parts by mass. The mass ratio of modified activated carbon, modified tourmaline powder, and binder is 82-86:8-10:6-8 by mass.
2. The preparation process of an automotive air conditioning filter material achieving multi-effect antibacterial properties according to claim 1, characterized in that, The adhesive is at least one of waterborne polyurethane and sodium alginate.
3. The process for preparing a multi-effect antibacterial automobile air conditioner filter element material according to claim 1, characterized in that, The conditions for activation by high-temperature heat treatment are calcination at 750–850°C for 2–3 hours under nitrogen protection.
4. The preparation process of a multi-effect antibacterial automobile air conditioner filter element material according to claim 1, characterized in that, The compression molding conditions are: press for 25-35 seconds under a pressure of 2-3 MPa, and after degassing, press for 110-130 seconds under a pressure of 7.5-8.5 MPa.
5. A multi-effect antibacterial automobile air conditioner filter element material, characterized by, The automotive air conditioning filter material with multi-effect antibacterial properties is prepared by the preparation process described in any one of claims 1 to 4.