Odor removal additive with lasting odor removal function as well as preparation method and application of odor removal additive

Abstract

The invention discloses an odor removal additive with a lasting odor removal function as well as a preparation method and application of the odor removal additive. The preparation method comprises the following steps: by taking water as a medium, uniformly mixing halloysite nanotubes, alkali and polyvinylpyrrolidone, reacting, carrying out solid-liquid separation, carrying out ultrasonic stirring dispersion on the obtained solid, a deodorant, an antibacterial agent and polyhedral oligomeric silsesquioxane in water, then vacuumizing, mixing the obtained product with an ethanol water solution of a hydrophilic polymer material at the temperature of 0 DEG C or below, and carrying out atomization granulation, thereby obtaining the halloysite nanotube deodorant. The odorless additive is obtained. After being sprayed on a fin dry film, the odor removing agent prepared from the additive is good in hydrophilicity, free of water washing and high in adhesive force. The deodorant has a lasting deodorizing effect on peculiar smells such as sour smells and sour and foul smells which are generated in a refrigeration air transfer stage.

Description

Technical Field

[0001] The invention belongs to the technical field of air purification, and in particular relates to a deodorizing additive with a lasting deodorizing function and a preparation method and application thereof. Background Art

[0002] As a typical application of heat exchangers, air conditioners bring people a comfortable feeling in summer, but they also cause odors due to various reasons, which makes people feel uncomfortable and even affects people's health. Therefore, in order to eliminate the odors related to heat exchangers, various cleaning agents and deodorizers are used. The effects of related products on the market are usually one-time, that is, they are effective immediately after treatment, but the effect cannot be maintained, or they will soon lose their effect as condensed water continues to flush. Moreover, some products only use fragrance ingredients to cover the odor, not completely eliminate the odor. In addition, these products target odors caused by the growth of microorganisms such as bacteria and mold, or dusty odors caused by dust accumulation, and odors caused by oil fume adsorption, etc. There are no products specifically targeting the sour odors blown out during the refrigeration and air transfer stage of the heat exchanger. In addition, these products do not take into account the impact of the product itself on the hydrophilic properties of the heat exchanger surface.

[0003] The sour smell (hereinafter referred to as refrigeration type odor) blown out by the heat exchanger during refrigeration means that the heat exchanger will accumulate trace malodorous substances produced by biological metabolism in the environment during the refrigeration process. These substances are concentrated and blown out when the air conditioner reaches the set temperature and switches to the air supply mode, showing as sour smell, sour smell, sweat smell, sweat acid smell and other similar odors. Since the biological metabolism in the working environment of the heat exchanger is always going on, odorous substances are continuously produced, and the heat exchanger is also constantly circulating from refrigeration to air supply, the phenomenon of the heat exchanger blowing out sour smells will continue to occur.

[0004] Therefore, it is necessary to develop a new product technology that can effectively remove refrigeration-type odors and has a long-lasting adhesion and deodorization effect without negatively affecting the hydrophilic properties of the heat exchanger fin surface. Summary of the invention

[0005] The primary purpose of the present invention is to overcome the shortcomings and deficiencies of the prior art and to provide a method for preparing a deodorizing additive with a long-lasting deodorizing function.

[0006] Another object of the present invention is to provide a deodorizing additive having a lasting deodorizing function obtained by the above preparation method.

[0007] Another object of the present invention is to provide the application of the above-mentioned odor-removing additive with a long-lasting deodorizing function.

[0008] The purpose of the present invention is achieved by the following technical solution: A method for preparing a deodorizing additive with a long-lasting deodorizing function comprises the following steps: (1) Halloysite nanotubes, an alkali solution and a polyvinyl pyrrolidone (PVP) aqueous solution are uniformly mixed, and the obtained reaction system is sealed and reacted at 120 to 180° C. for 1 to 8 hours; after the reaction is completed, the reaction is cooled to room temperature, the solid and liquid are separated, and the obtained solid is washed with water and then dried; the halloysite nanotubes, the alkali and the polyvinyl pyrrolidone in the reaction system are mixed in a mass ratio of 10:0.89 to 5.34:0.2; (2) dispersing the deodorant, antibacterial agent and cage-type polysilsesquioxane in water, adding the solid dried in step (1), stirring and dispersing with ultrasonic stirring, and then evacuating to -0.1 kPa and maintaining for 3 to 6 hours, using capillary force and pressure to allow the mixed material to enter the inner cavity of the halloysite, and then separating the solid and liquid and drying; repeating the above steps, the only difference is that the halloysite used each time is the halloysite prepared in the previous step, to obtain functional halloysite; (3) The hydrophilic polymer material and the ethanol aqueous solution are mixed, cooled to below 0°C, and then the functional halloysite is added and stirred to mix the hydrophilic polymer material with the functional halloysite, and then atomized and granulated to obtain a deodorizing additive with a long-lasting deodorizing function.

[0009] The alkali described in step (1) is preferably at least one of sodium hydroxide, lithium hydroxide, calcium hydroxide and potassium hydroxide.

[0010] The concentration of the alkali solution in step (1) is preferably 1 to 6% by mass.

[0011] The concentration of the polyvinyl pyrrolidone aqueous solution in step (1) is preferably 15-25% by mass; more preferably 20% by mass.

[0012] The mixing conditions in step (1) are preferably: a stirring speed of 500 to 600 rpm and a stirring time of 5 to 10 min.

[0013] The closed reaction conditions in step (1) are preferably 130-180° C. for 1.5-4 hours.

[0014] The water described in step (1) is preferably distilled water, deionized water or purified water.

[0015] The solid-liquid separation method in step (1) is preferably centrifugation.

[0016] The centrifugal conditions are preferably 600-1000 rpm for 5-15 min; more preferably 800 rpm for 10 min.

[0017] The drying method described in step (1) is preferably vacuum drying at room temperature.

[0018] The drying time in step (1) is preferably 30 to 90 minutes, more preferably 60 minutes.

[0019] The deodorant described in step (2) is preferably at least one of zinc ricinoleate, zinc ricinoleate ester, zinc phytate and primary amino polyol.

[0020] The antibacterial agent described in step (2) is preferably a silver ion antibacterial agent.

[0021] The cage-type polysilsesquioxane in step (2) is preferably at least one of cage-type polysilsesquioxane-octaamine (amino), tetramethylammonium cage-type polysilsesquioxane and POSS monoamino.

[0022] The dosage of each substance in step (2) is preferably as follows: the deodorant, antibacterial agent, cage-type polysilsesquioxane and halloysite are preferably mixed in a mass ratio of 38-39:1-2:0.2-0.4:15; more preferably, the mass ratio is 38-39:1.5:0.2-0.4:15.

[0023] The water described in step (2) is preferably distilled water, deionized water or purified water.

[0024] The water described in step (2) is used as a dispersion medium, and its amount can be conventional; preferably 1.0 to 1.2 times the total mass of the deodorant, antibacterial agent, cage-type polysilsesquioxane and halloysite; more preferably 1.05 to 1.1 times the total mass of the deodorant, antibacterial agent, cage-type polysilsesquioxane and halloysite.

[0025] The ultrasonic stirring conditions in step (2) are preferably: 30-50 KHz and 600-1000 rpm for at least 3 min; more preferably: 40 KHz and 800 rpm for 5 min.

[0026] The holding time in step (2) is preferably 5 h.

[0027] The solid-liquid separation method in step (2) is preferably centrifugation.

[0028] The centrifugal conditions are preferably 600-1000 rpm for 5-15 min; more preferably 800 rpm for 5 min.

[0029] The drying method described in step (2) is preferably vacuum drying; more preferably vacuum drying at 40-60° C. for 8-12 h; more preferably vacuum drying at 50° C. for 10 h.

[0030] The number of repetitions in step (2) is 0 to 3 times, preferably 2 times.

[0031] The hydrophilic polymer material in step (3) is a polyacrylate; preferably at least one of magnesium polyacrylate, calcium polyacrylate, aluminum polyacrylate and zirconium polyacrylate.

[0032] The molar ratio of carboxylic acid to carboxylic acid metal salt in the polyacrylate is 1.4-4.5, and the effective solid content of the resin is 15-25%; preferably, the molar ratio of carboxylic acid to carboxylic acid metal salt is 1.8-2.2, and the effective solid content of the resin is 18-22%; more preferably, the molar ratio of carboxylic acid to carboxylic acid metal salt is 2, and the effective solid content of the resin is 20%.

[0033] The polyacrylic acid salt is preferably prepared by the following steps: neutralizing polyacrylic acid with hydroxide; more preferably prepared by the following steps: dropping a hydroxide aqueous dispersion into a stirred polyacrylic acid aqueous solution, and continuing stirring after the dropwise addition is completed to obtain the polyacrylic acid salt.

[0034] The hydroxide is preferably at least one of magnesium hydroxide, zirconium hydroxide, calcium hydroxide and aluminum hydroxide.

[0035] The average molecular weight of the polyacrylic acid is preferably 400,000 to 600,000, and more preferably 400,000 to 500,000.

[0036] The concentration of the ethanol aqueous solution in step (3) is 15-25% by mass, and more preferably 20% by mass.

[0037] The purpose of the ethanol aqueous solution in step (3) is to further dilute the hydrophilic polymer material. The amount used is conventional, preferably 2 to 3 times the mass of the hydrophilic polymer material.

[0038] The hydrophilic polymer material and the functional halloysite in step (3) are preferably mixed in a mass ratio of 20 to 30:10; more preferably in a mass ratio of 25:10.

[0039] The cooling temperature in step (3) is preferably -5 to -10°C, more preferably -10°C.

[0040] The stirring condition in step (3) is preferably 200-400 rpm for 3-8 min; more preferably 300 rpm for 5 min.

[0041] The conditions for the atomization granulation in step (3) are preferably a rotation speed of 15,000 to 25,000 rpm and an inlet air temperature of 200 to 300° C.; more preferably a rotation speed of 20,000 rpm and an inlet air temperature of 250° C.

[0042] A deodorizing additive with a lasting deodorizing function is obtained by the preparation method.

[0043] Application of the above-mentioned deodorizing additive with long-lasting deodorizing function in the preparation of deodorizing agent.

[0044] A deodorizing agent contains the deodorizing additive with a lasting deodorizing function.

[0045] The deodorizing agent contains the following ingredients in percentage by mass: 3-10% of the above-mentioned deodorizing additive with a lasting deodorizing function, 0.1-1% of a thickener, and the balance is water; preferably contains the following ingredients in percentage by mass: 7-9% of the above-mentioned deodorizing additive with a lasting deodorizing function, 0.4-0.6% of a thickener, and the balance is water; more preferably contains the following ingredients in percentage by mass: 8% of the above-mentioned antibacterial deodorizing additive with a sustained-release function, 0.5% of a thickener, and the balance is water.

[0046] The thickener is preferably a cellulose thickener, and more preferably carboxymethyl cellulose.

[0047] The preparation method of the deodorizing agent comprises the following steps: dissolving a thickener in water, and then adding the deodorizing additive with a lasting deodorizing function and mixing evenly to obtain the deodorizing agent.

[0048] The application of the deodorant comprises the following steps: spraying the deodorant on the surface of the heat exchanger fins and drying to form a film. The deodorant has the effect of removing sour smell, sour smell and other odors generated in the cooling transfer air stage.

[0049] The heat exchanger fins are preferably heat exchanger fins of an air conditioner.

[0050] The drying is achieved by turning on the air supply mode or the heating mode.

[0051] Compared with the prior art, the present invention has the following advantages and effects: The present invention provides a deodorizing additive with a lasting deodorizing function. The deodorizing agent prepared by the additive is applied to the surface of the heat exchanger fins. The hydrophilic angle after the dry film is 7 to 10 degrees, which shows that it has good hydrophilicity, thereby not affecting the hydrophilicity of the fins, avoiding water washing, and reducing the construction steps. In addition, the material on the surface of the fins is usually a hydrophilic coating. Due to the scientific formula of the deodorizing additive, it can be seen from the test data of the present invention that the adhesion between the deodorizing agent and the hydrophilic coating on the surface of the fins is level 1, and the adhesion is strong; and the deodorizing performance is more lasting. DETAILED DESCRIPTION

[0052] The present invention is further described in detail below in conjunction with examples, but the embodiments of the present invention are not limited thereto. In the following examples and comparative examples, parts refer to parts by mass.

[0053] Example 1 (1) Halloysite pretreatment: Halloysite nanotubes (JN-3, Guangdong Jina New Materials Technology Co., Ltd.), 3wt% sodium hydroxide solution and 20wt% polyvinyl pyrrolidone (PVP, K70) aqueous solution were added to a three-necked flask equipped with a stirrer and a thermometer at a mass ratio of 10:89:1, stirred for 5 min at room temperature and a stirring rate of 550 r / min, then transferred to a high-pressure reactor, sealed at 130°C for 4 h, and the reaction product was cooled to room temperature after the reaction was completed. Centrifuged at 800 rpm for 10 min, the obtained solid was washed with distilled water, centrifuged again, and the precipitate was vacuum dried at room temperature for 1 h.

[0054] (2) Preparation of functional halloysite 1) 38.5 parts of zinc ricinoleate, 1.5 parts of silver ion antibacterial agent (Fulexbo AD-4) and 0.3 parts of tetramethylammonium cage-type polysilsesquioxane are dispersed in 59.7 parts of deionized water, 15 parts of the halloysite product finally obtained in step (1) are added, and then ultrasonic (40KHz) is applied while stirring at 800 rpm for 5 minutes, and then vacuum pump is used to evacuate to -0.1 kPa and maintain for 5 hours, and finally centrifuged and vacuum dried at 50°C for 10 hours; 2) repeating step 1), wherein the halloysite used is the halloysite containing the deodorant, the antibacterial agent and the tetramethylammonium cage-type polysilsesquioxane prepared in step 1); 3) Repeat step 1), wherein the halloysite used is the halloysite containing the deodorant, the antibacterial agent and the tetramethylammonium cage-type polysilsesquioxane prepared in step 2).

[0055] (3) Preparation of odor-free additives 1) Calculate the amount of hydroxide based on the acid value of polyacrylic acid and the desired target product. Disperse 0.03 mol of magnesium hydroxide in water to obtain a magnesium hydroxide aqueous dispersion with a total mass of 20 g; add the hydroxide aqueous dispersion dropwise to 80 g of polyacrylic acid resin aqueous solution with an average molecular weight of 450,000 under stirring conditions of 600-900 rpm, and continue stirring for 30 minutes after the dropwise addition to obtain a hydrophilic polymer material magnesium polyacrylate solution. Among them, the effective solid content of the magnesium polyacrylate solution is 20% by mass, and the molar ratio of carboxylic acid to magnesium carboxylate is 2.

[0056] 2) Add 25 parts of magnesium polyacrylate to a mixed solution formed by 52 parts of deionized water and 13 parts of anhydrous ethanol, mix well and cool to -10°C, then add 10 parts of functional halloysite, stir at 300 r / min for 5 minutes, and then quickly transfer to a high-speed centrifugal spray dryer for atomization granulation. The conditions for atomization granulation are a rotation speed of 20,000 rpm and an inlet air temperature of 250°C to obtain a deodorizing additive.

[0057] Example 2 (1) Halloysite pretreatment: Halloysite nanotubes (JN-3, Guangdong Jina New Materials Technology Co., Ltd.), 1wt% potassium hydroxide solution and 20wt% polyvinyl pyrrolidone (PVP, K70) aqueous solution were added to a three-necked flask equipped with a stirrer and a thermometer at a mass ratio of 10:89:1, stirred for 5 min at room temperature and a stirring rate of 550 r / min, then transferred to a high-pressure reactor, sealed at 160°C for 3 h, and the reaction product was cooled to room temperature after the reaction was completed. Centrifuged at 800 rpm for 10 min, the obtained solid was washed with distilled water, then centrifuged, and the obtained solid was vacuum dried at room temperature for 1 h.

[0058] (2) Preparation of functional halloysite 1) Disperse 39 parts of zinc ricinoleate, 1.5 parts of silver ion antibacterial agent (Fulaisibo AD-4) and 0.4 parts of tetramethylammonium cage-type polysilsesquioxane in 59.1 parts of deionized water, add 15 parts of the product finally obtained in step (1), ultrasonicate (40KHz) and stir at 800 rpm for 5 minutes, then use a vacuum pump to evacuate to -0.1 kPa and maintain for 5 hours, finally centrifuge and vacuum dry at 50°C for 10 hours; 2) repeating step 1), wherein the halloysite used is the halloysite containing the deodorant, the antibacterial agent and the tetramethylammonium cage-type polysilsesquioxane prepared in step 1); 3) Repeat step 1), wherein the halloysite used is the halloysite containing the deodorant, the antibacterial agent and the tetramethylammonium cage-type polysilsesquioxane prepared in step 2).

[0059] (3) Preparation of odor-free additives The preparation of the hydrophilic polymer material calcium polyacrylate solution is basically the same as the magnesium polyacrylate solution in Example 1, except that calcium hydroxide is used instead of magnesium hydroxide. The effective solid content of the calcium polyacrylate solution is 20% by mass, and the molar ratio of carboxylic acid to calcium carboxylate is 2.

[0060] 25 parts of hydrophilic polymer calcium polyacrylate are added to a mixed solution formed by 52 parts of deionized water and 13 parts of anhydrous ethanol, mixed and cooled to -10°C, and then 10 parts of functional halloysite are added, stirred at 300r / min for 5 minutes, and then quickly transferred to a high-speed centrifugal spray dryer for atomization granulation. The conditions for atomization granulation are a rotation speed of 20,000 rpm and an inlet air temperature of 250°C to obtain a deodorizing additive.

[0061] Example 3 (1) Halloysite pretreatment: Halloysite nanotubes (JN-3, Guangdong Jina New Materials Technology Co., Ltd.), 6wt% lithium hydroxide solution and 20wt% polyvinyl pyrrolidone (PVP, K70) aqueous solution were added to a three-necked flask equipped with a stirrer and a thermometer at a mass ratio of 10:89:1, stirred for 5 min at room temperature and a stirring rate of 550 r / min, then transferred to a high-pressure reactor, sealed at 180°C for 1.5 h, and the reaction product was cooled to room temperature after the reaction was completed. Centrifuged at 800 rpm for 10 min, the obtained solid was washed with distilled water, then centrifuged, and the obtained solid was vacuum dried at room temperature for 1 h.

[0062] (2) Preparation of functional halloysite 1) Disperse 38 parts of zinc ricinoleate, 1.5 parts of silver ion antibacterial agent (Fulaisibo AD-4) and 0.2 parts of tetramethylammonium cage-type polysilsesquioxane in 60.3 parts of deionized water, add 15 parts of the product finally obtained in step (1), ultrasonicate (40KHz) and stir at 800 rpm for 5 minutes, then use a vacuum pump to evacuate to -0.1 kPa and maintain for 5 hours, finally centrifuge and vacuum dry at 50°C for 10 hours; 2) repeating step 1), wherein the halloysite used is the halloysite containing the deodorant, the antibacterial agent and the tetramethylammonium cage-type polysilsesquioxane prepared in step 1); 3) Repeat step 1), wherein the halloysite used is the halloysite containing the deodorant, the antibacterial agent and the tetramethylammonium cage-type polysilsesquioxane prepared in step 2).

[0063] (3) Preparation of odor-free additives 25 parts of hydrophilic polymer material magnesium polyacrylate (same as in Example 1) were added to a mixed solution formed by 52 parts of deionized water and 13 parts of anhydrous ethanol, mixed and cooled to -10°C, and then 10 parts of functional halloysite were added, stirred at 300r / min for 5min, and then quickly transferred to a high-speed centrifugal spray dryer for atomization granulation. The conditions for atomization granulation were a rotation speed of 20,000 rpm and an inlet air temperature of 250°C to obtain a deodorizing additive.

[0064] Comparative Example 1 Comparative Example 1 is used to illustrate the importance of cage-type polysilsesquioxane. The operation of Comparative Example 1 is basically the same as that of Example 1, except that tetramethylammonium cage-type polysilsesquioxane is not added in step (2). Specific steps: (1) Halloysite pretreatment: Halloysite nanotubes (JN-3, Guangdong Jina New Materials Technology Co., Ltd.), 3wt% sodium hydroxide solution and 20wt% polyvinyl pyrrolidone (PVP, K70) aqueous solution were added to a three-necked flask equipped with a stirrer and a thermometer at a mass ratio of 10:89:1, stirred for 5 min at room temperature and a stirring rate of 550 r / min, then transferred to a high-pressure reactor, sealed at 130°C for 4 h, and the reaction product was cooled to room temperature after the reaction was completed. Centrifuged at 800 rpm for 10 min, the obtained solid was washed with distilled water, then centrifuged, and the obtained solid was vacuum dried at room temperature for 1 h.

[0065] (2) Preparation of functional halloysite 1) Disperse 38.5 parts of zinc ricinoleate and 1.5 parts of silver ion antibacterial agent (Fulaisibo AD-4) in 60 parts of deionized water, add 15 parts of the product obtained in step (1), ultrasonicate (40KHz) and stir at 800 rpm for 5 minutes, then use a vacuum pump to evacuate to -0.1 kPa and maintain for 5 hours, finally centrifuge and vacuum dry at 50°C for 10 hours; 2) repeating step 1), wherein the halloysite used is the halloysite containing the deodorant and the antibacterial agent prepared in step 1); 3) Repeat step 1), wherein the halloysite used is the halloysite containing the deodorant and the antibacterial agent prepared in step 2).

[0066] (3) 25 parts of magnesium polyacrylate prepared according to Example 1 were added to a mixed solution formed by 52 parts of deionized water and 13 parts of anhydrous ethanol, mixed and cooled to -10°C, and then 10 parts of functional halloysite were added. The mixture was stirred at 300 r / min for 5 min, and then quickly transferred to a high-speed centrifugal spray dryer for atomization and granulation. The conditions for atomization and granulation were a rotation speed of 20,000 rpm and an inlet air temperature of 250°C to obtain a deodorizing additive.

[0067] Comparative Example 2 Comparative Example 2 is used to illustrate the importance of deodorants. The operation of Comparative Example 2 is basically the same as that of Example 1, except that zinc ricinoleate is not added in step (2). The specific steps are: (1) Halloysite pretreatment: Halloysite nanotubes (JN-3, Guangdong Jina New Materials Technology Co., Ltd.), 3wt% sodium hydroxide solution and 20wt% polyvinyl pyrrolidone (PVP, K70) aqueous solution were added to a three-necked flask equipped with a stirrer and a thermometer at a mass ratio of 10:89:1, stirred for 5 min at room temperature and a stirring rate of 550 r / min, then transferred to a high-pressure reactor, sealed at 130°C for 4 h, and the reaction product was cooled to room temperature after the reaction was completed. Centrifuged at 800 rpm for 10 min, the obtained solid was washed with distilled water, then centrifuged, and the obtained solid was vacuum dried at room temperature for 1 h.

[0068] (2) Preparation of functional halloysite 1) Disperse 1.5 parts of silver ion antibacterial agent (Fulaishibo AD-4) and 0.3 parts of tetramethylammonium cage-type polysilsesquioxane in 98.2 parts of deionized water, add 15 parts of the product obtained in step (1), ultrasonicate (40 kHz) and stir at 800 rpm for 5 min, then use a vacuum pump to evacuate to -0.1 kPa and maintain for 5 h, finally centrifuge and vacuum dry at 50°C for 10 h; 2) repeating step 1), wherein the halloysite used is the halloysite containing the antibacterial agent and tetramethylammonium cage-type polysilsesquioxane prepared in step 1); 3) Repeat step 1), wherein the halloysite used is the halloysite containing the antibacterial agent and tetramethylammonium cage-type polysilsesquioxane prepared in step 2).

[0069] (3) 25 parts of magnesium polyacrylate prepared according to Example 1 were added to a mixed solution formed by 52 parts of deionized water and 13 parts of anhydrous ethanol, mixed and cooled to -10°C, and then 10 parts of functional halloysite were added. The mixture was stirred at 300 r / min for 5 min, and then quickly transferred to a high-speed centrifugal spray dryer for atomization and granulation. The conditions for atomization and granulation were a rotation speed of 20,000 rpm and an inlet air temperature of 250°C to obtain a deodorizing additive.

[0070] Comparative Example 3 Comparative Example 3 is used to illustrate the importance of halloysite. Halloysite is not used, and the specific steps are as follows: 15.6 parts of zinc ricinoleate, 0.61 parts of silver ion antibacterial agent (Fulaisibo AD-4), 0.4 parts of 20wt% polyvinyl pyrrolidone (PVP, K70) aqueous solution and 0.12 parts of tetramethylammonium cage-type polysilsesquioxane were dispersed in a mixed solvent of 45.27 parts of deionized water and 13 parts of anhydrous ethanol, and ultrasonically (40KHz) was stirred at 800 rpm for 5 minutes, and then 25 parts of magnesium polyacrylate prepared according to Example 1 were added, mechanically stirred for 5 minutes, cooled to -10°C, and finally quickly transferred to a high-speed centrifugal spray dryer for atomization granulation. The conditions of atomization granulation were a rotation speed of 20,000 rpm and an inlet air temperature of 250°C to obtain a deodorizing additive.

[0071] Comparative Example 4 Comparative Example 4 is used to illustrate the importance of hydrophilic polymer materials. The product of Comparative Example 4 is prepared according to step (1) and step (2) of Example 1, that is, the product of Comparative Example 4 is functional halloysite. The specific steps are as follows: (1) Halloysite pretreatment: Halloysite nanotubes (JN-3, Guangdong Jina New Materials Technology Co., Ltd.), 3wt% sodium hydroxide solution and 20wt% polyvinyl pyrrolidone (PVP, K70) aqueous solution were added to a three-necked flask equipped with a stirrer and a thermometer at a mass ratio of 10:89:1, stirred for 5 min at room temperature and a stirring rate of 550 r / min, then transferred to a high-pressure reactor, sealed at 130°C for 4 h, and the reaction product was cooled to room temperature after the reaction was completed. Centrifuged at 800 rpm for 10 min, the obtained solid was washed with distilled water, then centrifuged, and the obtained solid was vacuum dried at room temperature for 1 h.

[0072] (2) Preparation of functional halloysite 1) Disperse 38.5 parts of zinc ricinoleate, 1.5 parts of silver ion antibacterial agent (Fulexbo AD-4) and 0.3 parts of tetramethylammonium cage-type polysilsesquioxane in 59.7 parts of deionized water, add 15 parts of the product finally obtained in step (1), ultrasonicate (40 kHz) and stir at 800 rpm for 5 min, then use a vacuum pump to evacuate to -0.1 kPa and maintain for 5 h, use capillary force and pressure to make the mixed material enter the inner cavity of halloysite, and finally centrifuge and vacuum dry at 50°C for 10 h; 2) repeating step 1), wherein the halloysite used is the halloysite containing the deodorant, the antibacterial agent and the tetramethylammonium cage-type polysilsesquioxane prepared in step 1); 3) Repeat step 1), wherein the halloysite used is the halloysite containing the deodorant, the antibacterial agent and the tetramethylammonium cage-type polysilsesquioxane prepared in step 2).

[0073] Comparative Example 5 In order to illustrate the importance of introducing specific metal ions into hydrophilic polymer materials, the operation of Comparative Example 5 is basically the same as that of Example 1, except that polyacrylic acid resin neutralized with sodium hydroxide (the molar ratio of carboxylic acid to sodium carboxylate is 2, and the average molecular weight of polyacrylic acid before neutralization is 450,000) is used as the hydrophilic polymer material to replace magnesium polyacrylate; the specific steps are as follows: (1) Halloysite pretreatment: Halloysite nanotubes (JN-3, Guangdong Jina New Materials Technology Co., Ltd.), 3wt% sodium hydroxide solution and 20wt% polyvinyl pyrrolidone (PVP, K70) aqueous solution were added to a three-necked flask equipped with a stirrer and a thermometer at a mass ratio of 10:89:1, stirred for 5 min at room temperature and a stirring rate of 550 r / min, then transferred to a high-pressure reactor, sealed at 130°C for 4 h, and the reaction product was cooled to room temperature after the reaction was completed. Centrifuged at 800 rpm for 10 min, the obtained solid was washed with distilled water, then centrifuged, and the obtained solid was vacuum dried at room temperature for 1 h.

[0074] (2) Preparation of functional halloysite 1) Disperse 38.5 parts of zinc ricinoleate, 1.5 parts of silver ion antibacterial agent (Fulexbo AD-4) and 0.3 parts of tetramethylammonium cage-type polysilsesquioxane in 59.7 parts of deionized water, add 15 parts of the product finally obtained in step (1), ultrasonicate (40 kHz) and stir at 800 rpm for 5 min, then use a vacuum pump to evacuate to -0.1 kPa and maintain for 5 h, use capillary force and pressure to make the mixed material enter the inner cavity of halloysite, and finally centrifuge and vacuum dry at 50°C for 10 h; 2) repeating step 1), wherein the halloysite used is the halloysite containing the deodorant, the antibacterial agent and the tetramethylammonium cage-type polysilsesquioxane prepared in step 1); 3) Repeat step 1), wherein the halloysite used is the halloysite containing the deodorant, the antibacterial agent and the tetramethylammonium cage-type polysilsesquioxane prepared in step 2).

[0075] (3) Preparation of odor-free additives 1) Calculate the amount of hydroxide based on the acid value of polyacrylic acid and the desired target product. Disperse 0.06 mol of sodium hydroxide in water to obtain a sodium hydroxide aqueous dispersion with a total mass of 20 g; add the hydroxide aqueous dispersion dropwise to 80 g of polyacrylic acid resin aqueous solution with an average molecular weight of 450,000 under stirring conditions of 600-900 rpm, and continue stirring for 30 minutes after the dropwise addition to obtain a hydrophilic polymer material sodium polyacrylate solution. Among them, the effective solid content of the sodium polyacrylate solution is 20% by mass.

[0076] 2) Add 25 parts of sodium polyacrylate to a mixed solution formed by 52 parts of deionized water and 13 parts of anhydrous ethanol, mix well and cool to -10°C, then add 10 parts of functional halloysite, stir at 300 r / min for 5 minutes, and then quickly transfer to a high-speed centrifugal spray dryer for atomization granulation. The conditions for atomization granulation are a rotation speed of 20,000 rpm and an inlet air temperature of 250°C to obtain a deodorizing additive.

[0077] Comparative Example 6 Comparative Example 6 is used to illustrate the importance of adding alkali during the pretreatment of halloysite, and includes most of the operating steps in Example 1, except that no alkali is added in step (1). The specific steps are as follows: (1) Halloysite pretreatment: Halloysite nanotubes (JN-3, Guangdong Jina New Materials Technology Co., Ltd.), deionized water and 20wt% polyvinyl pyrrolidone (PVP, K70) aqueous solution were added to a three-necked flask equipped with a stirrer and a thermometer at a mass ratio of 10:89:1, stirred for 5 min at room temperature and a stirring rate of 550 r / min, then transferred to a high-pressure reactor, sealed at 130°C for 4 h, and the reaction product was cooled to room temperature after the reaction was completed. Centrifuged at 800 rpm for 10 min, the obtained solid was washed with distilled water, then centrifuged, and the obtained solid was vacuum dried at room temperature for 1 h.

[0078] (2) Preparation of functional halloysite 1) Disperse 38.5 parts of zinc ricinoleate, 1.5 parts of silver ion antibacterial agent (Fulexbo AD-4) and 0.3 parts of tetramethylammonium cage-type polysilsesquioxane in 59.7 parts of deionized water, add 15 parts of the product finally obtained in step (1), ultrasonicate (40 kHz) and stir at 800 rpm for 5 min, then use a vacuum pump to evacuate to -0.1 kPa and maintain for 5 h, use capillary force and pressure to make the mixed material enter the inner cavity of halloysite, and finally centrifuge and vacuum dry at 50°C for 10 h; 2) repeating step 1), wherein the halloysite used is the halloysite containing the deodorant, the antibacterial agent and the tetramethylammonium cage-type polysilsesquioxane prepared in step 1); 3) Repeat step 1), wherein the halloysite used is the halloysite containing the deodorant, the antibacterial agent and the tetramethylammonium cage-type polysilsesquioxane prepared in step 2).

[0079] (3) 25 parts of magnesium polyacrylate prepared according to Example 1 were added to a mixed solution formed by 52 parts of deionized water and 13 parts of anhydrous ethanol, mixed and cooled to -10°C, and then 10 parts of functional halloysite were added. The mixture was stirred at 300 r / min for 5 min, and then quickly transferred to a high-speed centrifugal spray dryer for atomization and granulation. The conditions for atomization and granulation were a rotation speed of 20,000 rpm and an inlet air temperature of 250°C to obtain a deodorizing additive.

[0080] Comparative Example 7 Comparative Example 7 is used to illustrate the importance of adding PVP during the pretreatment of halloysite. The operation of Comparative Example 7 is basically the same as that of Example 1, except that PVP is not added in step (1). The specific steps are as follows: (1) Halloysite pretreatment: Halloysite nanotubes (JN-3, Guangdong Jina New Materials Technology Co., Ltd.), deionized water and 3wt% sodium hydroxide solution were added to a three-necked flask equipped with a stirrer and a thermometer at a mass ratio of 10:1:89, stirred for 5 min at room temperature and a stirring rate of 550 r / min, then transferred to a high-pressure reactor, sealed at 130°C for 4 h, and the reaction product was cooled to room temperature after the reaction was completed. Centrifuged at 800 rpm for 10 min, the obtained solid was washed with distilled water, then centrifuged, and the obtained solid was vacuum dried at room temperature for 1 h.

[0081] (2) Preparation of functional halloysite 1) Disperse 38.5 parts of zinc ricinoleate, 1.5 parts of silver ion antibacterial agent (Fulexbo AD-4) and 0.3 parts of tetramethylammonium cage-type polysilsesquioxane in 59.7 parts of deionized water, add 15 parts of the product finally obtained in step (1), ultrasonicate (40 kHz) and stir at 800 rpm for 5 min, then use a vacuum pump to evacuate to -0.1 kPa and maintain for 5 h, use capillary force and pressure to make the mixed material enter the inner cavity of halloysite, and finally centrifuge and vacuum dry at 50°C for 10 h; 2) repeating step 1), wherein the halloysite used is the halloysite containing the deodorant, the antibacterial agent and the tetramethylammonium cage-type polysilsesquioxane prepared in step 1); 3) Repeat step 1), wherein the halloysite used is the halloysite containing the deodorant, the antibacterial agent and the tetramethylammonium cage-type polysilsesquioxane prepared in step 2).

[0082] (3) 25 parts of magnesium polyacrylate prepared according to Example 1 were added to a mixed solution formed by 52 parts of deionized water and 13 parts of anhydrous ethanol, mixed and cooled to -10°C, and then 10 parts of functional halloysite were added. The mixture was stirred at 300 r / min for 5 min, and then quickly transferred to a high-speed centrifugal spray dryer for atomization and granulation. The conditions for atomization and granulation were a rotation speed of 20,000 rpm and an inlet air temperature of 250°C to obtain a deodorizing additive.

[0083] Application Examples The additives prepared in the above Examples 1 to 3 and Comparative Examples 1 to 7 were respectively formulated into deodorants for performance evaluation. The preparation steps of the deodorant are as follows: 0.5 parts of carboxymethyl cellulose are pre-dissolved in 91.5 parts of deionized water, and then 8 parts of additives are added and mixed to obtain the deodorant. The deodorant is then immediately sprayed on the surface of the heat exchanger fins. 2P air conditioners use 300g of deodorant, and then the air supply mode is turned on for 1 hour or the heating mode is turned on for 30 minutes to achieve drying and film formation.

[0084] Effect Example Performance Testing: 1. Adhesion test: The additives prepared in Examples 1 to 3 and Comparative Examples 1 to 7 were prepared into deodorants according to the steps of the application examples and then sprayed on the hydrophilic aluminum foil. The spraying amount was 6 to 7 g / m2 of dry film. 2 After drying at 80℃ / 30min, use 3M tape to rate the paint and varnish according to the GB / T9286-2021 cross-cut test.

[0085] (II) Hydrophilicity test: The additives prepared in Examples 1 to 3 and Comparative Examples 1 to 7 were prepared into deodorants according to the steps of the application examples and then sprayed on the hydrophilic aluminum foil. The spraying amount was 6 to 7 g / m2 of dry film. 2 After drying at 80℃ / 30min, the hydrophilic angle of a 5μL water droplet was tested using a contact angle tester.

[0086] (III) Deodorization performance test: In an office with a length and width of approximately 18m×11m, five small rooms with a size of 2m×4m and good sealing are built side by side as test rooms. The humidity in each test room is fixed at 35-45%RH, and a new 2P air conditioner is installed in each room. Except for the small rooms, there are 45 fixed people in the office area (blank area) to carry out normal office activities.

[0087] After 45 people used the blank area for a week (the doors of the small rooms were all open during this week), the experiment was started: a test room was selected, the additive prepared in Example 1 was used to prepare a deodorant according to the steps of the application example, and then sprayed on the surface of the new 2P air conditioner fins in the test room (the application amount for a single air conditioner was 300g), and then the air conditioner heating mode (30°C, maximum wind speed) was turned on for 30 minutes to dry. Then, according to: 1) Close the door, turn on the air conditioning cooling mode (set to 16℃, maximum wind speed and ensure that the air output is cooling air, that is, the air conditioning outdoor unit is always in operation), run for 30 minutes, then switch to the air supply mode (set to low wind speed), and smell the odor at intervals of 2 minutes in the air supply mode, and the evaluation time lasts for 30 minutes; 2) After the evaluation, turn off the air conditioner and open the room door for 30 minutes to exchange the air between the test room and the blank area.

[0088] As a test cycle for odor judgment, the deodorization persistence is evaluated in multiple cycles.

[0089] For the first 20 cycles with an odor level of A, odor evaluation can be performed every 5 cycles. In order to speed up the experiment, the other four test rooms can be used simultaneously to evaluate other examples or comparative examples. When a test room completes the performance evaluation of an example or comparative example, a new 2P air conditioner of the same model from the same manufacturer is replaced, and the next example or comparative example is evaluated until the evaluation of the examples and comparative examples is completed.

[0090] During the evaluation, the tester approaches and faces the air outlet, inhales normally, and evaluates the odor level by physical sensation. The evaluation work is generally carried out by three fixed testers, who should have completed odor sniffing training and be able to independently evaluate the odor level. If the evaluation results of each tester differ by more than two levels, it is necessary to increase the number of testers or replace another group of testers to repeat the test. The test result uses the arithmetic mean of the corresponding scores of the maximum odor level smelled by each tester within 30 minutes as the final evaluation result. Record the number of cycles required to reach Class C of the odor level. The odor level and the corresponding score are evaluated according to Table 1.

[0091] Table 1 Odor levels and corresponding scores

[0092] The test results of the additives obtained in Examples 1 to 3 and Comparative Examples 1 to 7 for preparing deodorants are entered in Table 2.

[0093] Table 2 Test results

[0094] The above embodiments are preferred implementation modes of the present invention, but the implementation modes of the present invention are not limited to the above embodiments. Any other changes, modifications, substitutions, combinations, and simplifications that do not deviate from the spirit and principles of the present invention should be equivalent replacement methods and are included in the protection scope of the present invention.

Claims

1. A method for preparing a deodorizing additive having a long-lasting deodorizing effect, characterized in that The steps include: (1) Halloysite nanotubes, alkali solution and polyvinyl pyrrolidone aqueous solution are uniformly mixed, and the obtained reaction system is reacted in a closed manner at 120-180° C. for 1-8 hours; after the reaction is completed, the reaction is cooled to room temperature, the solid-liquid separation is performed, and the obtained solid is washed with water and then dried; the halloysite nanotubes, alkali and polyvinyl pyrrolidone in the reaction system are mixed in a mass ratio of 10:0.89-5.34:0.2; (2) dispersing the deodorant, antibacterial agent and cage-type polysilsesquioxane in water, adding the solid dried in step (1), stirring and dispersing with ultrasonic stirring, and then evacuating to -0.1 kPa and maintaining for 3 to 6 hours, using capillary force and pressure to allow the mixed material to enter the inner cavity of the halloysite, and then separating the solid and liquid and drying; repeating the above steps, the only difference is that the halloysite used each time is the halloysite prepared in the previous step, to obtain functional halloysite; (3) The hydrophilic polymer material and the ethanol aqueous solution are mixed, cooled to below 0°C, and then the functional halloysite is added and stirred to mix the hydrophilic polymer material with the functional halloysite, and then atomized and granulated to obtain a deodorizing additive with a long-lasting deodorizing function.

2. The method for preparing the odor-removing additive with a lasting deodorizing function according to claim 1, characterized in that: The base in step (1) is at least one of sodium hydroxide, lithium hydroxide, calcium hydroxide and potassium hydroxide; The water described in step (1) is distilled water, deionized water or purified water; The deodorant in step (2) is at least one of zinc ricinoleate, zinc ricinoleate ester, zinc phytate and primary amino polyol; The antibacterial agent described in step (2) is a silver ion antibacterial agent; The cage-type polysilsesquioxane described in step (2) is at least one of cage-type polysilsesquioxane-octaamine (amino), tetramethylammonium cage-type polysilsesquioxane and POSS monoamino; The water in step (2) is distilled water, deionized water or purified water; The hydrophilic polymer material in step (3) is polyacrylate, wherein the molar ratio of carboxylic acid to carboxylic acid metal salt is 1.4 to 4.5, and the effective solid content of the resin is 15 to 25%.

3. The method for preparing the odor-removing additive with a lasting deodorizing function according to claim 1, characterized in that: The mixing conditions in step (1) are: stirring speed 500-600 rpm, stirring time 5-10 min; The closed reaction conditions in step (1) are 130-180° C. for 1.5-4 hours; The solid-liquid separation method in step (1) is centrifugation; The drying method in step (1) is vacuum drying at room temperature; The ultrasonic stirring conditions in step (2) are: 30-50 kHz and 600-1000 rpm for at least 3 minutes; The solid-liquid separation method in step (2) is centrifugation; The drying method in step (2) is vacuum drying; The cooling temperature in step (3) is -5 to -10°C; The stirring condition in step (3) is 200-400 rpm stirring for 3-8 min; The conditions for the atomization granulation described in step (3) are a rotation speed of 15,000 to 25,000 rpm and an inlet air temperature of 200 to 300°C.

4. The method for preparing the odor-removing additive with a lasting deodorizing function according to claim 1, characterized in that: The concentration of the alkali solution in step (1) is 1 to 6% by mass; The concentration of the polyvinyl pyrrolidone aqueous solution in step (1) is 15-25% by mass; The dosage of each substance in step (2) is as follows: the deodorant, the antibacterial agent, the cage-type polysilsesquioxane and the halloysite are mixed in a mass ratio of 38-39:1-2:0.2-0.4:15; The amount of water used in step (2) is 1.0 to 1.2 times the total mass of the deodorant, antibacterial agent, cage-type polysilsesquioxane and halloysite; The concentration of the ethanol aqueous solution in step (3) is 15-25% by mass; The amount of the ethanol aqueous solution in step (3) is calculated to be 2 to 3 times the mass of the hydrophilic polymer material; The hydrophilic polymer material and the functional halloysite in step (3) are mixed in a mass ratio of 20 to 30:

10.

5. A deodorizing additive with a lasting deodorizing function, characterized in that: The method is obtained by the preparation method according to any one of claims 1 to 4.

6. Use of the deodorizing additive with a lasting deodorizing function as claimed in claim 5 in the preparation of a deodorizing agent.

7. A deodorant, characterized in that: Contains the deodorizing additive with a lasting deodorizing function as claimed in claim 5.

8. The deodorant according to claim 7, characterized in that The composition comprises the following ingredients in percentage by mass: 3-10% of the deodorizing additive with a lasting deodorizing function as claimed in claim 5, 0.1-1% of a thickener, and the balance being water.

9. The method for preparing the deodorant according to claim 8, characterized in that The method comprises the following steps: dissolving a thickener in water, and then adding the deodorizing additive with a lasting deodorizing function as claimed in claim 7 and mixing evenly to obtain a deodorizing agent.

10. Use of the deodorant according to claim 7 or 8, characterized in that The method comprises the following steps: spraying the deodorizing agent described in claim 7 or 8 on the surface of the heat exchanger fins and drying to form a film.

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