Formaldehyde removing and negative ion releasing car essence and preparation method thereof

Abstract

The application relates to the technical field of automobile essence preparation, and particularly discloses automobile essence capable of removing formaldehyde and releasing negative ions and a preparation method thereof, which comprises the following raw materials in parts by weight: deionized water 500-600 parts, a negative ion release enhancement component 18-24 parts, an aldehyde removal component 12-20 parts, anhydrous ethanol 30-40 parts, a dispersing agent 8-14 parts, phenoxyethanol 14-18 parts, an initiator solution 22-26 parts and citral 6-10 parts; the negative ion release enhancement component and the aldehyde removal component are added in the application, the negative ion release enhancement component is prepared from silane coupling agent modified core-shell particles, the outer layer of the core-shell particles is a porous titanium dioxide structure, and the inner core is modified tourmaline powder; the aldehyde removal component is prepared from sodium alginate and allyl glycidyl ether through ring-opening esterification reaction, and then is prepared from chemical crosslinking of hydroxypropyl acrylate and methacrylic acid, so that the removal capacity of formaldehyde, the negative ion release capacity and the bacteriostatic effect are coordinated and enhanced.

Description

TECHNICAL FIELD

[0001] The application relates to the preparation technology of automobile essence, in particular to automobile essence for removing formaldehyde and releasing negative ions and a preparation method thereof. BACKGROUND

[0002] As a kind of automobile care product, the automobile essence can not only clean the dirt on the surface and interior of the automobile efficiently, but also provide comprehensive maintenance and protection for the automobile, and has a wide application in the field of automobile beauty and maintenance.

[0003] Since the adhesive, paint and plastic parts used in the interior decoration materials of the automobile mostly use formaldehyde as solvent or additive, with the passage of time, the pollution gas mainly containing formaldehyde will be emitted, which can cause harm to human body. With the improvement of health consciousness, it is particularly important to provide automobile essence for removing formaldehyde and releasing negative ions.

[0004] The patent application file 202011011529.5 discloses automobile essence for removing formaldehyde and releasing negative ions and a preparation method thereof, wherein the raw materials are as follows in terms of weight parts: 800-1000 parts of distilled water, 60-80 parts of nano-shell powder, 8-10 parts of natural pure extract liquid, 30-40 parts of negative ion powder, 40-60 parts of titanate, 30-40 parts of ethanol, 60-80 parts of formaldehyde removal additive, 8-14 parts of stable dispersing agent, and 4-8 parts of phenoxyethanol. The automobile essence prepared by the patent application file has good formaldehyde purification effect, can purify the air in the car, remove odor, release negative ions, and is beneficial to human health. However, the formaldehyde removal additive in the application is only a simple mixture of activated carbon powder, nano-titanium dioxide and nano-silicon dioxide and other functional core-shell particles. These functional core-shell particles are prone to agglomeration, resulting in that the automobile essence prepared has general formaldehyde removal performance, negative ion release capacity and antibacterial performance, which is difficult to meet the market demand.

[0005] Based on the above-mentioned defects, the application provides automobile essence for removing formaldehyde and releasing negative ions and a preparation method thereof, which has excellent antibacterial effect. SUMMARY

[0006] In order to solve the problems mentioned in the background art, the application provides automobile essence for removing formaldehyde and releasing negative ions and a preparation method thereof.

[0007] The automobile essence for removing formaldehyde and releasing negative ions comprises the following raw materials in terms of weight parts: 500-600 parts of deionized water, 18-24 parts of negative ion release enhancement component, 12-20 parts of formaldehyde removal component, 30-40 parts of anhydrous ethanol, 8-14 parts of dispersing agent, 14-18 parts of phenoxyethanol, 22-26 parts of initiator solution and 6-10 parts of citral.

[0008] The preparation method of the automobile essence for removing formaldehyde and releasing negative ions comprises the following steps:

[0009] The formaldehyde removal component and anhydrous ethanol are added into deionized water and stirred uniformly, and the negative ion release enhancement component, dispersant, phenoxy ethanol and initiator solution are added while stirring, the temperature is raised to 76-80 DEG C, the stirring is continued for 2-4 h, the temperature is cooled to room temperature, the citral is added and stirred uniformly, and the automobile essence for removing formaldehyde and releasing negative ions is obtained.

[0010] Preferably, the dispersant is Orotan 731A or BYK-190.

[0011] Preferably, the initiator solution is an ammonium persulfate aqueous solution with a mass fraction of 12-16%.

[0012] Preferably, the negative ion release enhancement component is prepared by the following steps:

[0013] In step A1, the tourmaline powder is added into Tris-HCl buffer solution with pH of 8-9 and stirred uniformly, and then dopamine is added and stirred for 18-22 h, and the pretreated tourmaline powder is obtained after filtration, washing and drying, wherein the mass ratio of the tourmaline powder, Tris-HCl buffer solution and dopamine is 1.2-1.6:50-60:0.8-1.4, and the phenolic hydroxyl structure contained in the dopamine has good adhesion, and the dopamine can self-polymerize in the Tris-HCl buffer solution to form a polydopamine layer on the surface of the tourmaline powder, thereby giving the tourmaline powder excellent adhesion;

[0014] In step A2, the pretreated tourmaline powder, cerium nitrate, lanthanum nitrate and zinc nitrate are added into deionized water and ultrasonically dispersed uniformly, 4-6 M ammonia water is added to adjust the pH to 8-9, and the stirring is continued for 25-35 min, and the modified tourmaline powder is obtained after filtration, drying, calcination at 430-460 DEG C for 24-28 min and cooling to room temperature, wherein the mass ratio of the pretreated tourmaline powder, cerium nitrate, lanthanum nitrate, zinc nitrate and deionized water is 4.5-5.5:0.65-0.85:0.6-0.8:0.4-0.5:20-40, the polydopamine layer contained on the surface of the pretreated tourmaline powder has good adhesion and can adsorb the cerium nitrate, lanthanum nitrate and zinc nitrate onto the surface of the pretreated tourmaline powder, the ammonia water as a precipitant can combine with cerium ions, lanthanum ions and zinc ions in the cerium nitrate, lanthanum nitrate and zinc nitrate to form hydroxides, and through calcination, the hydroxide precipitates are pyrolyzed to form cerium oxide, lanthanum oxide and zinc oxide, thereby forming nano cerium oxide, nano lanthanum oxide and nano zinc oxide on the surface of the pretreated tourmaline powder;

[0015] Step A3, the modified tourmaline powder is mixed with a crosslinking agent, the pH is adjusted to 2-2.2, tetrabutyl titanate is added, a mixed solution a of polyoxyethylene polyoxypropylene ether, polyvinyl alcohol and anhydrous ethanol is added dropwise while stirring, the dropping is completed within 10 min, the temperature is raised to 128-134℃, the stirring is continued for 24-28 h, the product is washed and dried, then is calcined at 490-510℃ for 2-2.2 h to obtain functionalized core-shell particles, the functionalized core-shell particles, deionized water, anhydrous ethanol and a silane coupling agent are mixed uniformly, the temperature is raised to 40-46℃, the stirring is continued for 6-8 h, the product is centrifuged, washed and dried to obtain anion release enhancing components, wherein the mass ratio of the modified tourmaline powder, the crosslinking agent, the tetrabutyl titanate and the mixed solution a is 1.4-1.6:40-60:3.2-3.6:20-24, the mass ratio of the polyoxyethylene polyoxypropylene ether, the polyvinyl alcohol and the anhydrous ethanol in the mixed solution a is 1:10-12:20, and the mass ratio of the functionalized core-shell particles, the deionized water, the anhydrous ethanol and the silane coupling agent is 2-4:10-16:32-40:1-1.4, in the above reaction process, the polyvinyl alcohol is used as a pore forming agent, the polyoxyethylene polyoxypropylene ether is used as a dispersant, and the hydroxyl groups generated by the hydrolysis of the tetrabutyl titanate can form hydrogen bonds with the hydroxyl groups in the crosslinking agent, so that the modified tourmaline powder is coated inside, thereby preparing the core-shell particles with the modified tourmaline powder as the inner layer and the porous structure of titanium dioxide structure as the shell, and then treating the core-shell particles with the silane coupling agent to obtain the anion release enhancing components.

[0016] Preferably, the silane coupling agent is KH-550 or KH-540.

[0017] Preferably, in step A3, the crosslinking agent is a chitosan aqueous solution with a mass fraction of 1-3%.

[0018] Preferably, in step A3, the polyvinyl alcohol is polyvinyl alcohol 1000.

[0019] Preferably, the aldehyde removing component is prepared by the following steps:

[0020] Step B1, sodium alginate and deionized water are mixed and stirred uniformly at room temperature, the pH value is adjusted to 10-11, then allyl glycidyl ether is added dropwise, the dropping is completed within 10 min, the temperature is raised to 64-70℃, the stirring is continued for 5.4-6.2 h, then the pH is adjusted to neutral, the product is washed and dried to obtain unsaturated sodium alginate, wherein the mass ratio of the sodium alginate, the deionized water and the allyl glycidyl ether is 3.2-4.4:70-80:15, under alkaline conditions, ring-opening esterification reaction occurs between the carboxyl groups on the sodium alginate and the epoxy groups on the allyl glycidyl ether to obtain the unsaturated sodium alginate.

[0021] Step B2, add hydroxypropyl acrylate, methacrylic acid into deionized water, mix uniformly, adjust pH to 6-6.6, warm up to 56-62 DEG C, stir and drop the mixed solution b of unsaturated sodium alginate, saturated calcium chloride aqueous solution, activated carbon, glycerol triglycidyl ether and anhydrous THF, control 15 min drop, continue stirring for 1.2-1.6 h, wash, dry, obtain the aldehyde removal component, wherein the mass ratio of hydroxypropyl acrylate, methacrylic acid, deionized water and mixed solution b is 1.2-1.6:40-50:20-28:0.06-0.08, in the mixed solution b, the mass ratio of unsaturated sodium alginate, saturated calcium chloride aqueous solution, activated carbon, glycerol triglycidyl ether and anhydrous THF is 2.6-3.2:14-18:0.6-0.8:0.2-0.4:25, in the above reaction process, the calcium ion in the saturated calcium chloride aqueous solution can be chemically crosslinked with sodium alginate, and the aldehyde removal component is obtained at the same time.

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

[0023] In order to improve the aldehyde removal performance, negative ion release capacity and bacteriostatic effect of the prepared automobile essence, the present application proceeds from two aspects, one is to add a negative ion release enhancement component, the negative ion release enhancement component is prepared from silane coupling agent modified core-shell particles, the outer layer of the core-shell particles is a porous titanium dioxide structure, and the inner core is modified tourmaline powder, the existence of the porous titanium dioxide structure not only has a very high specific surface area, can effectively adsorb formaldehyde, but also plays a nano-titanium dioxide photocatalytic performance, not only has excellent bacteriostatic performance, but also can decompose the formaldehyde in the car, on the other hand, the hydroxyl radicals generated by titanium dioxide can have a chain reaction with the negative oxygen ions on the surface of tourmaline, generating more negative ions, the modified tourmaline powder is prepared from cerium ions, lanthanum ions and zinc ion doped modified tourmaline powder, through co-doping, not only can expand the light absorption range of tourmaline to the visible light region, enhance the ability of photocatalytic decomposition of organic matter, indirectly generate more negative ions, but also can refine the grain through it, improve the negative ion release efficiency of the automobile essence, the other is to add an aldehyde removal component, on the one hand, the surface of the sodium alginate in the aldehyde removal component contains rich carboxyl and hydroxyl groups, which can produce hydrogen bond with formaldehyde molecules, on the other hand, the allyl glycidyl ether grafted on the surface of the aldehyde removal component can generate a three-dimensional network structure with hydroxypropyl acrylate and methacrylic acid, not only improve its removal capacity for formaldehyde, but also can effectively fix the high surface area activated carbon, which can be introduced into the automobile essence, can coordinate with the negative ion release enhancement component, enhance the removal capacity for formaldehyde, negative ion release capacity and bacteriostatic effect. DETAILED DESCRIPTION

[0024] In order to make the embodiments of the present application more easily understood, the present application will be described in detail below in conjunction with specific examples, which are merely illustrative and not limited to the scope of the application.

[0025] The main raw materials used in the examples and comparative examples and the content of their components are shown as follows:

[0026] Polyvinyl alcohol 1000 is commercially available from Shandong Xuanhao Environmental Protection Technology Co., Ltd., activated carbon is produced by Tianjin Tundong Zhengcheng Fine Chemical Reagent Factory, tourmaline powder is 3000 mesh tourmaline powder commercially available from Lingshou County Yunshi Mine Product Processing Factory, and sodium alginate is commercially available from Anhui Linan Biological Technology Co., Ltd.

[0027] The present application will be further described in detail below in conjunction with examples and comparative examples.

[0028] Preparation Examples 1-3 and Comparative Preparation Examples 1-3 provide a method for preparing functionalized core-shell particles.

[0029] Preparation Example 1

[0030] The present preparation example provides a negative ion release enhancing component, which is prepared by the following steps:

[0031] Step A1, the tourmaline powder is added to the Tris-HCl buffer solution with pH 8, stirred at a speed of 510 rpm for 12 min to be uniform, dopamine is added, the stirring speed is kept unchanged, and the reaction is continued for 18 h, filtered, washed with deionized water for 3 times, and dried at 52℃ to constant weight to obtain the pretreated tourmaline powder, wherein the mass ratio of the tourmaline powder, the Tris-HCl buffer solution and the dopamine is 1.2:50:0.8;

[0032] Step A2, the pretreated tourmaline powder, cerium nitrate, lanthanum nitrate and zinc nitrate are added to deionized water, the ultrasonic frequency is controlled at 40 kHz, the ultrasonic power is 600 w, and the ultrasonic is performed for 14 min to be uniform, 4M ammonia water is added to adjust the pH to 8 while stirring at a speed of 460 rpm, and the stirring is performed for 25 min, filtered, dried at 46℃ to constant weight, placed at 430℃, calcined for 24 min, cooled to room temperature, and the modified tourmaline powder is obtained, wherein the mass ratio of the pretreated tourmaline powder, cerium nitrate, lanthanum nitrate, zinc nitrate and deionized water is 4.5:0.65:0.6:0.4:20;

[0033] Step A3, the modified tourmaline powder is stirred with 1% chitosan aqueous solution at a rotation speed of 480 rpm for 16 min until uniform, the pH is adjusted to 2 with 18% acetic acid solution, then tetrabutyl titanate is added, stirring and adding dropwise a mixed solution a of polyoxyethylene polyoxypropylene ether, polyvinyl alcohol 1000 and anhydrous ethanol, controlling the dropwise addition to be completed within 10 min, after dropping, the temperature is raised to 128℃, the rotation speed is kept unchanged, and the stirring reaction is continued for 24 h, then the product is washed with anhydrous ethanol and deionized water for 3 times respectively, dried at 56℃ until constant weight, then placed at 490℃ and calcined for 2 h to obtain functional core-shell particles, then the functional core-shell particles, deionized water, anhydrous ethanol and KH-550 are stirred at a rotation speed of 620 rpm for 14 min until uniform, the temperature is raised to 40℃, and the stirring reaction is carried out for 6 h, then centrifuged, the precipitate is washed with anhydrous ethanol and deionized water for 3 times respectively, and dried at 46℃ until constant weight to obtain the anion release enhancing component, wherein the mass ratio of the modified tourmaline powder, chitosan aqueous solution, tetrabutyl titanate and mixed solution a is 1.4:40:3.2:20, and the mass ratio of polyoxyethylene polyoxypropylene ether, polyvinyl alcohol 1000 and anhydrous ethanol in the mixed solution a is 1:10:20, and the mass ratio of the functional core-shell particles, deionized water, anhydrous ethanol and KH-550 is 2:10:32:1.

[0034] Preparation Example 2

[0035] The preparation example provides an anion release enhancing component, which is prepared by the following steps:

[0036] Step A1, the tourmaline powder is added into Tris-HCl buffer solution with pH of 8.5, stirred at a rotation speed of 530 rpm for 16 min until uniform, then dopamine is added, the rotation speed is kept unchanged, and the stirring reaction is continued for 20 h, then filtered, washed with deionized water for 4 times, and dried at 54℃ until constant weight to obtain the pretreated tourmaline powder, wherein the mass ratio of the tourmaline powder, Tris-HCl buffer solution and dopamine is 1.4:55:1.1;

[0037] Step A2, the pretreated tourmaline powder, cerium nitrate, lanthanum nitrate and zinc nitrate are added into deionized water, ultrasonic frequency is controlled to be 35 kHz and ultrasonic power is 550 w, and ultrasonic is carried out for 18 min until uniform, then 5M ammonia water is added under stirring at a rotation speed of 500 rpm to adjust the pH to 8.5, stirred for 30 min, then filtered, dried at 50℃ until constant weight, placed at 445℃ and calcined for 26 min, cooled to room temperature to obtain the modified tourmaline powder, wherein the mass ratio of the pretreated tourmaline powder, cerium nitrate, lanthanum nitrate, zinc nitrate and deionized water is 5:0.75:0.7:0.45:30;

[0038] Step A3, the modified tourmaline powder was stirred with 2% chitosan aqueous solution at a rotation speed of 500 rpm for 20 min until uniform, the pH was adjusted to 2.1 with 20% acetic acid solution, then tetrabutyl titanate was added, and the mixture was stirred and dropwise added with a mixed solution a of polyoxyethylene polyoxypropylene ether, polyvinyl alcohol 1000 and anhydrous ethanol, the dropwise addition was completed within 10 min, then the temperature was raised to 131°C, the rotation speed was kept unchanged, and the stirring was continued for 26 h, then the product was washed with anhydrous ethanol and deionized water for 4 times respectively, dried at 60°C until constant weight, then placed at 500°C and calcined for 2.1 h to obtain functional core-shell particles, then the functional core-shell particles, deionized water, anhydrous ethanol and KH-540 were stirred at a rotation speed of 640 rpm for 18 min until mixed uniformly, the temperature was raised to 43°C, and the stirring was continued for 7 h, then centrifuged, the precipitate was washed with anhydrous ethanol and deionized water for 4 times respectively, and dried at 48°C until constant weight to obtain anion release enhancement component, wherein the mass ratio of the modified tourmaline powder, chitosan aqueous solution, tetrabutyl titanate and mixed solution a was 1.5:50:3.4:22, and the mass ratio of polyoxyethylene polyoxypropylene ether, polyvinyl alcohol 1000 and anhydrous ethanol in the mixed solution a was 1:11:20, and the mass ratio of the functional core-shell particles, deionized water, anhydrous ethanol and KH-540 was 3:13:36:1.2.

[0039] Preparation Example 3

[0040] The preparation example provides an anion release enhancement component, which is prepared by the following steps:

[0041] Step A1, the tourmaline powder was added into Tris-HCl buffer solution with pH of 9, and stirred at a rotation speed of 550 rpm for 20 min until uniform, then dopamine was added, the rotation speed was kept unchanged, and the stirring was continued for 22 h, then filtered, washed with deionized water for 5 times, and dried at 56°C until constant weight to obtain pretreated tourmaline powder, wherein the mass ratio of the tourmaline powder, Tris-HCl buffer solution and dopamine was 1.6:60:1.4;

[0042] Step A2, the pretreated tourmaline powder, cerium nitrate, lanthanum nitrate and zinc nitrate were added into deionized water, and ultrasonic treatment was performed at an ultrasonic frequency of 50 kHz and an ultrasonic power of 500 w for 22 min until uniform, then 6M ammonia water was added while stirring to adjust the pH to 9, and the stirring was continued for 35 min, then filtered, dried at 54°C until constant weight, placed at 460°C and calcined for 28 min, and cooled to room temperature to obtain modified tourmaline powder, wherein the mass ratio of the pretreated tourmaline powder, cerium nitrate, lanthanum nitrate, zinc nitrate and deionized water was 5.5:0.85:0.8:0.5:40;

[0043] Step A3, the modified tourmaline powder was stirred with 3% chitosan aqueous solution at a rotation speed of 520 rpm for 24 min until uniform, the pH was adjusted to 2.2 with 22% acetic acid solution, then tetrabutyl titanate was added, and the mixture was stirred and dropwise added with a mixed solution a of polyoxyethylene polyoxypropylene ether, polyvinyl alcohol 1000 and anhydrous ethanol, the dropwise addition was completed within 10 min, then the temperature was raised to 134°C, the rotation speed was kept unchanged, and the stirring was continued for 28 h, then the product was washed with anhydrous ethanol and deionized water for 5 times respectively, dried at 64°C until constant weight, then placed at 510°C and calcined for 2.2 h to obtain functional core-shell particles, then the functional core-shell particles, deionized water, anhydrous ethanol and KH-550 were stirred at a rotation speed of 660 rpm for 22 min until uniformly mixed, the temperature was raised to 46°C, and the stirring was continued for 8 h, then centrifuged, the precipitate was washed with anhydrous ethanol and deionized water for 5 times respectively, and dried at 50°C until constant weight to obtain anion release enhancement component, wherein the mass ratio of modified tourmaline powder, chitosan aqueous solution, tetrabutyl titanate and mixed solution a is 1.6:60:3.6:24, and in the mixed solution a, the mass ratio of polyoxyethylene polyoxypropylene ether, polyvinyl alcohol 1000 and anhydrous ethanol is 1:12:20, and the mass ratio of functional core-shell particles, deionized water, anhydrous ethanol and KH-550 is 4:16:40:1.4.

[0044] Comparative Preparation Example 1

[0045] The present comparative preparation example provides an anion release enhancement component prepared by the following steps:

[0046] Step A1, the tourmaline powder was added to Tris-HCl buffer solution with pH of 8, and stirred at a rotation speed of 510 rpm for 12 min until uniform, then dopamine was added, the rotation speed was kept unchanged, and the stirring was continued for 18 h, then filtered, washed with deionized water for 3 times, and dried at 52°C until constant weight to obtain pretreated tourmaline powder, wherein the mass ratio of tourmaline powder, Tris-HCl buffer solution and dopamine is 1.2:50:0.8;

[0047] Step A2, the pretreated tourmaline powder, lanthanum nitrate and zinc nitrate were added to deionized water, and ultrasonic treatment was performed at an ultrasonic frequency of 40 kHz and an ultrasonic power of 600 w for 14 min until uniform, then 4M ammonia water was added while stirring to adjust the pH to 8, and the stirring was continued for 25 min, then filtered, dried at 46°C until constant weight, placed at 430°C and calcined for 24 min, and cooled to room temperature to obtain modified tourmaline powder, wherein the mass ratio of pretreated tourmaline powder, lanthanum nitrate, zinc nitrate and deionized water is 4.5:0.6:0.4:20;

[0048] Step A3, the modified tourmaline powder was stirred with 1% chitosan aqueous solution at a rotation speed of 480 rpm for 16 min until uniform, the pH was adjusted to 2 with 18% acetic acid solution, then tetrabutyl titanate was added, the mixture was stirred and a mixed solution a of polyoxyethylene polyoxypropylene ether, polyvinyl alcohol 1000 and anhydrous ethanol was added dropwise, the dropping was completed within 10 min, then the temperature was raised to 128℃, the rotation speed was kept constant, and the stirring was continued for 24 h, then the product was washed with anhydrous ethanol and deionized water for 3 times respectively, dried at 56℃ until constant weight, then placed in a furnace at 490℃ and calcined for 2 h to obtain functional core-shell particles, then the functional core-shell particles, deionized water, anhydrous ethanol and KH-550 were stirred at a rotation speed of 620 rpm for 14 min until uniform, the temperature was raised to 40℃, and the stirring was continued for 6 h, then centrifuged, the precipitate was washed with anhydrous ethanol and deionized water for 3 times respectively, and dried at 46℃ until constant weight to obtain the anion release enhancing component, wherein the mass ratio of modified tourmaline powder, chitosan aqueous solution, tetrabutyl titanate and mixed solution a is 1.4:40:3.2:20, and the mass ratio of polyoxyethylene polyoxypropylene ether, polyvinyl alcohol 1000 and anhydrous ethanol in the mixed solution a is 1:10:20, and the mass ratio of functional core-shell particles, deionized water, anhydrous ethanol and KH-550 is 2:10:32:1.

[0049] Comparative Preparation Example 2

[0050] The present comparative preparation example provides an anion release enhancing component prepared by the following steps:

[0051] Step A1, tourmaline powder was added to Tris-HCl buffer solution with pH of 8, stirred at a rotation speed of 510 rpm for 12 min until uniform, then dopamine was added, the rotation speed was kept constant, and the stirring was continued for 18 h, then filtered, washed with deionized water for 3 times, and dried at 52℃ until constant weight to obtain pretreated tourmaline powder, wherein the mass ratio of tourmaline powder, Tris-HCl buffer solution and dopamine is 1.2:50:0.8;

[0052] Step A2, the pretreated tourmaline powder, cerium nitrate and lanthanum nitrate were added to deionized water, and ultrasonic frequency of 40 kHz and ultrasonic power of 600 w were controlled to ultrasonically stir for 14 min until uniform, then 4M ammonia water was added to adjust the pH to 8 while stirring at a rotation speed of 460 rpm, and the stirring was continued for 25 min, then filtered, dried at 46℃ until constant weight, placed in a furnace at 430℃ and calcined for 24 min, and cooled to room temperature to obtain modified tourmaline powder, wherein the mass ratio of pretreated tourmaline powder, cerium nitrate, lanthanum nitrate and deionized water is 4.5:0.65:0.6:20;

[0053] Step A3, the modified tourmaline powder was stirred with 1% chitosan aqueous solution at a rotation speed of 480 rpm for 16 min until uniform, the pH was adjusted to 2 with 18% acetic acid solution, then tetrabutyl titanate was added, the mixture was stirred and a mixed solution a of polyoxyethylene polyoxypropylene ether, polyvinyl alcohol 1000 and anhydrous ethanol was added dropwise, the dropping was completed within 10 min, then the temperature was raised to 128°C, the rotation speed was kept constant, and the stirring was continued for 24 h, then the product was washed with anhydrous ethanol and deionized water for 3 times respectively, dried at 56°C until constant weight, then placed at 490°C and calcined for 2 h to obtain functional core-shell particles, then the functional core-shell particles, deionized water, anhydrous ethanol and KH-550 were stirred at a rotation speed of 620 rpm for 14 min until uniform, the temperature was raised to 40°C, and the stirring was continued for 6 h, then centrifuged, the precipitate was washed with anhydrous ethanol and deionized water for 3 times respectively, and dried at 46°C until constant weight to obtain the anion release enhancing component, wherein the mass ratio of the modified tourmaline powder, chitosan aqueous solution, tetrabutyl titanate and mixed solution a is 1.4:40:3.2:20, and the mass ratio of polyoxyethylene polyoxypropylene ether, polyvinyl alcohol 1000 and anhydrous ethanol in the mixed solution a is 1:10:20, and the mass ratio of the functional core-shell particles, deionized water, anhydrous ethanol and KH-550 is 2:10:32:1.

[0054] Comparative Preparation Example 3

[0055] The present comparative preparation example provides an anion release enhancing component prepared by the following steps:

[0056] Step A1, the tourmaline powder was added to Tris-HCl buffer solution with pH of 8, stirred at a rotation speed of 510 rpm for 12 min until uniform, then dopamine was added, the rotation speed was kept constant, and the stirring was continued for 18 h, then filtered, washed with deionized water for 3 times, and dried at 52°C until constant weight to obtain the pretreated tourmaline powder, wherein the mass ratio of the tourmaline powder, Tris-HCl buffer solution and dopamine is 1.2:50:0.8;

[0057] Step A2, the pretreated tourmaline powder, cerium nitrate, lanthanum nitrate and zinc nitrate were added to deionized water, ultrasonic frequency was controlled at 40 kHz and ultrasonic power was 600 w, and ultrasonic was performed for 14 min until uniform, then 4M ammonia water was added to adjust the pH to 8 while stirring at a rotation speed of 460 rpm, and the stirring was continued for 25 min, then filtered, dried at 46°C until constant weight, placed at 430°C and calcined for 24 min, and cooled to room temperature to obtain the modified tourmaline powder, wherein the mass ratio of the pretreated tourmaline powder, cerium nitrate, lanthanum nitrate, zinc nitrate and deionized water is 4.5:0.65:0.6:0.4:20;

[0058] Step A3, the modified tourmaline powder was stirred with 1% chitosan aqueous solution at a rotation speed of 480 rpm for 16 min until uniform, the pH was adjusted to 2 with 18% acetic acid solution, then tetrabutyl titanate was added, and the mixture was stirred and a mixed solution a of polyoxyethylene polyoxypropylene ether and anhydrous ethanol was added dropwise, which was controlled to be completed within 10 min, after dropping, the temperature was increased to 128°C, the rotation speed was kept unchanged, and the stirring reaction was continued for 24 h, then the product was washed with anhydrous ethanol and deionized water for 3 times respectively, dried at 56°C until constant weight, then placed at 490°C and calcined for 2 h to obtain functional core-shell particles, then the functional core-shell particles, deionized water, anhydrous ethanol and KH-550 were stirred at a rotation speed of 620 rpm for 14 min until uniformly mixed, the temperature was increased to 40°C, and the stirring reaction was carried out for 6 h, then centrifugation was performed, the precipitate was washed with anhydrous ethanol and deionized water for 3 times respectively, and dried at 46°C until constant weight to obtain anion release enhancement component, wherein the mass ratio of modified tourmaline powder, chitosan aqueous solution, tetrabutyl titanate and mixed solution a is 1.4:40:3.2:20, the mass ratio of polyoxyethylene polyoxypropylene ether and anhydrous ethanol in the mixed solution a is 1:20, and the mass ratio of functional core-shell particles, deionized water, anhydrous ethanol and KH-550 is 2:10:32:1.

[0059] Preparation Examples 4-6 and Comparative Preparation Example 4 provide an aldehyde-removing component.

[0060] Preparation Example 4

[0061] The present preparation example provides an aldehyde-removing component, which is prepared by the following steps:

[0062] Step B1, sodium alginate and deionized water were mixed, stirred at a rotation speed of 510 rpm for 14 min at room temperature until uniform, the pH value was adjusted to 10 with 0.006% sodium hydroxide aqueous solution, then allyl glycidyl ether was added dropwise, which was controlled to be completed within 10 min, the temperature was increased to 62°C, the rotation speed was kept unchanged, and the stirring was continued for 5.4 h, then the pH was adjusted to neutral with 0.01% hydrochloric acid aqueous solution, washed with deionized water for 3 times, and dried at 56°C until constant weight to obtain unsaturated sodium alginate, wherein the mass ratio of sodium alginate, deionized water and allyl glycidyl ether is 3.2:70:15;

[0063] Step B2, add hydroxypropyl acrylate, methacrylic acid into deionized water, control the rotating speed at 600 rpm, stir for 15 min until uniform, adjust the pH to 6 with 2% citric acid aqueous solution, warm up to 56℃, stir and drop the mixture b of unsaturated sodium alginate, saturated calcium chloride aqueous solution, activated carbon, glycerol triglycidyl ether and anhydrous THF, control the dropping within 15 min, continue to stir for 1.2 h, wash with deionized water for 3 times, dry at 62℃ until constant weight to obtain the aldehyde-removing component, wherein the mass ratio of hydroxypropyl acrylate, methacrylic acid, deionized water and mixture b is 1.2:40:20:0.06, and the mass ratio of unsaturated sodium alginate, saturated calcium chloride aqueous solution, activated carbon, glycerol triglycidyl ether and anhydrous THF in the mixture b is 2.6:14:0.6:0.2:25.

[0064] Preparation Example 5

[0065] The present preparation example provides an aldehyde-removing component, which is prepared by the following steps:

[0066] Step B1, mix sodium alginate and deionized water, stir at room temperature at a rotating speed of 530 rpm for 16 min until uniform, adjust the pH to 10.5 with 0.0022% sodium hydroxide aqueous solution, then drop allyl glycidyl ether, control the dropping within 10 min, warm up to 67℃, maintain the rotating speed, continue to stir for 5.8 h, then adjust the pH to neutral with 0.015% hydrochloric acid aqueous solution, wash with deionized water for 4 times, dry at 60℃ until constant weight to obtain the unsaturated sodium alginate, wherein the mass ratio of sodium alginate, deionized water and allyl glycidyl ether is 3.8:75:15;

[0067] Step B2, add hydroxypropyl acrylate, methacrylic acid into deionized water, control the rotating speed at 640 rpm, stir for 18 min until uniform, adjust the pH to 6.3 with 3% citric acid aqueous solution, warm up to 59℃, stir and drop the mixture b of unsaturated sodium alginate, saturated calcium chloride aqueous solution, activated carbon, glycerol triglycidyl ether and anhydrous THF, control the dropping within 15 min, continue to stir for 1.4 h, wash with deionized water for 4 times, dry at 66℃ until constant weight to obtain the aldehyde-removing component, wherein the mass ratio of hydroxypropyl acrylate, methacrylic acid, deionized water and mixture b is 1.4:45:24:0.07, and the mass ratio of unsaturated sodium alginate, saturated calcium chloride aqueous solution, activated carbon, glycerol triglycidyl ether and anhydrous THF in the mixture b is 2.9:16:0.7:0.3:25.

[0068] Preparation Example 6

[0069] The present preparation example provides an aldehyde-removing component, which is prepared by the following steps:

[0070] Step B1, sodium alginate and deionized water were mixed, stirred at room temperature for 18 min at 550 rpm until uniform, adjusted to pH 11 with 0.04% sodium hydroxide solution, then added dropwise allyl glycidyl ether, controlled to drop in 10 min, heated to 70°C, continue to stir for 6.2 h, then adjusted to neutral pH with 0.02% hydrochloric acid solution, washed with deionized water 5 times, dried at 64°C to constant weight, to obtain unsaturated sodium alginate, wherein the mass ratio of sodium alginate, deionized water and allyl glycidyl ether is 4.4:80:15;

[0071] Step B2, hydroxypropyl acrylate and methacrylic acid were added to deionized water, the stirring speed was controlled at 680 rpm, and stirred for 21 min until uniform, the pH was adjusted to 6.6 with 4% citric acid solution, heated to 62°C, and the mixture liquid b of unsaturated sodium alginate, saturated calcium chloride solution, activated carbon, glycerol triglycidyl ether and anhydrous THF was added dropwise while stirring, controlled to drop in 15 min, the stirring speed was maintained, and the reaction was continued for 1.6 h, washed with deionized water 5 times, and dried at 70°C to constant weight to obtain the de-aldehyde component, wherein the mass ratio of hydroxypropyl acrylate, methacrylic acid, deionized water and mixture liquid b is 1.6:50:28:0.08, and the mass ratio of unsaturated sodium alginate, saturated calcium chloride solution, activated carbon, glycerol triglycidyl ether and anhydrous THF in the mixture liquid b is 3.2:18:0.8:0.4:25.

[0072] Comparative Preparation Example 4

[0073] The present comparative preparation example provides a de-aldehyde component, which is prepared by the following steps:

[0074] Step B1, sodium alginate and deionized water were mixed, stirred at room temperature for 18 min at 550 rpm until uniform, adjusted to pH 11 with 0.04% sodium hydroxide solution, then added dropwise allyl glycidyl ether, controlled to drop in 10 min, heated to 70°C, continue to stir for 6.2 h, then adjusted to neutral pH with 0.02% hydrochloric acid solution, washed with deionized water 5 times, dried at 64°C to constant weight, to obtain unsaturated sodium alginate, wherein the mass ratio of sodium alginate, deionized water and allyl glycidyl ether is 4.4:80:15;

[0075] Step B2, add hydroxypropyl acrylate, methacrylic acid into deionized water, control the rotating speed at 600 rpm, stir for 15 min until uniform, adjust the pH to 6 with 2% citric acid aqueous solution, heat to 56℃, stir and drop the mixed solution b of unsaturated sodium alginate, saturated calcium chloride aqueous solution, activated carbon, glycerol triglycidyl ether and anhydrous THF, control the dropping time at 15 min, continue to stir for 1.2 h, wash with deionized water for 3 times, dry at 62℃ until constant weight to obtain the aldehyde removal component, wherein the mass ratio of hydroxypropyl acrylate, methacrylic acid, deionized water and mixed solution b is 1.2:40:20:0.06, and the mass ratio of unsaturated sodium alginate, saturated calcium chloride aqueous solution, activated carbon, glycerol triglycidyl ether and anhydrous THF in the mixed solution b is 2.6:14:0.6:0.2:25.

[0076] Examples 1-3 and Comparative Examples 1-4 provide a car essence for removing formaldehyde and releasing negative ions and a preparation method thereof.

[0077] Example 1

[0078] The present embodiment provides a car essence for removing formaldehyde and releasing negative ions, which comprises the following raw materials by weight:

[0079] deionized water 500 parts, the negative ion release enhancement component prepared in Preparation Example 1 18 parts, the aldehyde removal component prepared in Preparation Example 4 12 parts, anhydrous ethanol 30 parts, Orotan 731A 8 parts, phenoxyethanol 14 parts, initiator solution 22 parts and citral 6 parts;

[0080] The preparation method of the car essence for removing formaldehyde and releasing negative ions comprises the following steps:

[0081] add the aldehyde removal component and anhydrous ethanol into deionized water, control the rotating speed at 840 rpm, stir for 18 min until uniform, maintain the rotating speed unchanged, add the negative ion release enhancement component, Orotan 731A, phenoxyethanol and initiator solution while stirring, heat to 76℃, continue to stir for 2 h, cool to room temperature, then add citral, control the rotating speed at 660 rpm, stir for 12 min until uniform to obtain the car essence for removing formaldehyde and releasing negative ions, wherein the initiator solution is 12% ammonium persulfate aqueous solution.

[0082] Example 2

[0083] The present embodiment provides a car essence for removing formaldehyde and releasing negative ions, which comprises the following raw materials by weight:

[0084] Deionized water 550 parts, the negative ion release enhancement component prepared in Preparation Example 2 21 parts, the aldehyde removal component prepared in Preparation Example 5 16 parts, anhydrous ethanol 35 parts, BYK-190 11 parts, phenoxy ethanol 16 parts, initiator solution 24 parts and citral 8 parts;

[0085] The preparation method of the automobile essence for removing formaldehyde and releasing negative ions comprises the following steps:

[0086] The aldehyde removal component and anhydrous ethanol are added into the deionized water, the stirring speed is controlled to be 880 rpm, and stirring is performed for 22 min until uniformity is achieved; the stirring speed is maintained unchanged, the negative ion release enhancement component, BYK-190, phenoxy ethanol and the initiator solution are added while stirring, the temperature is raised to 78℃, and stirring is continuously performed for 3 h; the temperature is cooled to room temperature, citral is added, the stirring speed is controlled to be 680 rpm, and stirring is performed for 16 min until uniformity is achieved; and the automobile essence for removing formaldehyde and releasing negative ions is obtained, and the initiator solution is an ammonium persulfate aqueous solution with a mass fraction of 14%.

[0087] Example 3

[0088] The example provides an automobile essence for removing formaldehyde and releasing negative ions, which comprises the following raw materials in parts by weight:

[0089] Deionized water 600 parts, the negative ion release enhancement component prepared in Preparation Example 3 24 parts, the aldehyde removal component prepared in Preparation Example 6 20 parts, anhydrous ethanol 40 parts, Orotan 731A 14 parts, phenoxy ethanol 18 parts, initiator solution 26 parts and citral 10 parts;

[0090] The preparation method of the automobile essence for removing formaldehyde and releasing negative ions comprises the following steps:

[0091] The aldehyde removal component and anhydrous ethanol are added into the deionized water, the stirring speed is controlled to be 920 rpm, and stirring is performed for 26 min until uniformity is achieved; the stirring speed is maintained unchanged, the negative ion release enhancement component, Orotan 731A, phenoxy ethanol and the initiator solution are added while stirring, the temperature is raised to 80℃, and stirring is continuously performed for 4 h; the temperature is cooled to room temperature, citral is added, the stirring speed is controlled to be 700 rpm, and stirring is performed for 20 min until uniformity is achieved; and the automobile essence for removing formaldehyde and releasing negative ions is obtained, and the initiator solution is an ammonium persulfate aqueous solution with a mass fraction of 16%.

[0092] Comparative Example 1

[0093] Comparative Example 1 is the same as Example 1, except that the negative ion release enhancement component in Example 1 is replaced by the negative ion release enhancement component prepared in Comparative Preparation Example 1.

[0094] Comparative Example 2

[0095] Comparative Example 2 is the same as Example 1, except that the negative ion release enhancing component in Example 1 is replaced by the negative ion release enhancing component prepared in Comparative Preparation Example 2.

[0096] Comparative Example 3

[0097] Comparative Example 3 is the same as Example 1, except that the negative ion release enhancing component in Example 1 is replaced by the negative ion release enhancing component prepared in Comparative Preparation Example 3.

[0098] Comparative Example 4

[0099] Comparative Example 4 is the same as Example 1, except that the aldehyde removing component in Example 1 is replaced by the aldehyde removing component prepared in Comparative Preparation Example 4.

[0100] Performance test

[0101] Formaldehyde gas adsorption test: the elimination of free formaldehyde in the wood-based panel is used as the evaluation index of formaldehyde removal rate.

[0102] 8 pieces of medium density board with an area of 1 m 2 and a formaldehyde emission of 5.0 mg / m 3 were respectively placed in 8 formaldehyde emission detection climate chambers, 3 of which were respectively placed in the automotive essence prepared in Examples 1-3, 4 of which were respectively placed in the automotive essence prepared in Comparative Examples 1-4 as the test group, and the remaining one was used as a blank control. The formaldehyde concentration in different climate chambers was measured after 72 h, and the formaldehyde removal rate of different adsorption particles was calculated, and the calculation formula is as follows:

[0103] Formaldehyde removal rate (%) = (blank control concentration-test group concentration) / blank control concentration;

[0104] Negative ion release test: the automotive essence in Examples 1-3 and Comparative Examples 1-4 was evenly coated on a polytetrafluoroethylene plate, the coating thickness was controlled to be 50 μm, and the size was cut to 16 cm x 16 cm, and then placed in a room temperature of 24±2℃ and a humidity of 70±2%, and then placed for 12 h, and the negative ion release amount was measured by ion meter measurement method;

[0105] Antibacterial performance test: the automotive essence in Examples 1-3 and Comparative Examples 1-4 was taken, and the antibacterial performance and antibacterial durability of the antibacterial coating were detected according to the detection method in GB / T 21866-2008 "Antibacterial Coatings (Paint Film) Antibacterial Property Determination and Antibacterial Effect", and the inhibition effect of Escherichia coli and Candida albicans was taken as an example, the average antibacterial rate of Escherichia coli and Candida albicans was calculated, and the test results are shown in Table 1.

[0106] Table 1 Performance test of automotive essence

[0107]

[0108] As can be seen from Table 1, compared with Comparative Examples 1-4, the automobile essence prepared in the application has more excellent formaldehyde removal capacity, anion release capacity and antibacterial effect.

[0109] The specific embodiments are only an explanation of the application, and are not a limitation of the application. Those skilled in the art can make modifications to the embodiments without creative contribution after reading the specification, and as long as the modifications are within the scope of the claims of the application, they are protected by the patent law.

Claims

1. A car essence for removing formaldehyde and releasing negative ions, characterized in that, The following raw materials are included by weight parts: Deionized water 500-600 parts, negative ion release enhancement component 18-24 parts, aldehyde removal component 12-20 parts, anhydrous ethanol 30-40 parts, dispersing agent 8-14 parts, phenoxy ethanol 14-18 parts, initiator solution 22-26 parts and citral 6-10 parts; The negative ion release enhancement component is first obtained by self-polymerization reaction of tourmaline powder and dopamine to obtain pretreated tourmaline powder, then by calcination of the pretreated tourmaline powder with cerium nitrate, lanthanum nitrate and zinc nitrate to obtain modified tourmaline powder, then by sol-gel method of the modified tourmaline powder with tetrabutyl titanate to obtain functionalized core-shell particles, and finally by modification of the functionalized core-shell particles with silane coupling agent to obtain the negative ion release enhancement component; The aldehyde removal component is obtained by ring-opening esterification reaction of sodium alginate and allyl glycidyl ether to obtain unsaturated sodium alginate, and then by chemical crosslinking of the unsaturated sodium alginate with hydroxypropyl acrylate and methacrylic acid; The aldehyde removal component is obtained by the following steps: Step B1, mix sodium alginate and deionized water, stir uniformly at room temperature, adjust pH value to 10-11, then drop allyl glycidyl ether, control the dropping time to be 10 min, heat to 64-70℃, continue to stir for 5.4-6.2h, then adjust pH to neutral, wash and dry to obtain unsaturated sodium alginate; Step B2, mix hydroxypropyl acrylate, methacrylic acid and deionized water, mix uniformly, adjust pH to 6-6.6, heat to 56-62℃, stir and drop the mixed liquid b of unsaturated sodium alginate, saturated calcium chloride solution, activated carbon, glycerol triglycidyl ether and anhydrous THF, control the dropping time to be 15 min, continue to stir for 1.2-1.6h, wash and dry to obtain the aldehyde removal component.

2. The automobile essence for removing formaldehyde and releasing negative ions according to claim 1, characterized in that, The negative ion release enhancement component is obtained by the following steps: Step A1, add tourmaline powder into Tris-HCl buffer solution, stir uniformly, add dopamine, stir for 18-22h, filter, wash and dry to obtain pretreated tourmaline powder; Step A2, add pretreated tourmaline powder, cerium nitrate, lanthanum nitrate and zinc nitrate into deionized water, ultrasonic dispersion, adjust pH to 8-9, stir for 25-35min, filter, dry, calcine at 430-460℃ for 24-28min, cool to room temperature to obtain modified tourmaline powder; Step A3, mix modified tourmaline powder and crosslinking agent uniformly, adjust pH to 2-2.2, then add tetrabutyl titanate, stir and drop the mixed liquid a of polyoxyethylene polyoxypropylene ether, polyvinyl alcohol and anhydrous ethanol, control the dropping time to be 10 min, after dropping, heat to 128-134℃, continue to stir for 24-28h, wash, dry, calcine at 490-510℃ for 2-2.2h to obtain functionalized core-shell particles, mix the functionalized core-shell particles, deionized water, anhydrous ethanol and silane coupling agent uniformly, heat to 40-46℃, stir for 6-8h, centrifuge, wash and dry the precipitate to obtain the negative ion release enhancement component.

3. The car essence for removing formaldehyde and releasing negative ions according to claim 2, characterized in that, In step A1, the mass ratio of tourmaline powder, Tris-HCl buffer solution and dopamine is 1.2-1.6: 50-60: 0.8-1.

4.

4. The automobile essence for removing formaldehyde and releasing negative ions according to claim 2, characterized in that, In the step A2, the mass ratio of the pre-treated tourmaline powder, cerium nitrate, lanthanum nitrate, zinc nitrate and deionized water is 4.5-5.5:0.65-0.85:0.6-0.8:0.4-0.5:20-40.

5. The automobile essence for removing formaldehyde and releasing negative ions according to claim 2, characterized in that, In the step A3, the mass ratio of the modified tourmaline powder, crosslinking agent, tetrabutyl titanate and mixed solution a is 1.4-1.6:40-60:3.2-3.6:20-24, and in the mixed solution a, the mass ratio of polyoxyethylene polyoxypropylene ether, polyvinyl alcohol and anhydrous ethanol is 1:10-12:20, and the mass ratio of functionalized core-shell particles, deionized water, anhydrous ethanol and silane coupling agent is 2-4:10-16:32-40:1-1.

4.

6. The automobile essence for removing formaldehyde and releasing negative ions according to claim 1, characterized in that, In the step B1, the mass ratio of sodium alginate, deionized water and allyl glycidyl ether is 3.2-4.4:70-80:

15.

7. The automobile essence of claim 1, wherein the automobile essence is capable of removing formaldehyde and releasing negative ions. In the step B2, the mass ratio of hydroxypropyl acrylate, methyl methacrylate, deionized water and mixed solution b is 1.2-1.6:40-50:20-28:0.06-0.

08.

8. The automobile essence of claim 1, wherein the automobile essence is capable of removing formaldehyde and releasing negative ions. In the mixed solution b, the mass ratio of unsaturated sodium alginate, saturated calcium chloride aqueous solution, activated carbon, glycerol triglycidyl ether and anhydrous THF is 2.6-3.2:14-18:0.6-0.8:0.2-0.4:

25.

9. A method for preparing the car essence of claim 1-8 for removing formaldehyde and releasing negative ions, characterized in that, The method comprises the following steps: The aldehyde-removing component and anhydrous ethanol are added into deionized water and stirred uniformly, the negative ion-releasing enhancing component, dispersant, phenoxyethanol and initiator solution are added while stirring, the temperature is raised to 76-80℃, the stirring is continued for 2-4h, the temperature is cooled to room temperature, citral is added and stirred uniformly, and thus a car essence capable of removing formaldehyde and releasing negative ions is obtained.

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