Preparation method of high-molecular reaction catalytic spray for formaldehyde treatment

Abstract

This invention discloses a method for preparing a polymeric reactive catalytic spray for formaldehyde treatment, belonging to the field of air purification technology. The method includes the following steps: liquefied amylase and a polyethyleneimine derivative undergo a cross-linking reaction in a buffer solution in the presence of a cross-linking agent; after the reaction, the mixture is purified and dried to obtain a solid catalytic-permeation complex; the catalytic-permeation complex obtained in step S1 is mixed with composite amino micropowder, liquefied amylase permeation agent, plant extract, and water to obtain a uniform spray material; the spray material obtained in step S2 is filled into the inner bag of a binary capsule, and propellant gas is introduced into the outer bag of the binary capsule. After sealing, a self-spraying package with an internal pressure of 0.65-0.75 MPa is formed. By constructing the catalytic-permeation complex, the catalytic and permeation functions are tightly combined at the molecular level, as polyethyleneimine and liquefied amylase form a stable composite structure through covalent bonds.

Description

Technical Field

[0001] This invention relates to the field of air purification technology, and in particular to a method for preparing a polymeric reactive catalytic spray for formaldehyde treatment. Background Technology

[0002] Formaldehyde, a common and significantly harmful indoor air pollutant, originates widely from various decorative and building materials, engineered wood products, furniture, textiles, and everyday chemicals. Its release period is long, lasting for several years, posing a serious threat to human health, particularly damaging the respiratory, immune, and nervous systems. It has been classified as a known carcinogen by the International Agency for Research on Cancer. With increasingly higher demands for indoor environmental quality, efficient, long-lasting, and safe formaldehyde removal technologies have become a key focus of research in this field.

[0003] Against this backdrop, formaldehyde removal technologies based on polymer catalysis have gradually attracted attention. These technologies utilize polymeric materials with specific functional groups (such as polyethyleneimine derivatives) to catalyze the polymerization or immobilization of formaldehyde with amino compounds, transforming formaldehyde into stable and harmless solid polymers, thereby achieving source removal and long-term control.

[0004] However, existing polymeric catalytic sprays generally employ a simple physical blending method to formulate various functional components, including catalysts, penetrants, and reactants. In actual application, differences in the physicochemical properties (such as polarity, surface tension, viscosity, and molecular weight distribution) between these components, along with poor interfacial compatibility in multiphase systems, easily lead to microscale phase separation or uneven distribution on the substrate surface after spraying. This microstructural inhomogeneity causes the absence or imbalance of functional components in local areas, preventing effective spatial coordination of catalytic active sites, penetration pathways, and reaction sites. This significantly restricts formaldehyde capture efficiency, reaction rate, and the stability of the final cured product, affecting the overall degradation performance and long-term durability of the product. Summary of the Invention

[0005] This invention overcomes the shortcomings of the prior art and provides a method for preparing a polymeric reaction catalytic spray for formaldehyde treatment.

[0006] To achieve the above objectives, the technical solution adopted by the present invention is as follows: a method for preparing a polymeric reaction catalytic spray for formaldehyde treatment, comprising the following steps:

[0007] S1. Liquefied amylase and polyethyleneimine derivative were cross-linked in a buffer solution in the presence of a cross-linking agent. After the reaction, the mixture was purified and dried to obtain a solid catalytic-permeation complex.

[0008] S2. The catalytic-penetrating complex obtained in step S1 is mixed with composite amino micro powder, liquefied amylase penetrant, plant extract and water to obtain a uniform spray material.

[0009] S3. The spray material obtained in step S2 is filled into the inner bag of the binary bag, and propellant gas is filled into the outer bag of the binary bag. After sealing, a self-spraying package with an internal pressure of 0.65-0.75 MPa is formed.

[0010] In a preferred embodiment of the present invention, in step S1, the mass ratio of the liquefied amylase to the polyethyleneimine derivative is 1:0.4-0.6, and the crosslinking agent is glutaraldehyde.

[0011] In a preferred embodiment of the present invention, in step S1, the crosslinking reaction is carried out by continuous stirring at 20-30°C for 1.5-2.5 hours.

[0012] In a preferred embodiment of the present invention, in step S2, the purification process is dialysis purification, and the molecular weight cutoff of the dialysis membrane used is 2000-5000 Da.

[0013] In a preferred embodiment of the present invention, in step S2, the spray material comprises, by weight percentage: 15-20% catalytic-penetrating complex, 20-30% composite amino micro powder, 3-8% liquefied amylase penetrant, 1-3% plant extract, and the remainder is water.

[0014] In a preferred embodiment of the present invention, the plant extract is lemongrass extract.

[0015] In a preferred embodiment of the present invention, the spray is contained in a self-spraying packaging structure, the packaging structure including an aluminum can, a binary bag disposed inside the can, and an ultra-fine atomizing nozzle connected to the can.

[0016] In a preferred embodiment of the present invention, the inner bladder of the binary bladder is made of polyethylene.

[0017] In a preferred embodiment of the present invention, the propellant gas is nitrogen or compressed air.

[0018] In a preferred embodiment of the present invention, the average particle size of the spray emitted by the ultrafine atomizing nozzle is 15-25 μm.

[0019] This invention addresses the shortcomings of the prior art and has the following beneficial effects:

[0020] (1) In this invention, by constructing a catalytic permeation complex, the catalytic function and the permeation function are closely combined at the molecular level. Since polyethyleneimine and liquefied amylase form a stable composite structure through covalent bonds, the two functional groups are permanently synergistic in space, thereby solving the phase separation phenomenon caused by weak intermolecular forces in traditional physical mixing systems. This allows the active components to be evenly distributed on the surface and inside of the substrate after spraying. Each complex molecule has both catalytic and permeation capabilities. Compared with the problem of uneven component distribution that is easy to occur in physical mixing formulations, this avoids the decrease in reaction efficiency caused by functional region differentiation, ensuring that formaldehyde molecules can be captured and converted in time during the permeation process, thereby improving the overall efficiency of formaldehyde removal.

[0021] (2) The catalytic permeation complex used in this invention has a stable covalent structure, which is not easily affected by changes in environmental temperature and humidity and will not cause functional degradation. The strength of the covalent bond is much higher than that of physical adsorption, so that the complex can maintain structural integrity and functional activity under complex environmental conditions, thus giving the product a longer effective period of action and being able to maintain stable formaldehyde removal performance for a longer period of time. Compared with the defects of physical mixing system that are prone to gradual failure due to component separation, it improves the durability and reliability of the product, further expands the scope of application of the product, and enables it to meet the long-term formaldehyde treatment needs under different environmental conditions.

[0022] (3) The catalytic permeation complex in this invention is designed to optimize the distribution of functional components at the microscale. Each complex molecule contains a certain proportion of catalytic and permeation groups. This precise control at the molecular level ensures the stability of the functional ratio. Thus, when processing porous materials, the active ingredients can penetrate into the deep layers of the material in a more balanced manner. Compared with the problem of limited penetration depth caused by uneven component distribution, a more uniform deep treatment effect is achieved, further enhancing the product's adaptability to various substrates, especially showing better processing performance for materials with complex porous structures. Attached Figure Description

[0023] To more clearly illustrate the technical solutions in the embodiments of the present invention or the prior art, the drawings used in the description of the embodiments or the prior art will be briefly introduced below. Obviously, the drawings described below are only some embodiments recorded in the present invention. For those skilled in the art, other drawings can be obtained based on these drawings without creative effort.

[0024] Figure 1 This is a flowchart of a preferred embodiment of the present invention;

[0025] Figure 2 This is a three-dimensional structural diagram of the aluminum tank body according to a preferred embodiment of the present invention;

[0026] Figure 3 This is a three-dimensional structural diagram of a binary capsule according to a preferred embodiment of the present invention;

[0027] In the picture: 1. Aluminum canister; 2. Binary capsule; 3. Ultra-fine atomizing nozzle. Detailed Implementation

[0028] The technical solutions of the embodiments of the present invention will be clearly and completely described below with reference to the accompanying drawings. Obviously, the described embodiments are only some embodiments of the present invention, and not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those skilled in the art without creative effort are within the scope of protection of the present invention.

[0029] Many specific details are set forth in the following description in order to provide a full understanding of the invention. However, the invention may also be practiced in other ways different from those described herein. Therefore, the scope of protection of the invention is not limited to the specific embodiments disclosed below.

[0030] Application Overview:

[0031] To improve the performance and practicality of formaldehyde removal products, existing technologies employ a combination of polyethyleneimine (PEI) derivatives as a polymeric catalyst and liquefied amylase as a penetrant. PEI derivatives possess abundant amino functional groups and high catalytic activity, effectively promoting the reaction between formaldehyde and amino compounds; liquefied amylase, on the other hand, exhibits excellent permeability and surface activity, helping the active ingredients penetrate deep into the material. Combining these two technologies achieves highly efficient catalytic conversion of formaldehyde while simultaneously enhancing the product's treatment depth on porous substrates.

[0032] However, in traditional processes where PEI and liquefied amylase are physically mixed, although each retains its functional properties, there are significant synergistic defects during actual spraying. Because PEI and liquefied amylase exist only in a physical coexistence state and lack stable chemical bonding, during spray atomization, surface deposition, and subsequent penetration, the two functional components are prone to phase separation and uneven distribution due to differences in the physicochemical properties of the components, changes in surface tension, and solvent evaporation. This microscopic separation leads to the differentiation of functional regions on the substrate surface: some regions are enriched in PEI but lack sufficient penetrant, making it difficult for formaldehyde to be effectively transported to the catalytic sites; while some regions are enriched in liquefied amylase but lack catalyst, preventing the timely conversion of penetrating formaldehyde. This spatial functional disconnect severely restricts formaldehyde capture efficiency and conversion rate, affects the integrity and stability of intermediate formation, ultimately making it difficult to further improve formaldehyde removal efficiency and limiting its long-term effectiveness.

[0033] To address the aforementioned issues and achieve stable synergy between catalysis and permeation at the microscopic scale, the key lies in overcoming the inherent phase separation tendency of physically mixed systems. Research has shown that chemical cross-linking to combine the two functional components at the molecular level can fundamentally solve the problem of uneven distribution caused by differences in their physical properties. The core idea of ​​this method is to construct a stable complex possessing both catalytic and permeation functions, ensuring that the two functions consistently work synergistically in a defined ratio and spatial relationship during the spraying process and subsequent effects.

[0034] To address this, this invention proposes a pre-crosslinking treatment of liquefied amylase and polyethyleneimine (PEI) to construct a structurally stable catalytic-permeation complex. This technique integrates the two functional components at the molecular level through covalent bonding, ensuring structural uniformity and functional synergy throughout the spray application and subsequent action. The spray using this approach achieves microscopic integration of catalytic and permeation functions, enabling formaldehyde to be simultaneously captured and catalytically converted during permeation, significantly improving reaction efficiency and depth of action. The final product, while maintaining safety and environmental friendliness, achieves a formaldehyde removal rate exceeding 98%, extends the effective action period to 720 days, and exhibits superior uniformity and durability when treating porous materials.

[0035] like Figure 1 and Figure 3 As shown, a method for preparing a polymeric reactive catalytic spray for formaldehyde treatment includes the following steps:

[0036] S1. Liquefied amylase and polyethyleneimine derivative were cross-linked in a buffer solution in the presence of a cross-linking agent. After the reaction, the mixture was purified and dried to obtain a solid catalytic-permeation complex.

[0037] S2. The catalytic-penetrating complex obtained in step S1 is mixed with composite amino micro powder, liquefied amylase penetrant, plant extract and water to obtain a uniform spray material.

[0038] S3. The spray material obtained in step S2 is filled into the inner bag of the binary bag 2, and propellant gas is filled into the outer bag of the binary bag 2. After sealing, a self-spraying package with an internal pressure of 0.65-0.75MPa is formed.

[0039] The core concept of this invention is to address the technical problem that the catalytic and penetrating components in traditional formaldehyde treatment sprays are prone to phase separation due to physical mixing, resulting in insufficient functional synergy. By covalently crosslinking polyethyleneimine catalyst and liquefied amylase penetrant, a structurally stable catalytic-penetrating complex is constructed, enabling the catalytic and penetrating functions to be permanently combined at the molecular level. This ensures that the active components are uniformly distributed and act synchronously on the surface and inside the substrate after spraying, realizing a synergistic mechanism of penetration and catalysis. Ultimately, this achieves the technical effects of improving formaldehyde removal efficiency, enhancing the durability of the effect, and ensuring safe use.

[0040] Each step will be explained in detail below.

[0041] S1. This step is the core process for preparing the catalytic-permeation complex. First, weigh the liquefied amylase and polyethyleneimine derivative, and dissolve them in a phosphate buffer solution with a pH of 6.8-7.2 at a mass ratio of 1:0.4-0.6. In a constant temperature environment of 20-30℃, stir continuously at a speed of 200-400 rpm for 30 minutes to fully disperse the enzyme molecules and polymer catalyst and establish preliminary interaction.

[0042] Subsequently, under constant stirring, a cross-linking agent solution was slowly added dropwise. Glutaraldehyde was selected as the cross-linking agent, and its addition amount was calculated according to a specific ratio of the total mass of amylase to PEI. The cross-linking reaction was completed within 1.5-2.5 hours. During the reaction, the cross-linking agent molecules specifically bound to the amino groups on the surface of amylase and the active sites on the PEI molecular chain, forming a stable covalent network structure.

[0043] After the reaction was completed, the reaction solution was transferred to a dialysis bag with a molecular weight cutoff of 2000-5000 Da and dialyzed against water at 4°C for 24-48 hours. The dialysis solution was replaced every 6-8 hours to thoroughly remove unreacted crosslinking agents, small molecule byproducts, and buffer salt ions. After dialysis, the purified solution was pre-frozen and then freeze-dried at -50°C to -60°C under a vacuum of less than 10 Pa for 24-36 hours to finally obtain a white or light yellow porous solid catalytic-permeation complex powder.

[0044] S2. This step completes the preparation and homogenization of the spray material. First, the catalytic-penetrating complex powder obtained in step S1, the composite amino micro powder (composed of urea and melamine in a specific ratio), the liquefied amylase penetrant, and the plant extract are weighed according to the formula ratio. According to the total mass percentage of the spray material, the distribution ratio of each component is: catalytic-penetrating complex 15-20%, composite amino micro powder 20-30%, liquefied amylase penetrant 3-8%, plant extract 1-3%, and the remainder is water.

[0045] The plant extract used is lemongrass extract, which not only provides auxiliary catalysis but also improves the product's aroma. At room temperature (20-25℃), the catalytic-penetration complex powder is first pre-dispersed with some water, and then the complex amino micro powder, liquefied amylase penetrant, and plant extract are added in sequence, and finally the remaining water is added.

[0046] Use a shear emulsifier to stir and mix at 2000-3000 rpm for 30-60 minutes until the system presents a homogeneous and stable milky white suspension. During the mixing process, the temperature should be controlled not to exceed 30℃ to avoid adverse effects of high temperature on enzyme activity and polymer structure.

[0047] S3. This step completes the final filling of the spray. The two-dimensional capsule bag self-spraying packaging is adopted. First, the capsule bag is pre-treated: the polyethylene inner capsule bag is rinsed with water and dried to ensure that there are no impurities. Then, the uniform spray material obtained in step S2 is quantitatively filled into the inner capsule bag through a precision filling equipment. After filling, the inner capsule bag interface is sealed immediately to prevent the material from evaporating or becoming contaminated.

[0048] Next, the filled inner bag is placed into the packaging, and the outer bag is connected and inflated. High-purity nitrogen or filtered compressed air is injected into the cavity between the inner and outer bags as the propellant gas. The pressure inside the can is stabilized within the range of 0.65-0.75 MPa using a pressure regulating device. Finally, the can is sealed to form a complete self-spraying packaging unit.

[0049] like Figure 2 and Figure 3 As shown, specifically, the packaging structure includes an aluminum can 1, a binary bag 2 disposed inside the can, and an ultra-fine atomizing nozzle 3 connected to the aluminum can 1.

[0050] Furthermore, the inner bag of the binary bag 2 is made of polyethylene. The binary bag 2 adopts a layered design, in which the inner bag is made of polyethylene, which has good chemical compatibility and flexibility, and can effectively contain the aerosol material without chemical reaction or leakage; the outer bag and the inner bag form an independent chamber for containing the propellant gas.

[0051] Furthermore, the propellant is either nitrogen or compressed air. Both gases are chemically stable, do not react with the aerosol components, and have suitable pressure characteristics, providing stable and uniform spray power. Nitrogen, as an inert gas, further ensures the long-term stability of the product.

[0052] It should be noted that the average particle size of the spray from the ultrafine atomizing nozzle 3 is 15-25μm. Its nozzle size and internal flow channel have been optimized and verified by experiments. This ensures that the spray has good suspension and diffusion in the air, and also ensures that the droplets can fully penetrate into the microporous structure of various substrates to achieve deep treatment effect.

[0053] To further simplify and make the present invention achieve its objectives and effects, the present invention will be further illustrated in conjunction with the following specific embodiments and comparative examples, but the present invention is not limited to the scope of the embodiments described herein.

[0054] It should be noted that the raw materials used in the examples and comparative examples are described below:

[0055] Liquefied amylase: content 98%, CAS number 9000-90-2, purchased from Wuhan Huajiu Pharmaceutical Technology Co., Ltd.;

[0056] Polyethyleneimine derivative: content 98%, CAS number 9002-98-6, purchased from Dezhou Huazhen New Materials Co., Ltd.;

[0057] Phosphate buffer solution: 97% purity, CAS number PM23538, purchased from Shanghai Chuangsai Technology Co., Ltd.

[0058] Glutaraldehyde crosslinking agent: content ≥50%, density 1.08-1.130 g / cm³ 3， Purchased from Shandong Longhui Chemical Co., Ltd.;

[0059] Urea: content 46%, specific surface area 2m² 2 / g, purchased from Jinan Mingjiang Chemical Co., Ltd.;

[0060] Melamine: content 99.8%, moisture 0.1%, CAS number 108-78-1, purchased from Wujiang Aokang Chemical Co., Ltd.;

[0061] Lemongrass extract: content 10%-98%, fineness 100 mesh, purchased from Lanzhou Waterles Biotechnology Co., Ltd.

[0062] Example 1:

[0063] S1. First, prepare the catalytic-permeation complex. Take 10g of liquefied amylase and 5g of polyethyleneimine derivative, dissolve them together in 200mL of pH7.0 phosphate buffer, and stir continuously at 300rpm for 30 minutes in a constant temperature water bath at 25℃. Then, slowly add 8mL of 2% glutaraldehyde solution as a crosslinking agent, and continue stirring at 25℃ for 2 hours. After the reaction, transfer the reaction solution to a dialysis bag with a molecular weight cutoff of 3000Da, and dialyze against water at 4℃ for 36 hours. During this period, change the dialysate every 8 hours. After dialysis, freeze-dry the purified solution at -55℃ and a vacuum of 8Pa for 30 hours to obtain a white porous solid catalytic-permeation complex powder with a yield of about 92%.

[0064] S2. Subsequently, the spray material is prepared by weighing 18% of the catalytic-penetration complex, 25% of the composite amino micro powder (composed of urea and melamine in a mass ratio of 3:1), 5% of the liquefied amylase penetrant, 2% of the lemongrass extract (content ≥30%), and the remainder being water. The above components are added to the mixing container in sequence and subjected to high-speed shear emulsification at 2500 rpm at room temperature of 25°C for 45 minutes until the system forms a uniform and stable milky white suspension, which is the spray material.

[0065] S3. Finally, complete the filling and packaging of the spray. Quantitatively fill the prepared spray material into an inner bag made of polyethylene material, with a filling volume of 100mL. Immediately after filling, seal the inner bag interface and place it into the aluminum can 1. Then, fill the outer bag of the binary bag 2 with high-purity nitrogen as the propellant gas, and control the pressure inside the can to be stabilized at 0.70MPa through a pressure regulating device. Finally, install the ultra-fine atomizing nozzle 3 (with an average spray particle size of approximately 20μm) and complete the overall sealing to obtain the self-spraying polymer reaction catalytic spray product.

[0066] Example 2:

[0067] This embodiment is basically the same as Example 1, except that the mass ratio of the raw materials in the preparation of the catalytic-permeation complex is different. Specifically, the mass ratio of liquefied amylase to polyethyleneimine derivative is adjusted to 1:0.4.

[0068] Example 3:

[0069] This embodiment is basically the same as Example 1, except that the mass ratio of the raw materials in the preparation of the catalytic-permeation complex is different. Specifically, the mass ratio of liquefied amylase to polyethyleneimine derivative is adjusted to 1:0.6.

[0070] Example 4:

[0071] This embodiment is basically the same as Example 1, except that the content of the catalytic-permeation complex is different. Specifically, 15% of the catalytic-permeation complex is weighed according to the mass percentage.

[0072] Example 5:

[0073] This embodiment is basically the same as Example 1, except that the content of the catalytic-permeation complex is different. Specifically, 20% of the catalytic-permeation complex is weighed according to the mass percentage.

[0074] Comparative Example 1:

[0075] This comparative example is basically the same as Example 1, except that the cross-linking reaction is cancelled. The specific steps of S1 are as follows: S1 Weigh 10g of liquefied amylase and 5g of polyethyleneimine derivative, dissolve them together in 200mL of pH7.0 phosphate buffer, stir and react at 25°C for 2 hours. After the reaction is completed, transfer the reaction solution to a dialysis bag with a molecular weight cutoff of 3000Da, and dialyze to water at 4°C for 36 hours. During this period, the dialysis solution is replaced every 8 hours. After dialysis, the purified solution is freeze-dried at -55°C and a vacuum of 8Pa for 30 hours to obtain a white porous solid catalytic-permeable complex powder with a yield of about 92%.

[0076] Comparative Example 2:

[0077] This comparative example is basically the same as Example 1, except that the cross-linking of the sample is insufficient. The specific steps of S1 are as follows: S1 First, prepare the catalytic-permeation complex. Take 10g of liquefied amylase and 5g of polyethyleneimine derivative, dissolve them together in 200mL of pH7.0 phosphate buffer, and stir continuously at 300rpm for 30 minutes in a constant temperature water bath at 25℃. Then, slowly add 8mL of 2% glutaraldehyde solution as a cross-linking agent, and continue to stir the reaction at 25℃ for 0.5 hours. After the reaction is completed, transfer the reaction solution to a dialysis bag with a molecular weight cutoff of 3000Da, and dialyze it with water at 4℃ for 36 hours. During this period, change the dialysate every 8 hours. After the dialysis is completed, freeze-dry the purified solution at -55℃ and vacuum degree 8Pa for 30 hours to obtain a white porous solid catalytic-permeation complex powder with a yield of about 92%.

[0078] Comparative Example 3:

[0079] This comparative example is basically the same as Example 1, except that the sample of penetrant is omitted. The specific steps of S2 are as follows: S2 is then the preparation of the spray material. Weigh 18% of the catalytic-penetration complex, 25% of the composite amino micro powder (composed of urea and melamine in a mass ratio of 3:1), and 2% of the lemongrass extract (content ≥30%) according to the mass percentage. The remainder is water. Add the above components to the mixing container in sequence and perform high-speed shear emulsification at 2500 rpm at room temperature of 25°C for 45 minutes until the system forms a uniform and stable milky white suspension, which is the spray material.

[0080] Comparative Example 4:

[0081] This comparative example is basically the same as Example 1, except that: for the traditionally packaged sample, the specific steps of S1 are as follows: S3, the spray material obtained in step S2 is directly poured into a single-layer aluminum aerosol can, and then the propellant gas (nitrogen) is directly injected into the can and contacts the upper space of the material through a pressurization method. After sealing, a traditional aerosol packaging with an internal pressure of 0.70 MPa is formed. Finally, the ultra-fine atomizing nozzle 3 is installed and the whole is sealed, thus obtaining the self-spraying polymer reaction catalytic spray product.

[0082] Comparative Example 5:

[0083] This comparative example is basically the same as Example 1, except that the mass ratio of the raw materials in the preparation of the catalytic-permeable complex is different. The specific steps of S1 are as follows: S1 First, the catalytic-permeable complex is prepared by taking 10g of liquefied amylase and 3g of polyethyleneimine derivative and dissolving them together in 200mL of pH7.0 phosphate buffer. The mixture is stirred continuously at 300rpm for 30 minutes in a constant temperature water bath at 25℃. Then, 8mL of 2% glutaraldehyde solution is slowly added as a crosslinking agent. The mixture is stirred and reacted for 2 hours at 25℃. After the reaction is completed, the reaction solution is transferred to a dialysis bag with a molecular weight cutoff of 3000Da and dialyzed against water at 4℃ for 36 hours. The dialysis solution is replaced every 8 hours. After dialysis, the purified solution is freeze-dried at -55℃ and a vacuum of 8Pa for 30 hours to obtain a white porous solid catalytic-permeable complex powder with a yield of about 92%.

[0084] Comparative Example 6:

[0085] This comparative example is basically the same as Example 1, except that the mass ratio of the raw materials in the preparation of the catalytic-permeable complex is different. The specific steps of S1 are as follows: S1 First, the catalytic-permeable complex is prepared by taking 10g of liquefied amylase and 7g of polyethyleneimine derivative and dissolving them together in 200mL of pH7.0 phosphate buffer. The mixture is stirred continuously at 300rpm for 30 minutes in a constant temperature water bath at 25℃. Then, 8mL of 2% glutaraldehyde solution is slowly added as a crosslinking agent. The mixture is stirred and reacted for 2 hours at 25℃. After the reaction is completed, the reaction solution is transferred to a dialysis bag with a molecular weight cutoff of 3000Da and dialyzed against water at 4℃ for 36 hours. The dialysis solution is replaced every 8 hours. After dialysis, the purified solution is freeze-dried at -55℃ and a vacuum of 8Pa for 30 hours to obtain a white porous solid catalytic-permeable complex powder with a yield of about 92%.

[0086] Comparative Example 7:

[0087] This comparative example is basically the same as Example 1, except that the content of the catalytic-penetrating complex is different. The specific steps of S2 are as follows: S2 is then used to prepare the spray material. Weigh 13% of the catalytic-penetrating complex, 25% of the composite amino micro powder (composed of urea and melamine in a mass ratio of 3:1), 5% of the liquefied amylase penetrant, and 2% of the lemongrass extract (content ≥30%) according to the mass percentage, with the remainder being water. Add the above components to the mixing container in sequence, and perform high-speed shear emulsification at 2500 rpm at room temperature of 25°C for 45 minutes until the system forms a uniform and stable milky white suspension, which is the spray material.

[0088] Comparative Example 8:

[0089] This comparative example is basically the same as Example 1, except that the content of the catalytic-penetrating complex is different. The specific steps of S2 are as follows: S2 is then used to prepare the spray material. Weigh 22% of the catalytic-penetrating complex, 25% of the composite amino micro powder (composed of urea and melamine in a mass ratio of 3:1), 5% of the liquefied amylase penetrant, and 2% of the lemongrass extract (content ≥30%) according to the mass percentage. The remainder is water. Add the above components to the mixing container in sequence and perform high-speed shear emulsification at 2500 rpm at room temperature of 25°C for 45 minutes until the system forms a uniform and stable milky white suspension, which is the spray material.

[0090] Performance testing: The self-spraying polymer reaction catalysts of Examples 1-6 and Comparative Examples 1-4 were tested for formaldehyde removal efficiency, duration of action, microscopic uniformity, penetration depth, spray atomization performance and storage stability, respectively. The results are shown in Table 2.

[0091] Formaldehyde removal efficiency: A standard formaldehyde release source was placed in a sealed environment chamber, and the initial formaldehyde concentration was controlled to 1.0 ± 0.1 mg / m³. 3 Temperature 25±1℃, humidity 50±5%. Spraying amount 50g / m² 2 The sample was uniformly sprayed onto the surface of the emission source, and air samples were collected from inside the chamber at 1h, 6h, 24h, 72h, and 168h after spraying. The formaldehyde concentration was determined using the phenol reagent spectrophotometric method, and the formaldehyde removal rate at different time points was calculated. A blank control and a physically mixed control sample were also set up to evaluate the product's improvement effect on catalytic reaction rate and final purification efficiency through horizontal comparison.

[0092] Durability of Function: To simulate long-term use, a combination of accelerated aging and natural attenuation methods was employed. The substrates after spraying were placed in a constant temperature and humidity chamber at 40℃ and 85%RH for 30 days of accelerated aging, with samples taken every 5 days to measure the formaldehyde removal rate. Simultaneously, the performance changes of the samples were continuously observed under natural conditions of 25℃ and 50%RH for 180 days. The product's functional durability was evaluated by comparing the removal rate decay curves before and after aging. Furthermore, the chemical structure and microstructure of the cured spray layer after aging were analyzed using Fourier Transform Infrared Spectroscopy (FTIR) and Scanning Electron Microscopy (SEM) to verify its structural stability and ability to retain functional groups.

[0093] Microscopic uniformity: Scanning electron microscopy (SEM) combined with energy dispersive spectroscopy (EDS) was used to characterize the microstructure and elemental distribution of the substrate surface and cross-section after spraying. After the samples were sprayed and cured, they were sputter-coated with gold and placed under SEM to observe the surface morphology (×500-×5000), focusing on the presence of phase separation, agglomeration, or cracks. The uniformity of nitrogen (derived from polyethyleneimine and amino powder) and oxygen (derived from amylase and plant extracts) distribution was analyzed by EDS surface scanning, and their coefficients of variation were calculated to quantitatively evaluate the degree of dispersion uniformity of the active components at the microscale.

[0094] Penetration Depth: Multilayer filter paper or standard porous building materials (such as gypsum board or MDF) were used as simulated substrates. Samples were sprayed after vertical cross-section cutting. After curing, the layers were peeled off one by one along the cross-section, and the content of the catalytic-penetration complex in each layer was detected using high-performance liquid chromatography (HPLC) or fluorescence labeling. By plotting the distribution curve of the active component concentration as a function of depth, the penetration depth (defined as the depth at which the concentration drops to 10% of the surface concentration) and the penetration uniformity index were calculated to evaluate the spray's ability to penetrate and cover complex porous structures.

[0095] Spray atomization performance: The spray particle size distribution was measured using a laser particle size analyzer. Spray samples were collected under standard spraying conditions (pressure 0.7 MPa, nozzle distance from detector 30 cm), and D10, D50, D90, and average particle size were statistically analyzed to evaluate atomization uniformity. Simultaneously, a high-speed camera system was used to record the spray morphology and diffusion angle to analyze whether droplet aggregation, drift, or uneven settling occurred during atomization. Actual spraying tests were conducted to observe the adhesion of the spray to vertical and inclined surfaces, and the application suitability and coverage effect were comprehensively evaluated based on the particle size data.

[0096] Storage stability: The filled finished product was subjected to long-term storage tests under different temperature conditions (4℃, 25℃, 40℃), with samples taken and tested at 0, 1, 3, 6, and 12 months. Evaluation indicators included: changes in can pressure, spray pattern observation, particle size distribution stability, and changes in pH, viscosity, and active ingredient content of the spray. Simultaneously, a high-temperature and high-humidity cycling test (40℃, 75%RH, 7 days per cycle) was conducted to examine whether the spray experienced stratification, precipitation, discoloration, or functional degradation under extreme storage conditions, ensuring product performance stability within the shelf life.

[0097] Table 1: Performance test results of self-spraying polymer reaction catalyst sprays in Examples 1-5 and Comparative Examples 1-8

[0098] Group Formaldehyde removal efficiency (168h, %) Durability of action (removal rate after 180 days, %) Microscopic uniformity (CV%) Penetration depth (mm) Spray atomization performance (average particle size, μm) Storage stability (activity retention after 12 months, %) Example 1 99.3 95.0 5.0 2.5 20.0 95.5 Example 2 92.0 85.0 10.0 1.8 20.0 88.2 Example 3 99.5 95.5 4.8 2.6 20.0 96.7 Example 4 98.2 94.5 5.2 2.4 20.0 94.1 Example 5 98.7 95.2 4.9 2.6 20.0 96.6 Comparative Example 1 85.0 70.0 15.0 1.5 20.0 80.5 Comparative Example 2 92.0 80.0 10.0 2.0 20.0 85.4 Comparative Example 3 88.0 75.0 12.0 0.8 20.0 82.8 Comparative Example 4 95.0 85.0 8.0 2.0 25.0 75.6 Comparative Example 5 87.0 72.0 14.0 1.8 20.0 81.4 Comparative Example 6 98.3 94.8 5.1 2.5 20.0 95.1 Comparative Example 7 86.0 71.0 13.5 1.6 20.0 80.9 Comparative Example 8 90.0 78.0 11.0 1.9 20.0 82.4

[0099] A comparison between Example 1 and Comparative Example 1 reveals that: In Comparative Example 1, no cross-linking reaction was performed, and the liquefied amylase and polyethyleneimine coexisted solely through physical mixing. Due to the lack of covalent bonds, they were highly susceptible to phase separation and uneven distribution during spraying due to surface tension, solvent evaporation, and differences in interfacial compatibility. The catalytic sites and penetration pathways could not effectively coordinate spatially, resulting in formaldehyde molecules not being captured and transformed in a timely manner during penetration. This led to a significant deterioration in microscopic uniformity (CV = 15.0%), a reduction in penetration depth (1.5 mm), and a substantial decrease in formaldehyde removal efficiency (85.0%) and persistence (70.0%). This demonstrates that simple physical mixing cannot achieve stable synergy of functional components; covalent cross-linking is crucial for ensuring superior performance.

[0100] A comparison between Example 1 and Comparative Example 2 reveals that the cross-linking reaction time in Comparative Example 2 was shortened to 0.5 hours, resulting in insufficient cross-linking and an incomplete covalent network construction in the catalytic-permeable complex. Some enzymes and polymers remained bound by physical adsorption or weak interactions, making them prone to dissociation under long-term use or environmental changes, thus reducing functional synergy. Although the formaldehyde removal efficiency (92.0%) was acceptable in the short term, its persistence (80.0%) and microstructure uniformity (CV=10.0%) were significantly lower than in Example 1, indicating that sufficient cross-linking time is a necessary condition for forming a stable complex and ensuring long-term performance.

[0101] A comparison between Example 1 and Comparative Example 3 reveals that Comparative Example 3 omitted the liquefied amylase penetrant, relying solely on the penetrating function of the catalytic-penetrating complex. While the complex itself possesses some permeability, the added liquefied amylase penetrant further reduces surface tension and enhances wetting and penetration into porous substrates. Without this component, the overall penetrating performance of the spray significantly decreased (penetration depth only 0.8 mm), preventing the active ingredients from penetrating deep into the material. This limited formaldehyde removal efficiency (88.0%) and persistence (75.0%), indicating that the auxiliary role of the penetrant is crucial for achieving deep treatment.

[0102] A comparison between Example 1 and Comparative Example 4 reveals that: Comparative Example 4 uses traditional single-layer aerosol can packaging, where the propellant gas directly contacts the material. During long-term storage, this may cause oxidation, denaturation, or stratification of the components, leading to decreased spray atomization performance (average particle size 25.0 μm) and significantly reduced storage stability (activity retention rate 75.6%). In contrast, Example 1 uses binary capsule 2 packaging, physically isolating the propellant gas from the material, maintaining the chemical stability of the components and the uniformity of atomization, thereby improving the long-term reliability and application performance of the product.

[0103] A comparison of Examples 1-3 and Comparative Examples 5-6 reveals that in Examples 2-3, the mass ratios of liquefied amylase to polyethyleneimine were 1:0.4 and 1:0.6, respectively, both within the preferred range (1:0.4-0.6) of this invention. In these cases, the catalytic and permeation functions of the cross-linked complex were well-coordinated, resulting in a good synergistic effect. In Comparative Example 5, the ratio decreased to 1:0.3, indicating an excessively low polyethyleneimine content, leading to insufficient catalytic sites in the complex and a reduced formaldehyde capture capacity. In Comparative Example 6, the ratio was increased to 1:0.7, but excessive polyethyleneimine may affect the cross-linking efficiency and the hydrophilicity of the complex, thus reducing permeation uniformity. This demonstrates that an imbalanced ratio disrupts the functional balance and affects overall performance.

[0104] A comparison of Examples 1 / 4-5 and Comparative Examples 7-8 reveals that the catalytic-penetrating complex content in Examples 4-5, at 15% and 20% respectively, falls within the preferred range (15-20%), ensuring sufficient activity while avoiding excessively high system viscosity that could negatively impact atomization and penetration. In Comparative Example 7, the content decreased to 13%, resulting in insufficient active ingredients and a significant reduction in formaldehyde removal efficiency and persistence. In Comparative Example 8, the content increased to 22%, leading to increased system viscosity, which may affect spray atomization and component dispersion, thereby reducing microscopic uniformity and penetration depth. This indicates that the complex content needs to be controlled within a reasonable range to balance activity, rheology, and application performance.

[0105] The above description is based on the preferred embodiments of the present invention. It will be apparent to those skilled in the art that the present invention is not limited to the details of the exemplary embodiments described above, and that the invention can be implemented in other specific forms without departing from its spirit or essential characteristics. Therefore, the embodiments should be considered exemplary and non-limiting in all respects. The scope of the invention is defined by the appended claims rather than the foregoing description, and all variations falling within the meaning and scope of equivalents of the claims are intended to be included within the present invention. No reference numerals in the claims should be construed as limiting the scope of the claims.

[0106] Furthermore, it should be understood that although this specification describes embodiments, not every embodiment contains only one independent technical solution. This narrative style is merely for clarity. Those skilled in the art should consider the specification as a whole, and the technical solutions in each embodiment can also be appropriately combined to form other embodiments that can be understood by those skilled in the art.

Claims

1. A method for preparing a molecular reaction catalytic spray for formaldehyde treatment, characterized in that, Includes the following steps: S1. Liquefied amylase and polyethyleneimine derivative were cross-linked in a buffer solution in the presence of a cross-linking agent. After the reaction, the mixture was purified and dried to obtain a solid catalytic-permeation complex. S2. The catalytic-penetrating complex obtained in step S1 is mixed with composite amino micro powder, liquefied amylase penetrant, plant extract and water to obtain a uniform spray material. S3. The spray material obtained in step S2 is filled into the inner bag of the binary bag, and propellant gas is filled into the outer bag of the binary bag. After sealing, a self-spraying package with an internal pressure of 0.65-0.75 MPa is formed.

2. The method for preparing a polymeric reaction catalytic spray for formaldehyde treatment according to claim 1, characterized in that: In step S1, the mass ratio of the liquefied amylase to the polyethyleneimine derivative is 1:0.4-0.6, and the crosslinking agent is glutaraldehyde.

3. The method for preparing a polymeric reaction catalytic spray for formaldehyde treatment according to claim 1, characterized in that: In step S1, the crosslinking reaction is carried out by continuous stirring at 20-30°C for 1.5-2.5 hours.

4. The method for preparing a polymeric reaction catalytic spray for formaldehyde treatment according to claim 1, characterized in that: In step S2, the purification process is dialysis purification, and the molecular weight cutoff of the dialysis membrane used is 2000-5000 Da.

5. The method for preparing a polymeric reaction catalytic spray for formaldehyde treatment according to claim 1, characterized in that: In step S2, the spray material comprises, by weight percentage: 15-20% catalytic-penetrating complex, 20-30% composite amino micro powder, 3-8% liquefied amylase penetrant, 1-3% plant extract, and the remainder is water.

6. The method for preparing a polymeric reaction catalytic spray for formaldehyde treatment according to claim 5, characterized in that: The plant extract is lemongrass extract.

7. A polymeric reaction catalytic spray for formaldehyde treatment, and a method of using the preparation method of the polymeric reaction catalytic spray for formaldehyde treatment according to any one of claims 1-6, characterized in that, The spray is contained in a self-spraying packaging structure, which includes an aluminum can, a binary bag disposed inside the can, and an ultra-fine atomizing nozzle connected to the can.

8. A polymeric reaction catalyst spray for formaldehyde treatment according to claim 7, characterized in that: The inner bladder of the binary bladder is made of polyethylene.

9. A polymeric reaction catalytic spray for formaldehyde treatment according to claim 8, characterized in that: The propellant is nitrogen or compressed air.

10. A polymeric reaction catalytic spray for formaldehyde treatment according to claim 9, characterized in that: The average particle size of the spray emitted by the ultra-fine atomizing nozzle is 15-25 μm.

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