Scavenging agent for efficiently removing TVOC (Total Volatile Organic Compounds) and formaldehyde and preparation method thereof

Abstract

The invention relates to the technical field of scavenging agents for efficiently removing TVOC and formaldehyde, in particular to a scavenging agent for efficiently removing TVOC and formaldehyde and a preparation method thereof.The scavenging agent is prepared from, by weight, 0.5-2 parts of natural plant extract, 0.5-2 parts of amino compound, 1.5-3 parts of high-molecular polymer emulsion, 0.5-2 parts of biological enzyme, 0.5-1 part of photocatalyst and 70-95 parts of deionized water. The scavenging agent for efficiently removing TVOC and formaldehyde, prepared by the invention, has an excellent formaldehyde removal effect under light and dark conditions, and the preparation process is simple, safe and environment-friendly.

Description

Technical Field

[0001] This invention relates to the field of scavengers for the efficient removal of TVOC and formaldehyde, and specifically to a scavenger for the efficient removal of TVOC and formaldehyde and its preparation method. Background Technology

[0002] The artificial boards, paints, adhesives, and other materials widely used in interior decoration continuously release formaldehyde, benzene compounds, and other TVOCs. These pollutants are highly toxic and can irritate the eyes, nose, and respiratory tract mucous membranes. Long-term exposure can also harm the human immune and nervous systems, seriously threatening the health of residents. As people become more health-conscious, their demands for indoor air quality are constantly increasing. There is an urgent need for effective removers that can effectively treat these complex pollutants to solve the air pollution problems in enclosed spaces such as homes and offices.

[0003] Patent CN112107998A discloses an environmentally friendly composite nano-photocatalyst formaldehyde remover and its preparation method, comprising the following raw materials in parts by weight: 1000 parts deionized water, 5-15 parts photocatalyst, 4-12 parts dispersant, 1-3 parts formaldehyde inducer, and 15-30 parts modified diatomaceous earth. It boasts advantages such as high and thorough formaldehyde removal, good dispersibility, the ability to form a thin water layer, and good durability, without causing secondary pollution, making it safe and environmentally friendly. It also exhibits excellent antibacterial properties. However, its formaldehyde removal performance is heavily dependent on light conditions; its efficiency drops sharply in the absence of light, and there is a risk of adsorption saturation and secondary release, essentially "temporarily storing" rather than completely removing pollutants.

[0004] Patent CN113351007A discloses a long-lasting bio-enzyme formaldehyde remover. The remover comprises a polymer binder, a bio-enzyme deodorizer, a photocatalyst powder, a bio-enzyme protectant, a protein cross-linking agent, a sealing agent, and deionized water. The main components of this product are a composite bio-enzyme, a sealing agent, and a photocatalyst component. It is convenient to use; simply spraying it in a home environment achieves good results. However, this remover is heavily dependent on light conditions.

[0005] Therefore, there is an urgent need in the market for a highly efficient scavenger that can remove TVOCs and formaldehyde with excellent formaldehyde removal performance under both light and dark conditions. Summary of the Invention

[0006] In view of the problems existing in the prior art, the purpose of this invention is to obtain a cleaning agent that has excellent formaldehyde and TVOC removal performance under both light and dark conditions, and whose preparation process is simple, safe and environmentally friendly.

[0007] To achieve the above objectives, the technical solution adopted by the present invention is as follows: This invention provides a highly efficient scavenger for removing TVOC and formaldehyde, comprising, by weight, the following raw materials: 0.5-2 parts of natural plant extract, 0.5-2 parts of amino compound, 1.5-3 parts of polymer emulsion, 0.5-2 parts of bio-enzyme, 0.5-1 part of photocatalyst, and 70-95 parts of deionized water.

[0008] This application presents a formaldehyde removal agent prepared by mixing natural plant extracts, amino compounds, polymer emulsions, bio-enzymes, photocatalysts, and deionized water. This agent exhibits excellent formaldehyde removal performance. Primarily composed of natural ingredients and bio-based materials, it releases no toxic or harmful substances, leaves no residue, and can be sprayed on furniture boards, sofas, mattresses, fabrics, leather, and walls without leaving any trace or causing secondary pollution. It does not rely on special reaction conditions, caters to purification needs in both light and dark environments, has a long effective period, and does not affect the appearance of the substrate. By cleverly utilizing polymers as a stable carrier, it avoids the inactivation of bio-enzymes and the aggregation of photocatalysts, significantly extending the product's lifespan. It ingeniously constructs a multi-level, synergistic system of "bio-enzyme pretreatment + deep photocatalytic oxidation + amino compound adsorption and neutralization + plant extract-assisted purification," achieving a purification effect greater than the sum of its parts (1+1>2).

[0009] Plant extracts contain active ingredients that remove formaldehyde. These ingredients have multiple phenolic hydroxyl groups, which can undergo nucleophilic addition reactions with formaldehyde. This process converts formaldehyde into a stable, harmless condensate, thereby achieving its removal.

[0010] The composite bio-enzyme acts as a catalyst, accelerating the decomposition of formaldehyde and TVOC. Under the action of the enzyme, pollutants are efficiently converted into carbon dioxide and water, and the enzyme itself can be recycled after the reaction.

[0011] The amino group in amino compounds is highly reactive and can undergo Schiff base reaction or nucleophilic addition reaction with formaldehyde. For components containing carbonyl or carboxyl groups in TVOC, the amino group can also undergo nucleophilic addition reaction with these components to generate stable nitrogen-containing compounds, which permanently "fix" the formaldehyde and prevent it from being released again.

[0012] Photocatalysts can stimulate the surrounding oxygen and water under visible light to produce free radicals with strong oxidizing properties. These free radicals can attack various organic compounds in TVOC and formaldehyde pollutants, ultimately decomposing the pollutants into carbon dioxide and water.

[0013] In some embodiments, the plant extract is one or more of green tea extract, artemisia extract, orange peel extract, aloe vera extract, peppermint extract, and chrysanthemum extract.

[0014] In some embodiments, the amino compound is a combination of an amino acid and triethanolamine.

[0015] Preferably, the mass ratio of the amino acid to triethanolamine is 1:(2-5).

[0016] Preferably, the amino acid is glycine or serine.

[0017] Currently available amino compounds often pose risks such as high toxicity and respiratory irritation, and have poor water solubility. This application prefers an amino composition obtained by combining amino acids and triethanolamine, which has the characteristics of high safety, harmlessness to the human body, and good water solubility. Furthermore, the combination of the two can make the system alkaline, further accelerating the decomposition of formaldehyde and improving the removal effect of the scavenger on formaldehyde.

[0018] In some embodiments, the preparation method of the polymer emulsion includes the following steps: adding MDI and a catalyst to a polyether polyol, reacting at 70-80°C for 2-4 hours, cooling to 50-60°C and adding 2,2-dimethylolpropionic acid for 1-2 hours, cooling to 35-40°C, adding triethylamine and reacting for 30-40 minutes, adding deionized water and acetylacetamide, and stirring at 5-10°C and 800-1000 rpm for 30-60 minutes to obtain the polymer emulsion.

[0019] Preferably, the catalyst is an organometallic catalyst.

[0020] This application describes a novel polymer emulsion prepared by reacting a polyether polyol with MDI, 2,2-dimethylolpropionic acid, triethylamine, and acetylacetamide. The presence of polyether segments in the polymer chain enhances its dispersibility in water. The NH and C=O groups on the urea bonds and urethane groups act as strong hydrogen bond donors and acceptors, forming hydrogen bonds with the oxygen and hydrogen atoms of formaldehyde. The benzene ring structure on the MDI segment provides strong van der Waals forces and specific π-π interactions, exhibiting excellent selective adsorption capacity, particularly for VOCs containing benzene rings (such as toluene and xylene). Furthermore, the addition of acetylacetamide during the emulsification stage not only ensures complete reaction of isocyanates in the system, reducing their consumption of amino compounds, but also introduces acetylacetamide segments into the polymer chain. The two carbonyl groups of this segment, separated by a methylene group, readily form a highly reactive enol structure that undergoes nucleophilic addition reactions with formaldehyde, rapidly consuming the formaldehyde adsorbed on the polymer chain.

[0021] Furthermore, in this system, the urea bonds and carbamate groups on the polymer can form strong hydrogen bonds with amino compounds, further increasing the formaldehyde consumption rate; the quaternary ammonium salt structure generated by the reaction of 2,2-dimethylolpropionic acid and triethylamine can synergistically interact with the composite bioenzyme and photocatalyst, significantly enhancing the formaldehyde removal efficiency and dispersion performance of each component of the entire system through electrostatic attraction, surface modification, and stabilization.

[0022] In some embodiments, the number-average molecular weight of the polyether polyol is 1000-2000.

[0023] In some embodiments, the mass ratio of MDI to polyether polyol is 1:(2-5).

[0024] In some embodiments, the mass ratio of MDI to 2,2-dimethylolpropionic acid is 1:(0.08-0.14).

[0025] In some embodiments, the mass ratio of MDI to acetylacetamide is 1:(0.13-0.17).

[0026] In some embodiments, the molar ratio of 2,2-dimethylolpropionic acid to triethylamine is 1:(1-1.1).

[0027] In some embodiments, the bioenzyme is one or more of FS complex bioenzyme, lysozyme, laccase, cellulase, and oxidoreductase.

[0028] Preferably, the bioenzyme is an FS complex bioenzyme.

[0029] In some embodiments, the photocatalyst is one or more of titanium dioxide, zinc oxide, tungsten trioxide, zirconium dioxide, iron oxide, tin dioxide, cadmium sulfide, and zinc sulfide.

[0030] Preferably, the photocatalyst is titanium dioxide.

[0031] Another aspect of the present invention provides a method for preparing a highly efficient scavenger for removing TVOCs and formaldehyde, comprising the following steps: S1. Add the polymer emulsion to deionized water and stir at 200-300 rpm for 2-4 minutes to obtain the emulsion; S2. Add natural plant extracts, amino compounds, bio-enzymes, and photocatalysts to the emulsion obtained in step S1, and stir at room temperature for 1-2 hours to obtain a highly efficient scavenger for removing TVOC and formaldehyde.

[0032] Compared with the prior art, the present invention has the following beneficial effects: (1) The present invention provides a highly efficient scavenger for removing TVOC and formaldehyde by mixing natural plant extracts, amino compounds, polymer emulsions, biological enzymes, photocatalysts and deionized water. It has excellent TVOC and formaldehyde removal effects under both light and dark conditions. The preparation process is simple, safe and environmentally friendly.

[0033] (2) The polymer obtained by reacting polyether polyol with MDI, 2,2-dimethylolpropionic acid, triethylamine and acetylacetamide contains polyether segments, which is beneficial to improving its dispersibility in water. The NH and C=O on the urea bond and urethane group can form hydrogen bonds with formaldehyde and adsorb formaldehyde. The benzene ring structure on the MDI segment provides strong van der Waals forces and specific π-π interactions, especially exhibiting excellent selective adsorption capacity for VOCs containing benzene rings.

[0034] (3) By adding acetylacetamide during the emulsification stage, this invention can not only completely react the isocyanate in the system and reduce its consumption of amino compounds, but also introduce acetylacetamide segments into the polymer chain segments, which can undergo nucleophilic addition reaction with formaldehyde, so that the formaldehyde adsorbed on the polymer chain segments can be rapidly consumed by the reaction.

[0035] (4) The urea bonds and urethane groups on the polymer in this invention can form strong hydrogen bonds with amino compounds, which further enhances the formaldehyde consumption rate; the quaternary ammonium salt structure generated by the reaction of 2,2-dimethylolpropionic acid and triethylamine can have a synergistic effect with the composite biological enzyme and photocatalyst, significantly enhancing the formaldehyde removal efficiency of the whole system and the dispersion performance of each component. Detailed Implementation

[0036] The present invention will be described below with reference to specific embodiments. It should be noted that the following embodiments are examples of the present invention and are used only to illustrate the invention, not to limit it. Other combinations and various modifications within the scope of the present invention can be made without departing from its spirit or scope.

[0037] In the following examples and comparative examples, except for the polymer emulsion, all other compounds and related reagents used were commercially available. The green tea extract was purchased from Shandong Huiheng Biotechnology Co., Ltd.; the FS complex bioenzyme was purchased from Hebei Fusai Biotechnology Development Co., Ltd.; the titanium dioxide with an average particle size of 5 nm was purchased from Hubei Langbowan Biomedical Co., Ltd.; and the polyether polyol PPG1000 was purchased from Lanxing Dongda.

[0038] Preparation Example 1 The preparation method of polymer emulsion-1 includes the following steps: 10g MDI and 0.02g dibutyltin dilaurate are added to 25g PPG1000 and reacted at 75℃ for 3h. The temperature is then lowered to 55℃ and 1g 2,2-dimethylolpropionic acid is added and reacted for 1.5h. The temperature is then lowered to 35℃ and 0.754g triethylamine is added and reacted for 35min. 100g deionized water and 1.53g acetylacetamide are added and the mixture is stirred at 8℃ and 900rpm for 45min to obtain polymer emulsion-1.

[0039] Preparation Example 2 The preparation method of polymer emulsion-2 is the same as that of preparation example 1, except that the amount of PPG1000 added is 15g.

[0040] Preparation Example 3 The preparation method of polymer emulsion-3 is the same as that of preparation example 1, except that the amount of 2,2-dimethylolpropionic acid added is 1.6g.

[0041] Preparation Example 4 The preparation method of polymer emulsion-4 is the same as that in preparation example 1, except that the amount of acetylacetamide added is 2g.

[0042] Preparation Example 5 The preparation method of polymer emulsion-5 includes the following steps: 10g MDI and 0.02g dibutyltin dilaurate are added to 25g PPG1000 and reacted at 75℃ for 3h. The temperature is then lowered to 55℃ and 1g 2,2-dimethylolpropionic acid is added and reacted for 1.5h. The temperature is then lowered to 35℃ and 0.754g triethylamine is added and reacted for 35min. 100g deionized water is added and the mixture is stirred at 8℃ and 900rpm for 45min to obtain polymer emulsion-5.

[0043] Example 1 A highly effective scavenger for removing TVOC and formaldehyde, comprising the following ingredients by weight: 1.5 parts green tea extract, 0.3 parts glycine, 1.2 parts triethanolamine, 2.5 parts high molecular weight polymer emulsion-1, 1.5 parts FS complex bio-enzyme, 0.7 parts titanium dioxide, and 85 parts deionized water.

[0044] The preparation method of the highly efficient scavenger for removing TVOC and formaldehyde in this embodiment includes the following steps: S1. Add polymer emulsion-1 to deionized water and stir at 250 rpm for 3 min to obtain the emulsion; S2. Add green tea extract, glycine, triethanolamine, FS complex bio-enzyme, and titanium dioxide to the emulsion obtained in step S1, and stir at room temperature for 1.5 hours to obtain a highly efficient scavenger for removing TVOC and formaldehyde.

[0045] Example 2 A highly effective scavenger for removing TVOC and formaldehyde, comprising the following ingredients by weight: 0.5 parts green tea extract, 0.1 parts glycine, 0.4 parts triethanolamine, 1.5 parts high molecular weight polymer emulsion-1, 0.5 parts FS complex bio-enzyme, 0.5 parts titanium dioxide, and 70 parts deionized water.

[0046] The preparation method of the highly efficient scavenger for removing TVOC and formaldehyde in this embodiment includes the following steps: S1. Add polymer emulsion-1 to deionized water and stir at 200 rpm for 4 min to obtain the emulsion. S2. Add green tea extract, glycine, triethanolamine, FS complex bio-enzyme, and titanium dioxide to the emulsion obtained in step S1, and stir at room temperature for 1 hour to obtain a highly efficient scavenger for removing TVOC and formaldehyde.

[0047] Example 3 A highly effective scavenger for removing TVOC and formaldehyde, comprising the following ingredients by weight: 2 parts green tea extract, 0.4 parts glycine, 1.6 parts triethanolamine, 3 parts high molecular weight polymer emulsion-1, 2 parts FS complex bio-enzyme, 1 part titanium dioxide, and 95 parts deionized water.

[0048] The preparation method of the highly efficient scavenger for removing TVOC and formaldehyde in this embodiment includes the following steps: S1. Add polymer emulsion-1 to deionized water and stir at 300 rpm for 2 min to obtain the emulsion; S2. Add green tea extract, glycine, triethanolamine, FS complex bio-enzyme, and titanium dioxide to the emulsion obtained in step S1, and stir at room temperature for 2 hours to obtain a highly efficient scavenger for removing TVOC and formaldehyde.

[0049] Example 4 A highly efficient scavenger for removing TVOC and formaldehyde and its preparation method are disclosed. The specific implementation method is the same as in Example 1, except that polymer emulsion-1 is replaced with an equal amount of polymer emulsion-2.

[0050] Example 5 A highly efficient scavenger for removing TVOC and formaldehyde and its preparation method are disclosed. The specific implementation method is the same as in Example 1, except that polymer emulsion-1 is replaced with an equal amount of polymer emulsion-3.

[0051] Example 6 A highly efficient scavenger for removing TVOC and formaldehyde and its preparation method are disclosed. The specific implementation method is the same as in Example 1, except that polymer emulsion-1 is replaced with an equal amount of polymer emulsion-4.

[0052] Example 7 A highly efficient scavenger for removing TVOC and formaldehyde and its preparation method are disclosed. The specific implementation method is the same as in Example 1, except that polymer emulsion-1 is replaced with an equal amount of polymer emulsion-5.

[0053] Comparative Example 1 A cleaning agent, by weight, comprises the following ingredients: 1.5 parts green tea extract, 0.3 parts glycine, 1.2 parts triethanolamine, 1.5 parts FS complex bio-enzyme, 0.7 parts titanium dioxide, and 85 parts deionized water.

[0054] The preparation method of the cleaning agent in this embodiment includes the following steps: adding green tea extract, glycine, triethanolamine, FS complex bio-enzyme, and titanium dioxide to deionized water and stirring for 1.5 hours to obtain the cleaning agent.

[0055] Performance testing The cleaning agents obtained in the above embodiments and comparative examples were tested: (1) Formaldehyde purification rate: Referring to standard JC / T1074-2008, 100g of each formaldehyde removal agent was taken and placed in a 1.5m container. 3 Take 100g of deionized water from the sealed sample chamber and place it at a depth of 1.5m. 3 In a sealed control chamber, 4.5 ± 0.25 μL of analytical grade formaldehyde and 4.5 ± 0.25 μL of toluene were injected, with the initial concentration recorded as C0. After 24 hours, the formaldehyde concentration in the sample chamber was measured and recorded as C1 and C2. After 24 hours, the concentrations of formaldehyde and toluene in the control chamber were measured and recorded as C11 and C22. The formaldehyde purification rate R1 and toluene purification rate R2 for each scavenger were calculated according to R1 = (C1 - C11) / C1 × 100% and R2 = (C2 - C22) / C2 × 100%.

[0056] (2) Durability: Referring to standard JC / T1074-2008, take 100g of each cleaning agent and place it in a 1.5m... 3 Inside the sealed chamber, 3 ± 0.25 μL of analytical grade formaldehyde solution was injected daily for four consecutive days. On the fifth day, the removed cleaning agents were placed at a depth of 1.5 m. 3 The formaldehyde purification rate was determined in the sealed experimental chamber according to the method in (1) above, and recorded as the persistence.

[0057] The test results are shown in Table 1: Table 1

[0058] As shown in Table 1, the scavengers in Examples 1-3 of this invention have high efficiency in removing TVOCs and formaldehyde. A comparison between Example 4 and Example 1 shows that changing the ratio of MDI to polyether polyol may leave residual isocyanate ions in the polymer emulsion, causing the amino compounds in the scavenger to be consumed, thus reducing the scavenger's formaldehyde removal performance. A comparison between Example 5 and Example 1 shows that changing the ratio of MDI to 2,2-dimethylolpropionic acid may leave some carboxylate ions in the polymer emulsion and affect the grafting of acetylacetamide segments. This leads to a decrease in the formaldehyde removal performance of the scavenger; a comparison between Example 6 and Example 1 shows that changing the ratio of MDI and acetylacetamide will cause the residual acetylacetamide in the system to react with amino compounds, thereby affecting the formaldehyde removal performance of the scavenger; a comparison between Example 7 and Example 1 shows that when the polymer chain segments do not contain acetylacetamide, the formaldehyde removal performance of the scavenger deteriorates; a comparison between Comparative Example 1 and Example 1 shows that the scavenger that does not contain polymer emulsion and is highly efficient at removing TVOC and formaldehyde has poor performance in removing TVOC and formaldehyde.

[0059] The above embodiments are only for illustrating the technical concept and features of the present invention, and are intended to enable those skilled in the art to understand the content of the present invention and implement it. They should not be used to limit the scope of protection of the present invention. All equivalent changes or modifications made in accordance with the spirit and essence of the present invention should be covered within the scope of protection of the present invention.

Claims

1. A scavenger capable of efficiently removing TVOC and formaldehyde, characterized in that, The natural plant extract is one or more of green tea extract, artemisia leaf extract, orange peel extract, aloe extract, mint extract, and chrysanthemum extract.

2. The scavenger for efficiently removing TVOC and formaldehyde according to claim 1, characterized in that, The amino compound is a combination of amino acid and triethanolamine. 3.The scavenger for efficiently removing TVOC and formaldehyde according to claim 1, characterized in that, The preparation method of the high molecular polymer emulsion comprises the following steps: adding MDI and a catalyst into polyether polyol, reacting at 70-80 DEG C for 2-4 h, cooling to 50-60 DEG C, adding 2,2-dimethylol propionic acid and reacting for 1-2 h, cooling to 35-40 DEG C, adding triethylamine and reacting for 30-40 min, adding deionized water and acetylacetamide, stirring at 5-10 DEG C and 800-1000 rpm for 30-60 min, and obtaining the high molecular polymer emulsion. 4.The scavenger for efficiently removing TVOC and formaldehyde according to claim 1, characterized in that, The number average molecular weight of the polyether polyol is 1000-2000. 5.The scavenger for efficiently removing TVOC and formaldehyde according to claim 4, characterized in that, The mass ratio of the MDI to the polyether polyol is 1: (2-5).

6. The preparation method of the highly efficient scavenger for removing TVOC and formaldehyde according to claim 4, characterized in that, The mass ratio of the MDI to 2,2-dimethylol propionic acid is 1: (0.08-0.14).

7. The scavenger for efficiently removing TVOC and formaldehyde according to claim 4, characterized in that, The mass ratio of the MDI to acetylacetamide is 1: (0.13-0.17). 8.The method of claim 4, wherein the method is characterized by, The biological enzyme is one or more of FS composite biological enzyme, lysozyme, laccase, cellulase, and oxidoreductase. 9.The scavenger for efficiently removing TVOC and formaldehyde according to claim 1, characterized in that, The preparation method comprises the following steps:

10. A method for preparing the scavenger for efficiently removing TVOC and formaldehyde according to any one of claims 1-9, characterized in that, S1, adding the high molecular polymer emulsion into deionized water, stirring at 200-300 rpm for 2-4 min, and obtaining an emulsion; S2, adding the natural plant extract, the amino compound, the biological enzyme, and the photocatalyst into the emulsion obtained in step S1, stirring at room temperature for 1-2 h, and obtaining the scavenger for efficiently removing TVOC and formaldehyde. ​

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