Phosphonyl ester composite material formaldehyde scavenger as well as preparation method and application thereof

Abstract

The invention discloses a phosphine oxide ester composite material formaldehyde scavenger as well as a preparation method and application thereof, and particularly discloses application of the phosphine oxide ester composite material formaldehyde scavenger to removal of formaldehyde in air, plates and human body specimens. The phosphine oxide ester composite material formaldehyde scavenger comprises the following components in percentage by weight: 20%-60% of trihydroxymethyl phosphine oxide tricarbamate, 0.01%-0.05% of a penetrant, 0.05%-0.10% of an impregnating compound and the balance of deionized water, and the effective component trihydroxymethyl phosphine oxide tricarbamate can be mixed and dissolved with water in any proportion. The formaldehyde scavenger can remove formaldehyde in air in a spraying manner, or is smeared on the surface of a formaldehyde releasing material and a specimen, or is added into the formaldehyde releasing material, so that long-term release of formaldehyde can be effectively inhibited, and formaldehyde is removed from the source.

Description

Technical Field

[0001] The invention belongs to the technical field of formaldehyde scavengers, and specifically relates to a phosphine oxide composite material formaldehyde scavenger and a preparation method and application thereof. Background Art

[0002] Formaldehyde is one of the most serious indoor pollutants. It ranks second on my country's priority list of toxic chemicals and has been identified by the World Health Organization (WHO) as a carcinogen and teratogen. Excessive formaldehyde in the air will cause obvious damage to the human body. When the indoor formaldehyde content reaches 0.1mg / m 3 Sometimes there is a peculiar smell; the content reaches 0.5mg / m 3 It can irritate the eyes and cause tears; the content is higher than 0.6mg / m 3 It can cause nausea, vomiting, coughing, chest tightness, asthma and even emphysema; when the content reaches 30mg / m 3 At present, the release period of free formaldehyde in artificial boards is 3 to 15 years. The problem of excessive free formaldehyde in artificial boards is still quite serious, and the emission of free formaldehyde in artificial boards is one of the important sources of formaldehyde pollution in indoor air. Indoor formaldehyde mainly comes from artificial boards such as plywood, joinery templates, medium-density fiberboard and particleboard, wood core board used in decoration, white latex, foam plastics, paints and coatings containing formaldehyde, and indoor decorative textiles, such as wall coverings, wallpapers, chemical fiber carpets, fabrics, etc. It can be seen that the formaldehyde emitted into the indoor air by artificial boards as decorative materials will have a long-term impact on people's health and is one of the important factors in the occurrence of bad building syndrome (SBS) and building-related syndrome (BRI). In addition, formaldehyde, as a fixing liquid, has the characteristics of fast penetration speed, good fixing effect and long-lasting action time. It has long been widely used in the teaching and scientific research of anatomical laboratories in the fields of medicine and biology. However, the harm of formaldehyde to human health makes it impossible for students to carefully observe the structure on the specimens, which directly affects the students' learning effect. Therefore, in anatomy teaching, a scavenger that can reduce the volatilization of formaldehyde is particularly needed, thereby fundamentally reducing the harm of formaldehyde to the human body. Therefore, controlling the release of free formaldehyde in artificial boards and human specimens, reducing indoor air pollution, improving the occupational environment, and protecting public health is a research and development work with important social significance and economic value.

[0003] At present, many conventional methods have been adopted at home and abroad to control the problem of excessive formaldehyde content in indoor air, mainly plant absorption method, physical adsorption method, photocatalyst method and chemical method. The plant absorption method is too slow to take effect and the effect is not obvious. Physical adsorption methods, such as activated carbon adsorption, are limited by the adsorption amount and have a short validity period. The photocatalyst method is limited by the lack of light at night. Without light, the photocatalyst cannot work. The chemical method uses chemical substances containing hydrazides, ureas, and cyanamides, as well as compounds such as ethyl acetoacetate and polyamines. This type of chemical substance has a good effect on removing formaldehyde, but there are certain toxicity and secondary pollution problems.

[0004] Previous research basis: Chinese patent number: ZL202410388705.9, name: A flame retardant and its preparation method and application, a new substance tris(hydroxymethyl)phosphine tricarbamate was synthesized, and a pilot production process has been developed, which can be used to replace the flame retardant in the commercial Pyrovatex CP and Proban-ammonia fumigation process. This research group further found that tris(hydroxymethyl)phosphine tricarbamate has good reaction activity with formaldehyde and can be used as a formaldehyde scavenger for the removal of formaldehyde. There are no relevant reports in this regard. With the enhancement of people's environmental protection concept, it is a trend to seek new, non-toxic formaldehyde scavengers to inhibit the release of formaldehyde from the source. Summary of the invention

[0005] The technical problem solved by the present invention is to provide a phosphine oxide ester composite material formaldehyde scavenger and a preparation method and application thereof. The formaldehyde scavenger containing trishydroxymethyl phosphine oxide triaminoformate prepared by the method can effectively control formaldehyde pollution in the air and can inhibit the long-term release of formaldehyde in plates and human specimens.

[0006] The present invention adopts the following technical scheme to solve the above technical problems: a phosphine oxide ester composite material formaldehyde scavenger, which comprises the following components in weight percentage: 20% to 60% of tris(hydroxymethyl)phosphine oxide tricarbamate, 0.01% to 0.05% of penetrant, 0.05% to 0.10% of wetting agent, and the balance is deionized water, wherein the penetrant is one or more of polyethylene glycol monoisotridecylethylene, fatty alcohol polyoxyethylene ether or alkyl sodium sulfonate, the wetting agent is one or more of alkyl glycoside, alcohol ether glycoside or glucose amide, and the structural formula of tris(hydroxymethyl)phosphine oxide tricarbamate is: .

[0007] The preparation method of the phosphine oxide ester composite material formaldehyde scavenger of the present invention comprises the following specific steps: 1) respectively weighing trishydroxymethyl phosphine oxide tricarbamate, a penetrant, an impregnant and deionized water according to weight percentage for standby use; 2) adding the penetrant and the impregnant into the deionized water and stirring and mixing them evenly; 3) adding trishydroxymethyl phosphine oxide tricarbamate into the solution obtained in step 2) and stirring and mixing them evenly to obtain the phosphine oxide ester composite material formaldehyde scavenger.

[0008] The phosphine oxide ester composite material formaldehyde scavenger of the present invention is used for removing formaldehyde in the environment.

[0009] The phosphine oxide ester composite material formaldehyde scavenger of the present invention can be sprayed in the air to effectively remove free formaldehyde in the air.

[0010] The phosphine oxide ester composite material formaldehyde scavenger of the present invention is applied on the surface of a material that releases formaldehyde or added into a material that releases formaldehyde to effectively inhibit the long-term release of formaldehyde in the material.

[0011] The above-mentioned phosphine oxide composite material formaldehyde scavenger was applied to artificial plywood, and the results showed that the phosphine oxide composite material formaldehyde scavenger of the present invention has a formaldehyde removal rate of 92.5% for the artificial plywood of E2 grade used as outdoor furniture board, which can upgrade the E2 grade artificial plywood to the E0 grade furniture board suitable for indoor children and pregnant women. For NAF grade (≤0.05mg / mL) artificial plywood with excellent environmental performance and extremely low formaldehyde emission, the formaldehyde removal rate reaches 68.3%. In addition, the phosphine oxide composite material formaldehyde scavenger of the present invention can be applied to the surface of a material containing formaldehyde or added to a material containing formaldehyde, thereby inhibiting the long-term release of formaldehyde in the material.

[0012] The above-mentioned phosphine oxide composite material formaldehyde scavenger was applied to human specimens, and the results showed that the phosphine oxide composite material formaldehyde scavenger described in the present invention can reduce the release of formaldehyde in human specimens, reducing the formaldehyde content in the anatomical laboratory from 1.21 ppm to 0.09 ppm, and the formaldehyde removal rate reached 92.6%, which can improve the occupational environment of anatomical laboratories in the medical and biological fields and protect public health.

[0013] The main component of the phosphine ester composite material formaldehyde scavenger of the present invention, trishydroxymethyl phosphine tricarbamate, was applied to cell experiments and it was found that when its concentration reached 800 μM, it had almost no effect on human immortalized epidermal cells and bronchial epithelial cells. The results show that the phosphine ester composite material formaldehyde scavenger has excellent safety, and accidental contact and inhalation of the product will not cause harm to the human body, nor will it cause secondary pollution to the environment.

[0014] The main component of the phosphine ester composite material formaldehyde scavenger of the present invention, trisaminomethyl trisphosphine ester, reacts with free formaldehyde in air and building materials to generate stable and non-toxic compounds. When used, the phosphine ester composite material formaldehyde scavenger can be sprayed in the air to effectively remove free formaldehyde in the air, or the phosphine ester composite material formaldehyde scavenger can be applied to materials containing formaldehyde to effectively inhibit the long-term release of formaldehyde in the materials. The phosphine ester composite material formaldehyde scavenger of the present invention can effectively control the release of formaldehyde in human specimens, thereby improving the occupational environment of anatomical laboratories in the fields of medicine and biology and protecting public health.

[0015] The beneficial effects of the present invention are: 1. The preparation method of the present invention is simple, the raw materials are extensive, and the cost is low; 2. The trisaminomethyl phosphine ester liquid, which is the main component of the phosphine ester composite material formaldehyde scavenger described in the present invention, can be miscible with water in any proportion, and the formaldehyde scavenger can be sprayed to remove formaldehyde in the air, or applied to the surface of a material that releases formaldehyde, or added to a material that releases formaldehyde, which can inhibit the long-term release of formaldehyde and achieve source removal of formaldehyde; 3. The trisaminomethyl phosphine ester formaldehyde scavenger, which is the main component of the formaldehyde scavenger described in the present invention, is colorless and non-toxic, reacts with formaldehyde to generate a non-toxic liquid compound, has no secondary pollution, and can be added to materials containing formaldehyde, such as coatings, paints, etc., without affecting the color of the material, and therefore does not affect the observation of human specimens, nor does it damage human specimens. BRIEF DESCRIPTION OF THE DRAWINGS

[0016] Figure 1 This study evaluated the toxicity of tris(hydroxymethyl)phosphine tricarbamate, an active ingredient of phosphine tricarbamate composite formaldehyde scavenger, on human immortalized epidermal cells (Hacat).

[0017] Figure 2 This study evaluated the toxicity of tris(hydroxymethyl)phosphine tricarbamate, an active ingredient of phosphine tris(hydroxymethyl) ...

[0018] Figure 3 Comparison of formaldehyde release after using different formaldehyde scavengers.

[0019] Figure 4 It is the formaldehyde emission of E2 grade plywood after applying the formaldehyde scavenger prepared in Example 2.

[0020] Figure 5 It is the formaldehyde emission of NAF grade plywood after applying the formaldehyde scavenger prepared in Example 2.

[0021] Figure 6 The formaldehyde release of the human specimen after spraying the formaldehyde scavenger prepared in Example 2. DETAILED DESCRIPTION

[0022] The above contents of the present invention are further described in detail below through examples, but this should not be understood as the scope of the above subject matter of the present invention being limited to the following examples, and all technologies implemented based on the above contents of the present invention belong to the scope of the present invention. Example 1

[0023] This embodiment is prepared by adjusting the composition and ratio of the raw materials as follows: by weight percentage, 0.01% of the penetrant polyethylene glycol monoisotridecylethylene and 0.05% of the wetting agent alkyl glycoside are dissolved in 79.94% deionized water, stirred appropriately, and then 20% of trishydroxymethylphosphine trisaminoacid ester is added to the solution, and continued to stir appropriately to obtain a green, non-toxic formaldehyde scavenger. Example 2

[0024] This embodiment is prepared by adjusting the composition and ratio of the raw materials as follows: by weight percentage, 0.02% of the penetrant fatty alcohol polyoxyethylene ether and 0.06% of the wetting agent alcohol ether glycoside are dissolved in 69.92% deionized water, stirred appropriately, and then 30% of trishydroxymethylphosphine triaminoacid is added to the solution, and continued to stir appropriately to obtain a green, non-toxic formaldehyde scavenger. Example 3

[0025] This embodiment is prepared by adjusting the composition and ratio of the raw materials as follows: by weight percentage, 0.04% of the penetrant sodium alkyl sulfonate and 0.08% of the wetting agent glucose amide are dissolved in 49.88% deionized water, stirred appropriately, and then 50% of trishydroxymethylphosphine triaminoformate is added to the solution, and continued to stir appropriately to obtain a green, non-toxic formaldehyde scavenger. Example 4

[0026] This embodiment is prepared by adjusting the composition and ratio of the raw materials as follows: by weight percentage, 0.05% of the penetrant fatty alcohol polyoxyethylene ether and 0.10% of the wetting agent alcohol ether glycoside are dissolved in 39.85% deionized water, stirred appropriately, and then 60% of trishydroxymethylphosphine triaminoacid is added to the solution, and continued to stir appropriately to obtain a green, non-toxic formaldehyde scavenger.

[0027] The main component of the formaldehyde scavenger of the present invention, tris(hydroxymethyl)phosphine tricarbamate, was applied to normal human immortalized epidermal cells, and the cytotoxicity was evaluated by CCK8 assay. Figure 1 The results showed that when the concentration of tris(hydroxymethyl)phosphine tricarbamate was between 0 and 800 μM, the cell survival rate was above 90%, indicating that tris(hydroxymethyl)phosphine tricarbamate had almost no effect on human immortalized epidermal cells, and accidental contact with this product would not cause harm to the human body.

[0028] The main component of the formaldehyde scavenger of the present invention, tris(hydroxymethyl)phosphine trisamino acid, was applied to human bronchial epithelial cells (BEAS-2B), and the cytotoxicity was evaluated by CCK8 assay. Figure 2 The results showed that when the concentration of tris(hydroxymethyl)phosphine tricarbamate was between 0 and 800 μM, the cell survival rate was above 90%, indicating that tris(hydroxymethyl)phosphine tricarbamate had almost no effect on human bronchial epithelial cells and inhalation of this product would not cause harm to the human body. Example 5

[0029] Trisaminoacid tris(hydroxymethyl)phosphine oxide was prepared into a 50% aqueous solution, and the same mass of formaldehyde aqueous solution (15 mg / mL) was added. The formaldehyde release after 48 hours was measured according to GB / T 17657-2013 Determination of formaldehyde release from artificial boards and veneer artificial boards-dryer method. In order to compare with the commercial formaldehyde scavengers, the formaldehyde release of urea and ethylene urea was measured using the same method. Figure 3 As shown. The results show that tris(hydroxymethyl)phosphine oxide tricarbamate, urea and ethylene urea all have good formaldehyde removal capabilities, and the order of formaldehyde removal capabilities is ethylene urea>tris(hydroxymethyl)phosphine oxide tricarbamate>urea. Although the formaldehyde removal capability of tris(hydroxymethyl)phosphine oxide tricarbamate is weaker than that of ethylene urea, the substance is a colorless liquid, easily soluble in water, and has good dispersibility, and it is easy to remove formaldehyde in the air by spraying. Example 6

[0030] The formaldehyde scavenger obtained in Example 2 was applied to both sides of 9 pieces of 100×100 mm and 5 mm thick artificial plywood (E2 grade) at a coating amount of 200 g / m 2 , air-dried at room temperature, placed for 24h, 48h, 72h, 96h and 120h, the formaldehyde emission of plywood was determined according to GB / T17657-2013 Determination of formaldehyde emission of artificial boards and veneer artificial boards-dryer method. The control group was smeared with distilled water, such as Figure 4As shown. As can be seen from the figure, the formaldehyde emission of commercially available E2-grade plywood in 24 hours is 3.81 mg / L, which meets the environmental protection requirements of the European standard board E2 level (≤5 mg / L). However, after the plywood is placed for 48 hours, 72 hours, 96 hours and 120 hours, the cumulative formaldehyde emission increases significantly, exceeding the environmental protection requirements of the E2 board. The above results show that even if it meets the environmental protection requirements of the European standard board, the long-term release of formaldehyde is an inevitable problem. However, after applying the formaldehyde scavenger prepared in Example 2, the formaldehyde emission is significantly reduced, especially after 120 hours, the formaldehyde emission is 2.36 mg / L, and the cumulative formaldehyde emission still meets the environmental protection requirements of the European standard board E2 level. The results show that the formaldehyde scavenger prepared by the present invention has the function of inhibiting the long-term release of formaldehyde, and the average removal rate of the formaldehyde scavenger for E2 board is 92.5%. After using this formaldehyde scavenger, the E2-grade artificial plywood can be upgraded to the E0 level suitable for indoor children and pregnant women. Example 7

[0031] The formaldehyde scavenger obtained in Example 2 was applied to both sides of 9 pieces of 100×100 mm and 5 mm thick artificial plywood (NAF grade) at a coating amount of 200 g / m 2 , air-dried at room temperature, and placed for 24h, 48h, 72h, 96h and 120h, the formaldehyde emission of plywood was determined according to GB / T 17657-2013 Determination of formaldehyde emission of wood-based panels and veneer wood-based panels-Desiccant method. Figure 5 As shown. It can be seen from the figure that the formaldehyde emission of commercially available NAF-grade plywood in 24 hours is 0.325 mg / L, which meets the environmental protection requirements of American standard board NAF (≤ 0.5 mg / L). However, after the plywood was placed for 48 hours, 72 hours, 96 hours and 120 hours, the cumulative formaldehyde emission increased significantly. If the cumulative formaldehyde emission is considered, it exceeds the environmental protection requirements of NAF board. The above results show that even for NAF boards with extremely low formaldehyde emission and no formaldehyde added, long-term formaldehyde release is an inevitable problem. However, after applying the formaldehyde scavenger prepared in Example 2 of the present invention, the formaldehyde emission is significantly reduced, especially the formaldehyde emission after 120 hours is 0.502 mg / L, and the cumulative formaldehyde emission basically meets the environmental protection requirements of American standard board NAF. The results show that the formaldehyde scavenger prepared by the present invention has the function of inhibiting the long-term release of formaldehyde, and the average removal rate of the formaldehyde scavenger for NAF board is 68.3%. Example 8

[0032] The human specimen was placed on the table and the ventilation system was turned on. After 1 hour, the formaldehyde content in the anatomy laboratory was measured to be 1.21 ppm. The formaldehyde scavenger obtained in Example 2 was then sprayed on the gross specimen, and the formaldehyde content was measured every 20 minutes until the formaldehyde content was basically stable. Figure 6As shown in the figure, the formaldehyde scavenger of the present invention can reduce the release of formaldehyde from human specimens, reducing the formaldehyde content in the anatomical laboratory from 1.21ppm to 0.09ppm, and the formaldehyde removal rate reaches 92.6%, which can improve the occupational environment of anatomical laboratories in the medical and biological fields and protect public health.

[0033] The basic principles, main features and advantages of the present invention are shown and described above. Without departing from the spirit and scope of the present invention, the present invention may also be subject to various changes and improvements, which all fall within the scope of the present invention to be protected.

Claims

1. A phosphine oxide composite material formaldehyde scavenger, characterized in that The invention comprises the following components in percentage by weight: 20% to 60% of tris(hydroxymethyl)phosphine tricarbamate, 0.01% to 0.05% of a penetrant, 0.05% to 0.10% of a wetting agent, and the balance being deionized water, wherein the penetrant is one or more of polyethylene glycol monoisotridecylethylene, fatty alcohol polyoxyethylene ether, or sodium alkyl sulfonate, the wetting agent is one or more of alkyl glycoside, alcohol ether glycoside, or glucose amide, and the structural formula of tris(hydroxymethyl)phosphine tricarbamate is: 。 2. A method for preparing the phosphine oxide ester composite material formaldehyde scavenger according to claim 1, characterized in that The specific steps are: 1) weighing trishydroxymethyl phosphine tricarbamate, a penetrant, an impregnant and deionized water respectively according to weight percentage for standby use; 2) adding the penetrant and the impregnant into the deionized water and stirring to mix evenly; 3) adding trishydroxymethyl phosphine tricarbamate into the solution obtained in step 2) and stirring to mix evenly to obtain a phosphine ester composite material formaldehyde scavenger.

3. Use of the phosphine oxide composite material formaldehyde scavenger according to claim 1 in removing formaldehyde in the environment.

4. The use according to claim 3, characterized in that: The phosphine oxide ester composite material formaldehyde scavenger is sprayed in the air to effectively remove free formaldehyde in the air.

5. The use according to claim 3, characterized in that: The phosphine oxide ester composite material formaldehyde scavenger is applied on the surface of a material that releases formaldehyde or added into a material that releases formaldehyde to effectively inhibit the long-term release of formaldehyde in the material.

6. The use according to claim 3, characterized in that: The phosphine oxide composite material formaldehyde scavenger is used to reduce the release of formaldehyde from human specimens and improve the occupational environment of anatomical laboratories in the medical and biological fields.

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