A phosphine oxide ester composite formaldehyde scavenger, its preparation method and application

Abstract

The present invention discloses a phosphine oxide ester composite formaldehyde scavenger, its preparation method and application. Specifically, it discloses the application of the phosphine oxide ester composite formaldehyde scavenger in removing formaldehyde in air, boards and human specimens. The phosphine oxide ester composite formaldehyde scavenger comprises the following components in percentage by weight: 20% - 60% of trihydroxymethyl phosphine triurethane, 0.01% - 0.05% of penetrant, 0.05% - 0.10% of wetting agent, and the balance being deionized water. Its active ingredient, trihydroxymethyl phosphine triurethane, can be miscible with water in any proportion, enabling the formaldehyde scavenger to remove formaldehyde in the air by spraying, or to be applied on the surface of materials or specimens releasing formaldehyde, or added to materials releasing formaldehyde, effectively inhibiting the long-term release of formaldehyde and achieving the removal of formaldehyde at the source.

Description

Technical Field

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

[0002] Excessive formaldehyde in the air will cause obvious damage to the human body. When the indoor formaldehyde content reaches 0.1 mg / m 3 there will be an odor; when the content reaches 0.5 mg / m 3 it can stimulate the eyes and cause tears; when the content is higher than 0.6 mg / m 3 it can cause nausea, vomiting, cough, chest tightness, asthma and even pulmonary emphysema; when the content reaches 30 mg / m 3 it can cause immediate death. At present, the release period of free formaldehyde in artificial boards is 3 to 15 years, and the problem of excessive free formaldehyde in artificial boards is still quite serious. 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 fiberboards, particleboards, and blockboards used in decoration, decoration materials containing formaldehyde components such as white latex, foam plastics, paints and coatings, and indoor decorative textiles, such as wall coverings, wallpapers, chemical fiber carpets, and fabrics. It can be seen that the formaldehyde emitted from artificial boards as decoration materials into indoor air will affect people's physical health for a long time, and is one of the important factors causing Sick Building Syndrome (SBS), Building-Related Illness (BRI), etc. In addition, as a fixative, formaldehyde has the characteristics of fast penetration speed, good fixation effect, and long action time, and has long been widely used in the teaching and scientific research work of anatomical laboratories in the fields of medicine and biology. However, the harm of formaldehyde to human health prevents students from carefully observing the structures on specimens, directly affecting the learning effect of students. Therefore, in anatomical teaching, there is a particular need for a scavenger that can reduce the volatilization of formaldehyde, 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 are research and development works of great social significance and economic value.

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

[0004] Previous research basis: Chinese Patent No.: ZL202410388705.9, titled "A Flame Retardant and Its Preparation Method and Application", synthesized a new substance, tris (hydroxymethyl) phosphine oxide triurethane, and has developed a pilot production process, which can be used to replace the flame retardants used in commercial Pyrovatex CP and Proban-ammonia fumigation processes. Further research by this research group found that tris (hydroxymethyl) phosphine oxide triurethane has good reactivity with formaldehyde and can be used as a formaldehyde scavenger for formaldehyde removal. There are currently no relevant reports in this regard. With the enhancement of people's environmental protection concept, it is the trend of the times to seek new and non-toxic formaldehyde scavengers to inhibit formaldehyde release from the source. Summary of the Invention

[0005] The technical problem solved by the present invention is to provide a formaldehyde scavenger based on a phosphine oxide composite material and its preparation method and application. The formaldehyde scavenger containing tris (hydroxymethyl) phosphine oxide triurethane prepared by this method can effectively control formaldehyde pollution in the air and inhibit the long-term release of formaldehyde in boards and human specimens.

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

[0007] .

[0008] The preparation method of the formaldehyde scavenger based on the phosphine oxide composite material of the present invention specifically comprises the following steps: 1) Weigh tris (hydroxymethyl) phosphine oxide triurethane, penetrant, wetting agent, and deionized water respectively according to the weight percentage for use; 2) Add the penetrant and wetting agent to deionized water and stir to mix evenly; 3) Add tris (hydroxymethyl) phosphine oxide triurethane to the solution obtained in step 2) and stir to mix evenly to obtain the formaldehyde scavenger based on the phosphine oxide composite material.

[0009] The application of the formaldehyde scavenger based on the phosphine oxide composite material of the present invention in removing formaldehyde from the environment.

[0010] The formaldehyde scavenger based on the phosphine oxide composite material of the present invention can effectively remove free formaldehyde in the air by spraying in the air.

[0011] The formaldehyde scavenger of the phosphine oxide ester composite material of the present invention can effectively inhibit the long-term release of formaldehyde in the material by being applied to the surface of the material releasing formaldehyde or added to the material releasing formaldehyde.

[0012] Applying the above-mentioned formaldehyde scavenger of the phosphine oxide ester composite material to artificial plywood, the results show that: the formaldehyde scavenger of the phosphine oxide ester composite material of the present invention has a formaldehyde removal rate of 92.5% for the formaldehyde released from E2-grade artificial plywood used for outdoor furniture boards, and can upgrade E2-grade artificial plywood to E0-grade furniture boards suitable for indoor use by children and pregnant women. For NAF-grade (≤0.05mg / mL) artificial plywood with excellent environmental protection performance and extremely low formaldehyde release, the formaldehyde removal rate reaches 68.3%. In addition, the formaldehyde scavenger of the phosphine oxide ester composite material of the present invention can be applied to the surface of the material containing formaldehyde or added to the material containing formaldehyde, thereby inhibiting the long-term release of formaldehyde in the material.

[0013] Applying the above-mentioned formaldehyde scavenger of the phosphine oxide ester composite material to human specimens, the results show that: the formaldehyde scavenger of the phosphine oxide ester composite material of the present invention can reduce the formaldehyde release amount of human specimens, reduce the formaldehyde content in the dissection laboratory from 1.21ppm to 0.09ppm, and the formaldehyde removal rate reaches 92.6%, which can improve the occupational environment of dissection laboratories in the medical and biological fields and protect public health.

[0014] Applying the main component of the formaldehyde scavenger of the phosphine oxide ester composite material of the present invention, tris(hydroxymethyl)phosphine triurethane, to cell experiments found that when its concentration reaches 800μM, it has almost no effect on human immortalized epidermal cells and bronchial epithelial cells. The results show that: the formaldehyde scavenger of the phosphine oxide ester composite material has better safety, accidental contact and inhalation of this product will not cause harm to the human body, nor will it cause secondary pollution to the environment.

[0015] The main component of the formaldehyde scavenger of the phosphine oxide ester composite material of the present invention, tris(hydroxymethyl)phosphine triurethane, reacts with free formaldehyde in the air and building materials to form stable and non-toxic compounds. When in use, the formaldehyde scavenger of the phosphine oxide ester composite material can be sprayed into the air to effectively remove free formaldehyde in the air, or the formaldehyde scavenger of the phosphine oxide ester composite material can be applied to the material containing formaldehyde to effectively inhibit the long-term release of formaldehyde in the material. The formaldehyde scavenger of the phosphine oxide ester composite material of the present invention can effectively control the formaldehyde release amount in human specimens, thereby improving the occupational environment of dissection laboratories in the medical and biological fields and protecting public health.

[0016] The beneficial effects of the present invention are as follows: 1. The preparation method of the present invention is simple, the raw materials are extensive, and the cost is relatively low; 2. In the formaldehyde scavenger of the phosphine oxide ester composite material of the present invention, the main component, trihydroxymethyl phosphine triurethane liquid, can be miscible with water in any proportion, and the formaldehyde scavenger can be used to remove formaldehyde in the air by spraying, or applied to the surface of materials releasing formaldehyde, or added to materials releasing formaldehyde, which can inhibit the long-term release of formaldehyde and achieve the removal of formaldehyde at the source; 3. The main component, trihydroxymethyl phosphine triurethane formaldehyde scavenger, in the formaldehyde scavenger of the present invention is colorless and non-toxic, reacts with formaldehyde to form a non-toxic liquid compound, has no secondary pollution, can be added to materials containing formaldehyde, such as coatings, paints, etc., does not affect the color of the materials, so it does not affect the observation of human specimens and will not damage human specimens. Description of the Drawings

[0017] Figure 1 It is the toxicity evaluation of trihydroxymethyl phosphine triurethane, the active ingredient of the formaldehyde scavenger of the phosphine oxide ester composite material, on human immortalized epidermal cells (Hacat).

[0018] Figure 2 It is the toxicity evaluation of trihydroxymethyl phosphine triurethane, the active ingredient of the formaldehyde scavenger of the phosphine oxide ester composite material, on human bronchial epithelial cells (BEAS-2B).

[0019] Figure 3 It is the comparison of formaldehyde release amounts after using different formaldehyde scavengers.

[0020] Figure 4 It is the formaldehyde release amount of E2-grade plywood after applying the formaldehyde scavenger prepared in Example 2.

[0021] Figure 5 It is the formaldehyde release amount of NAF-grade plywood after applying the formaldehyde scavenger prepared in Example 2.

[0022] Figure 6 It is the formaldehyde release amount of human specimens after spraying the formaldehyde scavenger prepared in Example 2. Detailed Description of the Invention

[0023] The above content of the present invention will be further described in detail below through examples, but it should not be understood that the scope of the above subject matter of the present invention is limited to the following examples. All technologies implemented based on the above content of the present invention belong to the scope of the present invention. Example 1

[0024] In this embodiment, by adjusting the composition and ratio of raw materials, it is prepared according to the following method: by weight percentage, 0.01% of penetrant polyethylene glycol mono-isotridecyl vinyl ether and 0.05% of wetting agent alkyl polyglycoside are dissolved in 79.94% deionized water, stirred appropriately, then 20% of tris(hydroxymethyl)phosphine oxide triurethane is added to the solution, and stirring is continued appropriately to obtain a green and non-toxic formaldehyde scavenger. Example 2

[0025] In this embodiment, by adjusting the composition and ratio of raw materials, it is prepared according to the following method: by weight percentage, 0.02% of penetrant fatty alcohol polyoxyethylene ether and 0.06% of wetting agent alcohol ether glycoside are dissolved in 69.92% deionized water, stirred appropriately, then 30% of tris(hydroxymethyl)phosphine oxide triurethane is added to the solution, and stirring is continued appropriately to obtain a green and non-toxic formaldehyde scavenger. Example 3

[0026] In this embodiment, by adjusting the composition and ratio of raw materials, it is prepared according to the following method: by weight percentage, 0.04% of penetrant sodium alkyl sulfonate and 0.08% of wetting agent glucamide are dissolved in 49.88% deionized water, stirred appropriately, then 50% of tris(hydroxymethyl)phosphine oxide triurethane is added to the solution, and stirring is continued appropriately to obtain a green and non-toxic formaldehyde scavenger. Example 4

[0027] In this embodiment, by adjusting the composition and ratio of raw materials, it is prepared according to the following method: by weight percentage, 0.05% of penetrant fatty alcohol polyoxyethylene ether and 0.10% of wetting agent alcohol ether glycoside are dissolved in 39.85% deionized water, stirred appropriately, then 60% of tris(hydroxymethyl)phosphine oxide triurethane is added to the solution, and stirring is continued appropriately to obtain a green and non-toxic formaldehyde scavenger.

[0028] The main component of the formaldehyde scavenger of the present invention, tris(hydroxymethyl)phosphine oxide triurethane, is applied to normal human immortalized epidermal cells, and the cytotoxicity is evaluated by CCK8 experiment, as Figure 1 shown. The results show that when the concentration of tris(hydroxymethyl)phosphine oxide triurethane is between 0 and 800 μM, the cell viability is above 90%, indicating that tris(hydroxymethyl)phosphine oxide triurethane has little effect on human immortalized epidermal cells, and accidental contact with this product will not cause harm to the human body.

[0029] The main component of the formaldehyde scavenger of the present invention, tris(hydroxymethyl)phosphine oxide triurethane, is applied to human bronchial epithelial cells (BEAS-2B), and the cytotoxicity is evaluated by CCK8 experiment, as Figure 2As shown in the figure. The results show that when the concentration of tris (hydroxymethyl) phosphine triurethane is between 0 and 800 μM, the survival rate of cells is above 90%, indicating that tris (hydroxymethyl) phosphine triurethane has little effect on human bronchial epithelial cells, and inhaling this product will not cause harm to the human body. Example 5

[0030] Prepare tris (hydroxymethyl) phosphine triurethane into a 50% aqueous solution, add the same mass of formaldehyde aqueous solution (15 mg / mL), and refer to "GB / T 17657-2013 Determination of formaldehyde release from wood-based panels and wood-based panels with surface decoration - Desiccator method" to determine the formaldehyde release amount after 48 h. In order to compare with the commercial formaldehyde scavenger, the formaldehyde release amounts of urea and ethylene urea were measured using the same method, as Figure 3 shown. The results show that tris (hydroxymethyl) phosphine triurethane, urea, and ethylene urea all have good ability to scavenge formaldehyde, and the order of their formaldehyde scavenging ability is ethylene urea > tris (hydroxymethyl) phosphine triurethane > urea. Although the formaldehyde scavenging ability of tris (hydroxymethyl) phosphine triurethane is slightly weaker than that of ethylene urea, this substance is a colorless liquid, easily soluble in water, has good dispersibility, and is easy to achieve the spraying method to remove formaldehyde in the air. Example 6

[0031] Apply the formaldehyde scavenger obtained in Example 2 to both sides of 9 pieces of artificial plywood (E2 grade) with a size of 100×100 mm and a thickness of 5 mm. The application amount is 200 g / m 2 , air dry at room temperature, and after standing for 24 h, 48 h, 72 h, 96 h, and 120 h, refer to "GB / T17657-2013 Determination of formaldehyde release from wood-based panels and wood-based panels with surface decoration - Desiccator method" to determine the formaldehyde release amount of the plywood. The control group is to apply distilled water, as Figure 4 shown. It can be seen from the figure that the formaldehyde release amount of the commercially available E2 grade plywood after 24 h is 3.81 mg / L, meeting the environmental protection requirements of European standard E2 grade panels (≤5 mg / L). However, after the plywood is placed for 48 h, 72 h, 96 h, and 120 h, the cumulative formaldehyde release amount increases significantly, exceeding the environmental protection requirements of E2 panels. The above results show that even if it meets the environmental protection requirements of European standard panels, the long-term release of formaldehyde is an inevitable problem. However, after applying the formaldehyde scavenger prepared in Example 2, the formaldehyde release amount is significantly reduced. Especially after 120 h, the formaldehyde release amount is 2.36 mg / L, and the cumulative formaldehyde release amount still meets the environmental protection requirements of European standard E2 grade panels. The results show that the formaldehyde scavenger prepared in the present invention has the function of inhibiting the long-term release of formaldehyde, and the average removal rate of this formaldehyde scavenger for E2 panels is 92.5%. After using this formaldehyde scavenger, the E2 grade artificial plywood can be upgraded to E0 grade, which is suitable for indoor use by children and pregnant women. Example 7

[0032] Apply the formaldehyde scavenger obtained in Example 2 on both sides of 9 pieces of artificial plywood (NAF grade) with a size of 100×100 mm and a thickness of 5 mm. The application amount is 200 g / m 2 , air dry at room temperature, and after placing for 24 h, 48 h, 72 h, 96 h and 120 h, refer to "GB / T 17657-2013 Determination of formaldehyde emission from wood-based panels and wood-based panels with surface decoration - Desiccator method" to measure the formaldehyde emission of the plywood, as Figure 5 shown. It can be seen from the figure that the formaldehyde emission of the commercially available NAF grade plywood after 24 h is 0.325 mg / L, meeting the environmental protection requirements of the US standard NAF board (≤ 0.5 mg / L). However, after the plywood is placed for 48 h, 72 h, 96 h and 120 h, the cumulative formaldehyde emission increases significantly. Considering the cumulative formaldehyde emission, it exceeds the environmental protection requirements of the NAF board. The above results show that: even for NAF boards without formaldehyde addition with extremely low formaldehyde emission, 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 after 120 h, the formaldehyde emission is 0.502 mg / L, and the cumulative formaldehyde emission basically meets the environmental protection requirements of the US standard NAF board. The results show that: the formaldehyde scavenger prepared by the present invention has the function of inhibiting long-term formaldehyde release, and the average removal rate of this formaldehyde scavenger for NAF boards is 68.3%. Example 8

[0033] Place the human specimen on the tabletop, turn on the ventilation system, and measure the formaldehyde content in the dissection laboratory after 1 h, which is 1.21 ppm. Then spray the formaldehyde scavenger obtained in Example 2 on the gross specimen, and measure the formaldehyde content every 20 min until the formaldehyde content is basically stable, as Figure 6 shown. It can be seen from the figure that the formaldehyde scavenger of the present invention can reduce the formaldehyde emission of the human specimen, reduce the formaldehyde content in the dissection laboratory from 1.21 ppm to 0.09 ppm, and the formaldehyde removal rate reaches 92.6%, which can improve the occupational environment of dissection laboratories in the medical and biological fields and protect public health.

[0034] The above shows and describes the basic principles, main features and advantages of the present invention. Without departing from the spirit and scope of the present invention, there are various changes and improvements to the present invention, and these changes and improvements all fall within the scope of the present invention claimed.

Claims

1. A formaldehyde scavenger based on a phosphine oxide ester composite material, characterized in that Comprising components in the following weight percentages: 20% - 60% of tris (hydroxymethyl) phosphine oxide triurethane, 0.01% - 0.05% of penetrant, 0.05% - 0.10% of wetting agent, and the balance being deionized water, wherein the penetrant is one or more of polyethylene glycol monoisotridecyl vinyl ether, fatty alcohol polyoxyethylene ether or alkyl sulfonate, the wetting agent is one or more of alkyl glycoside, alcohol ether glycoside or glucamide, and the structural formula of tris (hydroxymethyl) phosphine oxide triurethane is The formaldehyde scavenger liquid containing tris (hydroxymethyl) phosphine oxide triurethane can be miscible with water in any proportion, enabling the formaldehyde scavenger to remove formaldehyde in the air by spraying, or applying it on the surface of materials releasing formaldehyde, or adding it to materials releasing formaldehyde, which can inhibit the long-term release of formaldehyde and achieve the removal of formaldehyde at the source.

2. A method for preparing the phosphine oxide ester composite formaldehyde scavenger according to claim 1, characterized in that The specific steps are as follows: 1) Weigh trihydroxymethyl phosphine triurethane, penetrant, wetting agent and deionized water respectively according to weight percentages for standby; 2) Add the penetrant and wetting agent into the deionized water and stir to mix evenly; 3) Add trihydroxymethyl phosphine triurethane into the solution obtained in step 2) and stir to mix evenly to obtain the formaldehyde scavenger of phosphine ester composite materials.

3. Application of the formaldehyde scavenger of phosphine ester composite materials described in claim 1 in removing formaldehyde in the environment.

4. The application according to claim 3, characterized in that: The formaldehyde scavenger of phosphine ester composite materials effectively removes free formaldehyde in the air by spraying in the air.

5. The application according to claim 3, characterized in that: The formaldehyde scavenger of phosphine ester composite materials effectively inhibits the long-term release of formaldehyde in the material by smearing on the surface of the material releasing formaldehyde or adding it into the material releasing formaldehyde.

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

Images