Foaming type polyurethane material and application thereof

Abstract

The invention provides a foamed polyurethane material and application thereof, and relates to the technical field of foamed polyurethane materials. The foaming type polyurethane material is composed of a component A and a component B. The component A comprises the following raw material components: 100 parts of polymer dihydric alcohol, 1-8 parts of a chain extender, 1-3 parts of a catalyst, 1-5 parts of modified silicone oil and 0.5-2 parts of water. And the component B is a polyisocyanate compound. Wherein the structure of the modified silicone oil contains a hydrophilic polyethylene glycol chain segment and an anthraquinone structure, so that the denitrification performance of the foaming type polyurethane material on nitrogen-containing sewage is improved.

Description

Technical Field

[0001] This invention belongs to the technical field of foamed polyurethane materials, and relates to a foamed polyurethane material and its applications. Background Technology

[0002] With the rapid advancement of industrial and agricultural development and urbanization, the ecological and environmental pollution and health risks caused by high-concentration nitrogen-containing wastewater are becoming increasingly prominent. For biological denitrification in anaerobic environments, redox mediators can effectively promote charge transfer between electron donors and acceptors. Simultaneously, certain mediator materials can significantly improve the biological activity and metabolic efficiency of the system by enhancing the extracellular electron transfer capacity of anaerobic microorganisms. Directly adding redox mediators to water bodies is prone to loss and secondary pollution. Therefore, loading redox mediators onto a carrier can simultaneously improve denitrification efficiency, enhance the persistence of action, and avoid secondary pollution. Existing technologies disclose carriers such as silicone rubber, polyolefins, and polyurethane. Chinese patent CN112480461A discloses a method of grafting aminoanthraquinone compounds and polyamines onto carbon nanotubes. The polyamines can participate in the preparation reaction of foamed polyurethane, allowing carbon nanotubes and anthraquinone compounds to be grafted onto a polyurethane carrier. However, this method still has the following problems: (1) Anthraquinone compounds are grafted onto the surface of carbon nanotubes, and the carbon nanotubes are dispersed inside the polyurethane, which reduces the chance of the anthraquinone compounds coming into contact with the wastewater, thus affecting their effect as a promoter of charge transfer between electron donors and acceptors; (2) The foamed polyurethane has poor hydrophilicity, especially the nonpolar structure of the benzene ring on the anthraquinone has hydrophobicity, which will improve the hydrophobicity of the foamed polyurethane. The wastewater to be tested will not wet and contact the polyurethane well, which will also affect the effect of the anthraquinone compounds.

[0003] Therefore, existing methods for preparing anthraquinone compounds-modified polyurethane foams need further improvement. Summary of the Invention

[0004] To address the aforementioned technical problems, this invention provides a foamed polyurethane material and its applications.

[0005] The technical solution of the present invention is as follows:

[0006] A foamed polyurethane material, composed of component A and component B;

[0007] The raw material components of component A include: 100 parts polymer diol, 1-8 parts chain extender, 1-3 parts catalyst, 1-5 parts modified silicone oil and 0.5-2 parts water;

[0008] The structure of the modified silicone oil is shown in formula (1) below.

[0009] R 1 Me2SiO(SiOMe2) a(SiOMeR 2 ) b (SiOMeR 3 ) c SiMe2R 1 (1)

[0010] Among them, R 1 Selected from C1-C4 alkyl, C2-C6 hydroxyalkyl, or amino-containing C3-C6 alkyl, R 2 Contains polyethylene glycol segments, R 3 It contains anthraquinone structures, Me is a methyl group, a = 10-100, b = 3-15, c = 5-20.

[0011] Component B is a polyisocyanate compound.

[0012] Preferably, the R 1 Selected from -(CH2) m OH, -(CH2) n NH2、-(CH2) o NH(CH2) p CH3 and -(CH2) q One or more combinations of NH(CH2)2NH2, wherein m = 2-6, n = 2-6, o = 2-6, p = 0-2, q = 2-6.

[0013] Preferably, the R 2 The structure is shown in equation (2) below.

[0014] -(CH2)3(OCH2CH2) d OR 4 (2)

[0015] Among them, R 4 Selected from H or C1-C4 alkyl groups, d = 4-50.

[0016] Preferably, the R 3 The structure is shown in equation (3) below.

[0017]

[0018] Among them, R 5 Selected from H, hydroxyl or C1-C4 alkyl, R 6 For the absence of oxygen atoms, e = 0 - 2.

[0019] Preferably, the polymeric diol is selected from polyether diols and / or polyester diols;

[0020] Preferably, the molar percentage of polyethylene glycol segments in the polyether diol is not less than 30%.

[0021] Preferably, the chain extender is selected from C2-C8 alkyl diols.

[0022] Preferably, the catalyst is selected from dihydroxyalkylamine.

[0023] Preferably, the polyisocyanate compound is selected from diisocyanate monomers and their trimers;

[0024] The molar ratio of active hydrogen in component A to NCO groups in component B is 1:1.08-1.2.

[0025] Preferably, the raw material components further include 0.1-2 parts of carbon-based material;

[0026] The carbon-based material is selected from one or a combination of two or more of carbon nanotubes, graphene, and fullerene.

[0027] An application of the foamed polyurethane material described in any of the above embodiments in the treatment of nitrogen-containing wastewater.

[0028] The beneficial effects of this invention are:

[0029] (1) The modified silicone oil added to the foamed polyurethane material of the present invention has the following characteristics: 1) The modified silicone oil contains hydrophilic polyether segments and anthraquinone compounds, which can improve the hydrophilicity of the foamed polyurethane material and also enable the anthraquinone compounds to promote the denitrification of nitrogen-containing wastewater; 2) The modified silicone oil can also be used as a foam leveling agent for the foamed polyurethane to improve the uniformity of foaming; 3) Some of the modified silicone oil can migrate to the surface of the foamed polyurethane material, increasing the contact opportunity between the anthraquinone compounds and the wastewater, and improving the effect of the anthraquinone compounds.

[0030] (2) When the end groups of the modified silicone oil at both ends contain hydroxyl and / or amino groups, they can participate in the preparation reaction of foamed polyurethane. The modified silicone oil can be stably dispersed in the foamed polyurethane material through chemical bonds, and play a more lasting role.

[0031] (3) Modified silicone oil is amphiphilic and can be used as a dispersant for carbon-based materials to improve the dispersibility of carbon-based materials in foamed polyurethane materials, reduce agglomeration, and enhance the effect of carbon-based materials. Detailed Implementation

[0032] The technical solution of the present invention will be further explained and described below through specific embodiments. In one aspect, the present invention proposes a foamed polyurethane material composed of component A and component B;

[0033] The raw material components of component A include: 100 parts polymer diol, 1-8 parts chain extender, 1-3 parts catalyst, 1-5 parts modified silicone oil and 0.5-2 parts water;

[0034] The structure of the modified silicone oil is shown in formula (1) below.

[0035] R 1 Me2SiO(SiOMe2) a (SiOMeR 2 ) b (SiOMeR 3 ) c SiMe2R 1 (1)

[0036] Among them, R 1 Selected from C1-C4 alkyl, C2-C6 hydroxyalkyl, or amino-containing C3-C6 alkyl, R 2 Contains polyethylene glycol segments, R 3 It contains anthraquinone structures, Me is a methyl group, a = 10-100, b = 3-15, c = 5-20.

[0037] Component B is a polyisocyanate compound.

[0038] This invention uses foamed polyurethane as a carrier. The density of the foamed polyurethane can be adjusted according to the degree of foaming, making it suitable for wastewater with different densities. The modified silicone oil mentioned above, which contains polyethylene glycol segments and anthraquinone structures, has the following effects: (1) The hydrophilicity of the polyethylene glycol segments can improve the hydrophilicity of the foamed polyurethane material, making it easier for wastewater to wet the foamed polyurethane material, which is beneficial to the effect of anthraquinone; (2) Anthraquinone, as a redox mediator, can improve the denitrification efficiency of nitrogen-containing wastewater; (3) The polyethylene glycol segments and anthraquinone structures are chemically bonded to the organosilicon structure, which has good stability and improves the persistence of the effect. When the end groups of the modified silicone oil contain When hydroxyl and / or amino groups are present, some or all of the modified silicone oil can participate in the preparation reaction of foamed polyurethane materials. The modified silicone oil is chemically bonded to the foamed polyurethane material, which further improves the durability of the modified silicone oil's effect; (4) The modified silicone oil is amphiphilic and can be used as a foam leveler and a filler dispersant to improve the dispersibility of the filler in the foamed polyurethane; (5) Some of the modified silicone oil will migrate to the surface of the foamed polyurethane material, further exerting the hydrophilicity and redox mediator effect of the modified silicone oil.

[0039] The preparation method of the modified silicone oil of the present invention is not particularly limited. For example, it can be prepared by hydrosilylation reaction, from the corresponding hydrogen-containing silicone oil R. 1 Me2SiO(SiOMe2) a (SiOMeH) b+c SiMe2R 1Hydrosilylation reactions are carried out separately with an alkenyl-containing anthraquinone compound and a terminal alkenyl polyether (or terminal alkenyl polyethylene glycol). Methods for preparing hydrogen-containing silicone oils are well known to those skilled in the art, such as using R... 1 Me2S iOS iMe2R 1 As end-capping agents, octamethylcyclotetrasiloxane (D4) and tetramethylcyclotetrasiloxane (D4) H It is obtained by ring-opening reaction under acidic catalysts (such as concentrated sulfuric acid, acidic clay, etc.).

[0040] For example, the weight percentage of modified silicone oil could be 1 part, 2 parts, 3 parts, 4 parts, or 5 parts. If the amount of modified silicone oil is too high, incompatibility may occur, which could hinder its effectiveness.

[0041] The role of water is to react with polyisocyanate compounds to produce CO2 gas, which causes the polyurethane material to foam. Examples of water weight percentages include 0.5 parts, 0.8 parts, 1 part, 1.2 parts, 1.5 parts, 1.8 parts, and 2 parts. Higher water content results in greater foaming of the polyurethane material, but may lead to insufficient density, lower mechanical strength, or even shrinkage and collapse.

[0042] In some embodiments, R 1 Selected from -(CH2) m OH, -(CH2) n NH2、-(CH2) o NH(CH2) p CH3 and -(CH2) q One or more combinations of NH(CH2)2NH2, wherein m = 2-6, n = 2-6, o = 2-6, p = 0-2, q = 2-6.

[0043] The above R 1 The presence of hydroxyl or amino groups in the structure that can react with NCO groups allows the modified silicone oil to be chemically dispersed into foamed polyurethane materials, improving its stability and promoting longer-lasting effectiveness. For example, R... 1 It can be -(CH2)3OH, -(CH2)4OH, -(CH2)6OH, -(CH2)3NH2, -(CH2)4NH2, -(CH2)3NHCH2CH3, -(CH2)3NHCH3 and -(CH2)3NH(CH2)2NH2, etc.

[0044] In some embodiments, R 2 The structure is shown in equation (2) below.

[0045] -(CH2)3(OCH2CH2) d OR 4 (2)

[0046] Among them, R 4 Selected from H or C1-C4 alkyl groups, d = 4-50.

[0047] For example, R 4 It can be H or methyl, and the number average molecular weight of the corresponding terminal alkenyl polyethylene glycol can be 200-2000. Terminal alkenyl polyethylene glycol can be terminal allyl polyethylene glycol methyl ether AMPEG, such as AMPEG-200 (200 represents the number average molecular weight), AMPEG-400, AMPEG-600, AMPEG-800, AMPEG-1000, AMPEG-1200, AMPEG-1500, AMPEG-2000, etc.

[0048] In some embodiments, R 3 The structure is shown in equation (3) below.

[0049]

[0050] Among them, R 5 Selected from H, hydroxyl or C1-C4 alkyl, R 6 For the absence of oxygen atoms, e = 0 - 2.

[0051] For example, R 3 The corresponding alkenyl anthraquinone compounds can be 1-allyloxy-4-methylanthraquinone, 1-allyloxyanthraquinone, 1-allyloxy-2-methylanthraquinone, 1-allyloxy-5-methylanthraquinone, 2-allyloxyanthraquinone, 2-allylanthraquinone, 1-allylanthraquinone, 1-allyloxy-4-hydroxyanthraquinone, etc. These alkenyl anthraquinone compounds can be obtained directly from the market or prepared using existing methods. Taking 1-allyloxy-4-methylanthraquinone as an example, it can be obtained by reacting 1-hydroxy-4-methylanthraquinone with bromopropyl or chloropropyl groups under alkaline conditions (such as sodium carbonate, potassium carbonate, sodium tert-butoxide, potassium tert-butoxide, etc.) as a catalyst to remove hydrogen bromide.

[0052] In some embodiments, the polymeric diol is selected from polyether diols and / or polyester diols; for polyether diols, it may be PPG homopolymer, PEG / PPG copolymer, PTMEG, etc.; for polyester diols, it may be polycarbonate diol, polylactide diol, polycaprolactone diol, etc. There are no particular limitations on the molecular weight of the polymeric diol, and the number average molecular weight may be 500-2000.

[0053] In some embodiments, the molar percentage of polyethylene glycol segments in the polyether diol is not less than 30%. The presence of polyethylene glycol segments in the polyether diol can further improve the hydrophilicity of the foamed polyurethane material. For example, the molar percentage of polyethylene glycol segments in the polyether diol can be any value or any value between 30%, 35%, 40%, 45%, 50%, 55%, and 60%.

[0054] In some embodiments, the chain extender is selected from C2-C8 alkyl diols, for example, ethylene glycol, 1,4-butanediol, 1,6-hexanediol, 1,8-octanediol, etc.

[0055] In some embodiments, the catalyst is selected from dihydroxyalkylamines, for example, dihydroxyethylamine, dihydroxypropylamine, etc. Dihydroxyalkylamines have two hydroxyl groups and one secondary amino group in their structure, and can be used not only as catalysts but also as crosslinking agents to improve the mechanical strength of foamed polyurethane materials.

[0056] In some embodiments, the polyisocyanate compound is selected from diisocyanate monomers and their trimers; for example, the polyisocyanate compound may be HMDI and its trimer, HDI and its trimer, IPDI and its trimer, TDI and its trimer, etc.

[0057] The molar ratio of active hydrogen in component A to NCO groups in component B is 1:1.08-1.2. Active hydrogen in component A refers to H atoms in component A that can react with NCO groups at temperatures not exceeding 80°C; for example, water contains two active hydrogen atoms. An excess of NCO groups favors the formation of CO2 gas. For example, the molar ratio of active hydrogen to NCO groups can be any value or any value in between, such as 1:1.08, 1:1.1, 1:1.12, 1:1.15, 1:1.18, or 1:1.2.

[0058] In some embodiments, the raw material components further include 0.1-2 parts of carbon-based material;

[0059] The carbon-based materials are selected from one or a combination of two or more of carbon nanotubes, graphene, and fullerene.

[0060] Carbon-based materials possess good electrical conductivity, which can enhance the performance of redox mediators and further improve the denitrification effect on nitrogen-containing wastewater. The weight percentage of carbon-based materials can be any value or any value between 0.1 parts, 0.3 parts, 0.5 parts, 0.7 parts, 0.8 parts, 1 part, 1.2 parts, 1.5 parts, 1.7 parts, 1.8 parts, and 2 parts. As an inorganic filler, carbon-based materials have poor compatibility with polyurethane materials. The modified silicone oil in this invention has good amphiphilicity and can also be used as a dispersant for carbon-based materials, improving their dispersibility in foamed polyurethane materials and helping to better utilize their performance.

[0061] Furthermore, the surface of carbon-based materials can be chemically modified, for example, by using surface treatment agents such as silane coupling agents, which is well known to those skilled in the art.

[0062] In addition, other inorganic fillers, such as talc, kaolin, wollastonite, silica, zeolite, and glass microspheres, can be added to the raw material components as needed. Using low-density fillers such as zeolite and hollow glass microspheres can also adjust the density of the foamed polyurethane material.

[0063] The foamed polyurethane material of this invention can be injection molded into the form of filler commonly used in the field of wastewater treatment, as specified in CJ / T 461-2014 "High-density polyethylene suspended carrier filler for water treatment". For the foaming of the mixture of component A and component B, the temperature can be 50-60℃ and the time can be 3-10 minutes.

[0064] On the other hand, the present invention also proposes an application of the foamed polyurethane material described in any of the above embodiments for the treatment of nitrogen-containing wastewater. Examples of nitrogen pollution sources in nitrogen-containing wastewater include azo dyes and nitrates.

[0065] The technical solution of the present invention will be further described and illustrated below with reference to various embodiments. Unless otherwise specified, the parts mentioned in the following embodiments are parts by weight.

[0066] Preparation Examples 1-2: Preparation of Modified Silicone Oil

[0067] Preparation Example 1

[0068] The molar ratio of hydrogen-containing silicone oil, 2-allyl anthraquinone, and AMPEG-800 is 1:11.4:7.2.

[0069] Under nitrogen protection, hydrogen-containing silicone oil Me3SiO (SiOMe2) is added to the container. 45.7 (SiOMeH) 18.2 SiMe3 and 2-allylanthraquinone were heated to 90°C, and Karstedt catalyst (50 ppm based on Pt) was added. The reaction temperature was controlled at 135-140°C for 5 hours. AMPEG-800 was then added, and the vacuum was adjusted to -0.08 MPa to -0.085 MPa until the Si-H bonds were undetectable. The mixture was then cooled to obtain modified silicone oil.

[0070] Preparation Example 2

[0071] The molar ratio of hydrogen-containing silicone oil, 1-allyloxy-4-hydroxyanthraquinone, and AMPEG-1200 is 1:18.1:11.

[0072] Under nitrogen protection, hydrogen-containing silicone oil HO(CH2)3Me2SiO(SiOMe2) is added to the container. 34.8 (SiOMeH) 28.6 SiMe2(CH2)3OH and 1-allyloxy-4-hydroxyanthraquinone were heated to 90°C, and Karstedt catalyst (40 ppm based on Pt) was added. The reaction temperature was controlled at 135-140°C for 5 hours. AMPEG-1200 was then added, and the vacuum was adjusted to -0.08 MPa to -0.085 MPa until the Si-H bonds were undetectable. The mixture was then cooled to obtain modified silicone oil.

[0073] Example 1

[0074] Foamed polyurethane material, composed of component A and component B;

[0075] The raw material components of component A include: 100 parts of PPG diol with a number average molecular weight of 1000, 4 parts of 1,4-butanediol, 1.5 parts of dihydroxyethylamine, 1 part of the modified silicone oil of Preparation Example 1, and 1 part of water.

[0076] Component B is a combination of HDI and HDI trimer in a weight ratio of 5:1.

[0077] The molar ratio of active H in component A to NCO groups in component B is 1:1.1.

[0078] The raw material components of component A are mixed and stirred evenly, and then mixed with component B through a dual-pipeline before being injected into a mold for foaming and shaping. The foaming temperature is 60℃ and the foaming time is 5 minutes to obtain a foamed polyurethane material.

[0079] Example 2

[0080] The difference between this embodiment and Embodiment 1 is that in Embodiment 1, the modified silicone oil used in the preparation of Embodiment 1 was changed from 1 part to 3 parts. The remaining steps remain unchanged.

[0081] Comparative Example 1

[0082] The difference between this comparative example and Example 2 is that in Example 2, 3 parts of modified silicone oil were replaced with a combination of 2.2 parts of silicone oil foam stabilizer and 0.8 parts of 2-methylanthraquinone. The remaining steps remained unchanged.

[0083] Comparative Example 2

[0084] The difference between this comparative example and Comparative Example 1 is that in Comparative Example 1, the combination of 2.2 parts silicone oil foam stabilizer and 0.8 parts 2-methylanthraquinone was replaced with a combination of 2 parts silicone oil foam stabilizer and 1 part 2-methylanthraquinone. The remaining steps remained unchanged.

[0085] Example 3

[0086] The difference between this embodiment and Embodiment 1 is that in Embodiment 1, the modified silicone oil used in Example 1 was changed from 1 part to 5 parts. The remaining steps remain unchanged.

[0087] Example 4

[0088] The difference between this embodiment and Embodiment 2 is that in Embodiment 2, the modified silicone oil in Preparation Example 1 is replaced with 3 parts of the modified silicone oil in Preparation Example 2. The remaining steps remain unchanged.

[0089] Example 5

[0090] The difference between this embodiment and Embodiment 2 is that in Embodiment 2, the raw material components of component A also include 0.1 parts of single-arm carbon nanotubes. The remaining steps remain unchanged.

[0091] Example 6

[0092] The difference between this embodiment and Embodiment 2 is that in Embodiment 2, the raw material components of component A also include 0.5 parts of single-arm carbon nanotubes. The remaining steps remain unchanged.

[0093] Example 7

[0094] Foamed polyurethane material, composed of component A and component B;

[0095] The raw material components of component A include: 100 parts of PEG / PPG polyether diol with a number average molecular weight of 1000 (PEG molar percentage of 40%), 4 parts of 1,6-hexanediol, 2 parts of dihydroxyethylamine, 3 parts of the modified silicone oil of Preparation Example 2, and 1.3 parts of water.

[0096] Component B is a combination of HDI and HDI trimer in a weight ratio of 7:1.

[0097] The molar ratio of active H in component A to NCO groups in component B is 1:15.

[0098] Example 8

[0099] The difference between this embodiment and Embodiment 7 is that in Embodiment 7, the raw material components of component A also include 0.5 parts of graphene. The remaining steps remain unchanged.

[0100] Comparative Example 3

[0101] The difference between this comparative example and Example 8 is that in Example 8, 3 parts of modified silicone oil were replaced with a combination of 2 parts silicone oil foam stabilizer and 1 part 2-methylanthraquinone. The remaining steps remained unchanged.

[0102] Performance testing

[0103] Hydrophilicity: The water contact angle was tested using a water contact angle tester. The foamed polyurethane materials of Examples 1-8 and Comparative Examples 1-3 were prepared into blocks with dimensions of 15cm×15cm×5mm. The water contact angle was tested at five locations on the same surface of each block, including the four corners and the middle. The average value of the five results is shown in Table 1 below.

[0104] Table 1 Results of water contact angle test

[0105] Example 1 Example 2 Comparative Example 1 Comparative Example 2 Example 3 Example 4 Water contact angle / ° 67.1 63.6 86.1 83.3 61.2 62.4 Example 5 Example 6 Example 7 Example 8 Comparative Example 3 Water contact angle / ° 62.8 63.1 58.7 59.6 75.2

[0106] As shown in Table 1 above, the foamed polyurethane material of the present invention exhibits good hydrophilicity. As shown in Comparative Examples 1 and 2, the use of silicone oil as a foaming agent resulted in poor hydrophilicity. When the polymer diol contains a certain amount of polyethylene glycol segments, the hydrophilicity can be further improved.

[0107] Nitrogen removal performance test: Prepare 500 ml of denitrification medium with an initial concentration of 50 mg / L (initial nitrate concentration of 50 mg / L), inoculate with 3% microorganisms activated and cultured in LB medium, and place the inoculated denitrification medium in a constant temperature shaker set at 36℃ and 120 r / min to ensure that 10 g of the test packing material in the medium is in a good fluidized state. Samples are taken every 5 hours. After centrifuging at 3000 rpm for 10 min, the supernatant of the sample is quantitatively diluted, and the absorbance is measured using a UV spectrophotometer to calculate the corresponding concentration and the nitrogen removal rate. The nitrogen removal rate at time t = (C0 - C...) / (C0 - C ... t ) / C0×100%, where C0 is the initial concentration of nitrate, C t Let t be the concentration of nitrate at time t. Each sample was measured three times, and the average of the three results was taken.

[0108] The results are shown in Table 2 below, where the blank group is the foamed polyurethane material prepared according to Comparative Example 2, which does not contain anthraquinone compounds.

[0109] Table 2 Nitrogen removal rate / %

[0110] 5h 10h 15h 20h 25h Blank group 1.8 3.7 16.4 40.1 88.5 Example 1 2.0 7.1 51.6 72.3 90.4 Example 2 4.7 15.3 60.2 80.4 90.8 Comparative Example 1 2.1 8.5 42.7 69.8 89.4 Comparative Example 2 2.4 9.7 50.5 75.2 90.6 Example 3 10.2 62.9 87.0 90.6 / Example 4 5.1 17.4 65.8 82.3 90.7 Example 5 9.8 74.5 90.3 / / Example 6 12.5 82.7 91.4 / / Example 7 5.8 19.8 69.2 85.3 91.0 Example 8 14.1 85.0 91.7 / / Comparative Example 3 7.7 28.9 65.8 82.4 90.6

[0111] Therefore, as can be seen from the data results in Table 2 above, the foamed polyurethane material of the present invention has better denitrification performance, and compared with the direct physical mixing of anthraquinone into the foamed polyurethane material, the modified silicone oil with hydrophilic grafted anthraquinone has a significantly faster denitrification efficiency. Comparing Example 7, Example 8 and Comparative Example 3, (1) Example 8 increased graphene compared with Example 7, which significantly improved the denitrification efficiency; (2) Compared with Example 7, Comparative Example 3 replaced the modified silicone oil with a physical combination of foam stabilizer and anthraquinone. The denitrification efficiency in the later stage of Comparative Example 3 was not better. This may be related to the distribution of anthraquinone in the foamed polyurethane material and the dispersion of graphene. In Comparative Example 3, the anthraquinone was distributed relatively evenly in the foamed polyurethane material, resulting in less anthraquinone on the surface. The dispersion of the foam stabilizer on graphene was not good enough, which also affected the performance of graphene.

[0112] Durability: The packing material to be tested was immersed in water for 96 hours, then removed and air-dried at room temperature for 24 hours. The denitrification performance was then tested according to the above-mentioned test, and the denitrification rate retention rate after 15 hours was measured. Denitrification rate retention rate = (Denitrification rate after immersion / Denitrification rate before immersion) × 100%. The higher the denitrification rate retention rate, the better the stability and durability of the packing material's denitrification performance.

[0113] The results are shown in Table 3 below.

[0114] Table 3. Denitrification rate retention rate (%)

[0115] Example 2 Comparative Example 1 Example 3 Example 4 Example 7 82.5 70.1 85.4 96.3 94.8

[0116] Therefore, as can be seen from the data in Table 3 above, when the modified silicone oil has hydroxyl groups at both ends, it can participate in the preparation reaction of polyurethane and stably bind in the foamed polyurethane material, resulting in a more lasting effect.

[0117] As described above, the basic principles, main features, and advantages of the present invention have been shown and described. Those skilled in the art should understand that the present invention is not limited to the above embodiments, which are merely preferred embodiments and should not be construed as limiting the scope of the invention. All equivalent changes and modifications made in accordance with the scope of the patent and the description should still fall within the scope of the present invention. The scope of protection of this invention is defined by the appended claims and their equivalents.

Claims

1. A foamed polyurethane material, characterized in that, It consists of component A and component B; The raw material components of component A include: 100 parts polymer diol, 1-8 parts chain extender, 1-3 parts catalyst, 1-5 parts modified silicone oil and 0.5-2 parts water; The structure of the modified silicone oil is shown in formula (1) below. R 1 Me2SiO(SiOMe2) a (SioMeR 2 ) b (SioMeR 3 ) c SiMe2R 1 (1) Among them, R 1 Selected from C1-C4 alkyl, C2-C6 hydroxyalkyl, or amino-containing C3-C6 alkyl, R 2 Contains polyethylene glycol segments, R 3 It contains anthraquinone structure, Me is a methyl group, a = 10-100, b = 3-15, c = 5-20; Component B is a polyisocyanate compound.

2. The foamed polyurethane material according to claim 1, characterized in that, The R 1 Selected from -(CH2) m OH, -(CH2) n NH2、-(CH2) o NH(CH2) p CH3 and -(CH2) q One or more combinations of NH(CH2)2NH2, wherein m = 2-6, n = 2-6, o = 2-6, p = 0-2, q = 2-6.

3. The foamed polyurethane material according to claim 1, characterized in that, The R 2 The structure is shown in equation (2) below. -(CH2)3(OCH2CH2) d OR 4 (2) Among them, R 4 Selected from H or C1-C4 alkyl groups, d = 4-50.

4. The foamed polyurethane material according to claim 1, characterized in that, The R 3 The structure is shown in equation (3) below. Among them, R 5 Selected from H, hydroxyl or C1-C4 alkyl, R 6 For the absence of oxygen atoms, e = 0 - 2.

5. The foamed polyurethane material according to claim 1, characterized in that, The polymer diol is selected from polyether diols and / or polyester diols; Preferably, the molar percentage of polyethylene glycol segments in the polyether diol is not less than 30%.

6. The foamed polyurethane material according to claim 1, characterized in that, The chain extender is selected from C2-C8 alkyl diols.

7. The foamed polyurethane material according to claim 1, characterized in that, The catalyst is selected from dihydroxyalkylamine.

8. The foamed polyurethane material according to claim 1, characterized in that, The polyisocyanate compound is selected from diisocyanate monomers and their trimers; The molar ratio of active hydrogen in component A to NCO groups in component B is 1:1.08-1.

2.

9. The foamed polyurethane material according to claim 1, characterized in that, The raw material components also include 0.1-2 parts of carbon-based materials; The carbon-based material is selected from one or a combination of two or more of carbon nanotubes, graphene, and fullerene.

10. An application of the foamed polyurethane material according to any one of claims 1-9, characterized in that, It is used for the treatment of nitrogen-containing wastewater.

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