A polyurethane foam and a method for its production and use

Abstract

The application provides a polyurethane foam and a preparation method and application thereof, relates to the technical field of functional materials, and the polyurethane foam comprises an A component and a B component, wherein the A component comprises the following components in parts by weight: MOFs material 1-20 parts; polyether polyol 80-90 parts; polymer polyol 5-10 parts; water 3-8 parts; organic metal catalyst 0.1-0.5 parts; amine catalyst 0.1-0.5 parts; silicone oil 0.1-0.5 parts; and the B component is a polyisocyanate. The polyurethane foam provided by the application has a stable three-dimensional porous structure, the integrated preparation of the MOFs polyurethane composite foam is realized through the high-efficiency polyurethane foaming technology, the MOFs are structured, the stability of the MOFs is enhanced, and the performance of the MOFs in efficient adsorption and photocatalytic degradation and removal of water organic pollutants is further improved.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of functional materials, in particular to a polyurethane foam and a preparation method and application thereof. BACKGROUND

[0002] Porous materials play an important role in the adsorption and catalytic degradation removal of organic pollutants in water environment. Among them, MOFs metal organic framework materials have attracted extensive research due to their large specific surface area, high porosity and rich active sites. However, the powder MOFs are easy to agglomerate, which limits their performance in practical application.

[0003] Currently, researchers mainly grow MOFs materials in situ on various substrates, such as electrospun nanofibers, carbon fibers, melamine foam, graphene aerogel and other substrates. However, the structure stability of the composite material constructed by this in-situ growth method needs to be improved, and the MOFs are easy to fall off from the interface during long-term use. Therefore, how to realize the stable structuring of MOFs materials and construct efficient multi-level porous structure environmental remediation materials is an important research topic. SUMMARY

[0004] In order to solve the problem of poor stability of the supported MOFs composite material in the prior art and the difficulty in directly removing water pollutants, the present application discloses a polyurethane foam and a preparation method and application thereof. The integration of MOFs polyurethane composite foam is realized by efficient polyurethane foaming technology, which not only realizes the structuring of MOFs and enhances its stability, but also further improves its adsorption and catalytic degradation removal performance for organic pollutants in water environment.

[0005] The technical scheme adopted by the present application to solve its technical problems is:

[0006] A polyurethane foam, the polyurethane foam comprises A component and B component, in terms of weight fraction,

[0007] The A component comprises the following components:

[0008] MOFs material 1-20 parts;

[0009] Polyether polyol 80-90 parts;

[0010] Polymer polyol 5-10 parts;

[0011] Water 3-8 parts;

[0012] Organometallic catalyst 0.1-0.5 parts;

[0013] Amine catalyst 0.1-0.5 parts;

[0014] Silicone oil 0.1-0.5 parts;

[0015] The B component is a polyisocyanate.

[0016] Optionally, the MOFs material is prepared by using a metal salt and an organic ligand molecule as raw materials, and synthesizing the MOFs material through a solvothermal method.

[0017] Optionally, the amine catalyst is selected from at least one of Dabco 33LV, DMAEE, A-300, and A-400.

[0018] Optionally, the organic metal catalyst is selected from at least one of an organic zinc catalyst, an organic tin catalyst, and an organic bismuth catalyst.

[0019] Optionally, the mass ratio of the metal salt and the organic ligand molecule is 1:5-8.

[0020] Optionally, the MOFs material has photocatalytic activity.

[0021] Optionally, the organic ligand molecule contains an active group, and the active group is selected from at least one of a hydroxyl group, an amino group, and a mercapto group.

[0022] Another object of the present application is to provide a preparation method of the polyurethane foam as described above, comprising the following steps: mixing the A component and the B component and then foaming to obtain the polyurethane foam.

[0023] Optionally, the mass ratio of the A component to the B component is 1:1-1.2.

[0024] Still another object of the present application is to provide the polyurethane foam as described above for adsorbing and catalytically degrading and removing organic pollutants in a water environment.

[0025] The present application has the following beneficial effects:

[0026] The MOFs polyurethane foam prepared by the present application has excellent removal rate and can effectively adsorb and degrade water pollutants through photocatalytic MOF foaming technology.

[0027] In addition, the inventors have found through extensive experimental research that by precisely regulating the foaming process to achieve structuring, the material can be customized according to different environmental management needs to adapt to the filling requirements of various reactors. By adjusting the foaming parameters, the density and pore characteristics of the foam can be precisely controlled to optimize the performance of the material in specific applications. This structured composite material not only improves the stability and durability of MOFs, but also enhances its practicality and flexibility in actual water purification systems. DETAILED DESCRIPTION

[0028] The application will now be further described. The examples described below are exemplary and are intended to serve to explain the application and cannot be understood as limiting the application. All other examples obtained by a person of ordinary skill in the art without creative labor based on the examples of the application fall within the scope of protection of the application.

[0029] Polyurethane-based foaming sponge is a good carrier with good flexibility, mechanical strength and porous structure. Mixing MOFs material with polyurethane resin realizes one-step in-situ foaming, which can construct MOFs polyurethane foam composite material at one time. The active groups in the MOFs ligand can participate in the formation of the polyurethane crosslinked network to increase the bonding strength. The porous coating of polyurethane can increase the load of MOFs and increase its pollutant removal effect.

[0030] Therefore, in order to solve the problem of poor stability of the supported MOFs composite material in the prior art and the difficulty in directly removing water pollutants, the application discloses a polyurethane foam, wherein the polyurethane foam comprises component A and component B, and the weight ratio of component A to component B is 1:1-1:2.

[0031] The component A comprises the following components:

[0032] MOFs material 1-20 parts;

[0033] Polyether polyol 80-90 parts;

[0034] Polymer polyol 5-10 parts;

[0035] Water 3-8 parts;

[0036] Organometallic catalyst 0.1-0.5 parts;

[0037] Amine catalyst 0.1-0.5 parts;

[0038] Silicone oil 0.1-0.5 parts;

[0039] The component B is a polyisocyanate.

[0040] The MOFs polyurethane foam prepared by the application has a stable three-dimensional porous structure, which not only provides a larger specific surface area to promote effective contact of pollutants with active sites of the MOFs, but also optimizes mass transfer efficiency, accelerates the adsorption and decomposition process of pollutants, and thus significantly improves the adsorption and degradation efficiency of environmental pollutants.

[0041] The organic metal catalyst can promote the establishment of the mechanical properties of the foaming material, and the amine catalyst can promote foaming and the formation of cells, and under the action of the two catalysts, the establishment of the strength of the foam and the cell rate can be promoted.

[0042] Specifically, the amine catalyst is preferably at least one selected from Dabco 33LV, DMAEE, A-300 and A-400.

[0043] Further, the amine catalyst is preferably triethylene imine.

[0044] The organic metal catalyst is preferably at least one selected from organic zinc catalysts, organic tin catalysts and organic bismuth catalysts.

[0045] Further, the organic metal catalyst is preferably at least one selected from zinc octoate, dibutyltin dilaurate, tin octoate, dibutyltin diacetate, dibutyltin bis (dodecylthio), bis (acetylacetate) dibutyltin, bismuth neodecanoate, bismuth laurate, bismuth isooctoate and bismuth naphthenate.

[0046] The polyether polyol is preferably at least one selected from EP330NG, MN-3050D and MN-1000.

[0047] Further, the polyether polyol is preferably MN-3050D.

[0048] The polymeric polyol is preferably at least one selected from POP36 / 28, POP93 / 28, HPOP40 and GPOP-2045.

[0049] Further, the polymeric polyol is preferably GPOP-2045.

[0050] The MOFs material is preferably prepared by the following method: taking a metal salt and an organic ligand molecule as raw materials, reacting at 30-180 DEG C in a methanol solution for 10-12 h, and centrifugally separating to obtain the MOFs material.

[0051] Further, the MOFs material has photocatalytic activity, so that the material can be activated under light conditions and effectively adsorb and degrade water pollutants, thereby improving the efficiency and speed of water pollutant treatment, while reducing energy consumption and operating cost; and the average particle size of the MOFs material is preferably 300-1000 nm; this particle size range is conducive to more uniform dispersion of the MOFs material in the polyurethane foam, reducing the agglomeration phenomenon, thereby increasing the available surface area of the material and the number of active sites.

[0052] The mass ratio of the metal salt and the organic ligand molecule is preferably 1:5-8; further, the mass ratio of the metal salt and the organic ligand molecule is preferably 1:5.

[0053] The metal ion in the metal salt is preferably at least one selected from Zn 2+ , Fe 3+ , Ti 4+ , and Zr 4+ .

[0054] To further enhance the adsorption and degradation capacity of the material, the organic ligand molecule preferably contains an active group selected from at least one of hydroxyl, amino, and mercapto.

[0055] Further, the organic ligand molecule is preferably at least one selected from hydroxyterephthalic acid, amino terephthalic acid, mercapto terephthalic acid, and tetracarboxyphenyl porphyrin.

[0056] Another object of the present application is to provide a preparation method of the polyurethane foam as described above, comprising the following steps:

[0057] S1: according to the formula amount, polyether polyol, polymer polyol, and MOFs material are added to a reaction kettle for mixing and stirring until there are no obvious undispersed particles, then the temperature is raised to 50-60℃, and stirring is carried out at a speed of 300-400 rpm for 50-60 min, then the temperature is lowered to 35-40℃ at a rate of 1℃ / min, to obtain a premixed base material;

[0058] S2: deionized water is added to the premixed base material, then silicone oil, organic metal catalyst, and amine catalyst are added, and stirring and dispersion are carried out for 40-50 min, then vacuum mixing is carried out at a speed of 100-120 rpm for 25-30 min, to obtain component A;

[0059] Component B is TDI;

[0060] After mixing component A and component B at a mass ratio of 1:1-1.2, foaming is carried out to obtain the polyurethane foam.

[0061] By precisely regulating the foaming process to achieve structuring, the material can be customized according to different environmental management needs to adapt to the filling requirements of various reactors. By adjusting the foaming parameters, the density and pore characteristics of the foam can be precisely controlled to optimize the performance of the material in specific applications. This structured composite material not only improves the stability and durability of MOFs, but also enhances their adsorption and catalytic degradation removal of organic pollutants in actual water environments.

[0062] Another object of the present application is to provide the use of the polyurethane foam as described above in the removal of organic pollutants in water bodies.

[0063] Preferably, the polyisocyanate of the present application is selected from at least one of HDI, HMDI, TDI, MDI, PM200, PM400, and PM700.

[0064] Further, the polyisocyanate of the present application is preferably TDI.

[0065] In order to make the above-mentioned objects, features and advantages of the present application more obvious and easy to understand, the specific embodiments of the present application are described in detail below.

[0066] Example 1

[0067] The present embodiment provides a polyurethane foam, wherein the polyurethane foam comprises a component A and a component B, and the component A and the component B are calculated by weight fraction,

[0068] The component A comprises the following components:

[0069] MOFs material 2 parts;

[0070] Polyether polyol 86 parts;

[0071] Polymer polyol 8 parts;

[0072] Water 5 parts;

[0073] Stannous octoate 0.2 parts;

[0074] Amine catalyst 0.25 parts;

[0075] Silicone oil 0.5 parts;

[0076] The component B is a polyisocyanate.

[0077] The MOFs material is prepared by the following method:

[0078] Zinc nitrate and hydroxyterephthalic acid with a mass ratio of 1:5 are used as raw materials, and the reaction is carried out in methanol solution at 180℃ for 12h, and the MOFs material is obtained by centrifugal separation;

[0079] The preparation method of the above-mentioned polyurethane foam comprises the following steps:

[0080] S1: according to the formula, the polyether polyol, the polymer polyol, the MOFs material, is added to the reaction kettle, mixed and stirred until there are no obvious undispersed particles, then heated to 50℃, stirred at 300rpm for 60min, then cooled to 35℃ at 1℃ / min, to obtain a premixed base;

[0081] S2: deionized water is added to the premixed base, then silicone oil, organometallic catalyst and amine catalyst are added, stirred and dispersed for 40min, then mixed at 120rpm under vacuum for 30min, to obtain component A;

[0082] S3: component A is mixed with component B at a mass ratio of 1:1, then foaming is carried out, to obtain a polyurethane foam.

[0083] Example 2

[0084] The embodiment provides a polyurethane foam, wherein the polyurethane foam comprises component A and component B, according to weight fraction,

[0085] The component A comprises the following components:

[0086] MOFs material 20 parts;

[0087] Polyether polyol 80 parts;

[0088] Polymer polyol 5 parts;

[0089] Water 8 parts;

[0090] Zinc octoate 0.5 parts;

[0091] Amine catalyst 0.1 parts;

[0092] Silicone oil 0.3 parts;

[0093] The component B is a polyisocyanate.

[0094] The MOFs material is prepared according to the following method:

[0095] Iron nitrate and amino terephthalic acid at a mass ratio of 1:5 are used as raw materials, reacted in a methanol solution at 120℃ for 10h, centrifuged to obtain the MOFs material;

[0096] The preparation method of the polyurethane foam comprises the following steps:

[0097] S1: according to the formula, the polyether polyol, the polymer polyol, the MOFs material, is added to the reaction kettle, mixed and stirred until there are no obvious undispersed particles, then heated to 60℃, stirred at 400rpm for 50min, then cooled to 40℃ at 1℃ / min, to obtain a premixed base;

[0098] S2: adding deionized water to the premixed base, then adding silicone oil, organometallic catalyst and amine catalyst, stirring and dispersing for 50 min, then mixing under vacuum at 100 rpm for 25 min to obtain component A;

[0099] S3: mixing component A and component B according to a mass ratio of 1:1-1.2 to foam, to obtain the polyurethane foam.

[0100] Example 3

[0101] The embodiment provides a polyurethane foam, wherein the polyurethane foam comprises component A and component B, according to weight fractions,

[0102] The component A comprises the following components:

[0103] MOFs material 10 parts;

[0104] Polyether polyol 90 parts;

[0105] Polymer polyol 10 parts;

[0106] Water 3 parts;

[0107] Bismuth octoate 0.1 part;

[0108] Amine catalyst 0.5 parts;

[0109] Silicone oil 0.1 part;

[0110] The component B is a polyisocyanate;

[0111] The MOFs material is prepared according to the following method:

[0112] Titanium tetrachloride and mercaptoterephthalic acid are used as raw materials according to a mass ratio of 1:5, and reacted at 100 DEG C for 12 h in a methanol solution, and the MOFs material is obtained by centrifugal separation;

[0113] The preparation method of the polyurethane foam comprises the following steps:

[0114] S1: according to the formula amount, polyether polyol, polymer polyol and MOFs material are added into a reaction kettle and mixed and stirred until there are no obvious undispersed particles, then the temperature is raised to 55 DEG C, and stirred at 350 rpm for 55 min, then the temperature is lowered to 40 DEG C at a rate of 1 DEG C / min, to obtain a premixed base;

[0115] S2: adding deionized water to the premixed base, then adding silicone oil, organometallic catalyst and amine catalyst, stirring and dispersing for 40 min, then mixing under vacuum at 120 rpm for 30 min to obtain component A;

[0116] S3: mixing the A component and the B component according to a mass ratio of 1:1.1 to foam, to obtain the polyurethane foam.

[0117] Example 4

[0118] The embodiment provides a polyurethane foam, wherein the polyurethane foam comprises an A component and a B component, and the A component and the B component are mixed according to a mass ratio of 1:1.1 to foam, to obtain the polyurethane foam.

[0119] The A component comprises the following components:

[0120] 5 parts of MOFs material;

[0121] 84 parts of polyether polyol;

[0122] 6 parts of polymer polyol;

[0123] 6 parts of water;

[0124] 0.4 parts of dibutyltin dilaurate;

[0125] 0.4 parts of amine catalyst;

[0126] 0.5 parts of silicone oil;

[0127] The B component is a polyisocyanate;

[0128] The MOFs material is prepared according to the following method:

[0129] Zirconium tetrachloride and hydroxyterephthalic acid are used as raw materials according to a mass ratio of 1:5, and are reacted in a methanol solution at 180 ℃ for 12 h, to obtain the MOFs material through centrifugal separation;

[0130] The preparation method of the polyurethane foam comprises the following steps:

[0131] S1: according to the formula amount, polyether polyol, polymer polyol and MOFs material are added into a reaction kettle and mixed and stirred until there is no obvious undispersed particle, then the temperature is increased to 60 ℃, and the stirring is performed at a speed of 300 rpm for 50 min, and then the temperature is decreased to 35 ℃ at a speed of 1 ℃ / min, to obtain a premixed base material;

[0132] S2: deionized water is added to the premixed base material, and then silicone oil, an organic metal catalyst and an amine catalyst are added, and stirring and dispersion are performed for 40 min, and then vacuum mixing is performed at a speed of 120 rpm for 30 min, to obtain the A component;

[0133] S3: the A component and the B component are mixed according to a mass ratio of 1:1.2 to foam, to obtain the polyurethane foam.

[0134] Example 5

[0135] The embodiment provides a polyurethane foam, wherein the polyurethane foam comprises an A component and a B component, and the A component and the B component are in a weight ratio of 1:1,

[0136] The A component comprises the following components:

[0137] MOFs material 15 parts;

[0138] Polyether polyol 85 parts;

[0139] Polymer polyol 5 parts;

[0140] Water 5 parts;

[0141] Bismuth neodecanoate 0.5 parts;

[0142] Amine catalyst 0.1 parts;

[0143] Silicone oil 0.3 parts;

[0144] The B component is a polyisocyanate;

[0145] The MOFs material is prepared by the following method:

[0146] Zinc nitrate and amino terephthalic acid in a mass ratio of 1:5 are used as raw materials, and the reaction is carried out in a methanol solution at 90 DEG C for 12 h; centrifugal separation is performed to obtain the MOFs material;

[0147] The preparation method of the polyurethane foam comprises the following steps:

[0148] S1: according to the formula amount, polyether polyol, polymer polyol and MOFs material are added into a reaction kettle and mixed and stirred until there are no obvious undispersed particles; then the temperature is increased to 55 DEG C, and stirring is performed at a speed of 400 rpm for 55 min; then the temperature is decreased to 40 DEG C at a rate of 1 DEG C / min; and a premixed base material is obtained;

[0149] S2: deionized water is added to the premixed base material; then silicone oil, an organic metal catalyst and an amine catalyst are added; stirring and dispersion are performed for 45 min; then vacuum mixing is performed at a speed of 120 rpm for 30 min; and the A component is obtained;

[0150] S3: the A component and the B component are mixed in a mass ratio of 1:1, and then foaming is performed, so that the polyurethane foam is obtained.

[0151] Comparative Example 1 is different from Example 1 in that the MOFs material is not added.

[0152] Comparative Example 2 is different from Example 1 in that the MOFs material is ZIF-8, and the ZIF-8 is prepared by the following method: zinc sulfate and 2-methylimidazole in a mass ratio of 1:5 are mixed in deionized water, and then the mixture is left to stand at room temperature for 24 h; after centrifugal separation, washing and drying, the ZIF-8 is obtained.

[0153] Comparative Example 3 differs from Example 1 in that no organic metal catalyst is added.

[0154] Comparative Example 4 differs from Example 1 in that the MOFs material is added in an amount of 25 parts.

[0155] Comparative Example 5 differs from Example 1 in that the average particle size of the MOFs material is 1200 nm.

[0156] According to the formulation amount, the polyurethane foam prepared in each example and comparative example of the present application and the removal effect after being applied to water pollutants are tested, and the specific test process is as follows:

[0157] 1. Preparation of wastewater sample

[0158] The wastewater sample to be treated is collected, and the initial chemical oxygen demand (COD) and phenol content of the pollutant indicators are recorded as the baseline data for subsequent testing.

[0159] 2. Catalytic degradation treatment

[0160] The polyurethane foam prepared in the present application is cut into a sample of 50mm x 50mm x 10mm and placed in a catalytic degradation tank, then the wastewater is subjected to preliminary impurity removal treatment and pumped into the catalytic degradation tank containing the polyurethane foam, and 3% hydrogen peroxide is added to adjust the pH value of the wastewater to 3-5, and ultraviolet light with an emission wavelength of 400nm is used for irradiation treatment; the irradiation time is set to 50 minutes.

[0161] 3. Analysis of test results

[0162] After the treatment is completed, the COD and phenol content of the wastewater are measured again, and compared with the initial data to calculate the removal rate.

[0163] The test results are shown in Table 1:

[0164] .

[0165] As can be seen from the data in the above table, the MOFs polyurethane foam prepared in the present application exhibits excellent removal rate through photocatalytic MOF foaming technology, and can effectively adsorb and degrade water pollutants; its stable three-dimensional porous structure provides a significant advantage for the foam: on the one hand, this structure greatly increases the specific surface area, so that the water pollutants can fully contact the active sites of the MOFs, thereby improving the adsorption efficiency; on the other hand, it also optimizes the mass transfer efficiency, accelerates the adsorption and decomposition process of the pollutants, thereby significantly improving the adsorption and degradation efficiency of the environmental pollutants.

[0166] With the above ideal embodiments according to the present application as the inspiration, through the above description, relevant staff can make various changes and modifications without deviating from the technical idea of the present application. The technical scope of the present application is not limited to the content of the specification, and must be determined according to the scope of the claims.

Claims

1. A polyurethane foam characterized by, The polyurethane foam comprises an A component and a B component, in terms of parts by weight, The A component comprises the following components: MOFs material 1-20 parts; Polyether polyol 80-90 parts; Polymer polyol 5-10 parts; Water 3-8 parts; Organometallic catalyst 0.1-0.5 parts; Amine catalyst 0.1-0.5 parts; Silicone oil 0.1-0.5 parts; The B component is a polyisocyanate; The MOFs material is prepared by using a metal salt and an organic ligand molecule as raw materials, and synthesizing the MOFs material through solvothermal synthesis; The average particle size of the MOFs material is 300-1000 nm; The organic ligand molecule contains an active group, and the active group is selected from at least one of a hydroxyl group, an amino group, and a mercapto group.

2. The polyurethane foam according to claim 1, wherein, The amine catalyst is selected from at least one of Dabco 33LV, DMAEE, A-300, and A-400.

3. The polyurethane foam according to claim 1, wherein The organometallic catalyst is selected from at least one of an organic zinc catalyst, an organic tin catalyst, and an organic bismuth catalyst.

4. The polyurethane foam according to claim 1, wherein, The mass ratio of the metal salt to the organic ligand molecule is 1:5-8.

5. The polyurethane foam according to claim 1, wherein, The MOFs material has photocatalytic activity.

6. A process for the production of a polyurethane foam as claimed in any of claims 1 to 5, characterized in that The method comprises the following steps: After the A component and the B component are mixed, foaming is performed to obtain the polyurethane foam.

7. The method of making a polyurethane foam according to claim 6, wherein, The mass ratio of the A component to the B component is 1:1-1.

2.

8. Use of the polyurethane foam according to any one of claims 1-7 in removal of organic pollutants in a water body.