Novel polyurethane foam as well as preparation method and application thereof

Abstract

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

Description

Technical Field

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

[0002] Porous materials play an important role in the adsorption and catalytic degradation of organic pollutants in water environments. Among them, MOFs metal organic framework materials have attracted extensive research due to their large specific surface area, high porosity and abundant active sites. However, powdered MOFs are easy to agglomerate and are difficult to use and collect in environmental remediation, which limits their performance in practical applications.

[0003] At present, researchers mainly grow MOFs materials in situ on various substrates, such as electrospun nanofibers, carbon fibers, melamine foam, graphene aerogels, etc. However, the structural stability of the composite materials constructed by this in situ growth method needs to be improved, and MOFs are prone to fall off from the interface after long-term use. Therefore, how to achieve the stable structuring of MOFs materials and construct efficient multi-level porous structure environmental remediation materials is an important research topic. Summary of the invention

[0004] In order to solve the problem that the supported MOFs composite materials in the prior art have poor stability and are difficult to be directly used for removing water pollutants, the present invention discloses a novel polyurethane foam and a preparation method and application thereof. The integrated preparation of MOFs polyurethane composite foam is realized through the high-efficiency polyurethane foaming technology, which can not only realize the structuring of MOFs and enhance its stability, but also further improve its adsorption and catalytic degradation and removal performance of organic pollutants in the water environment.

[0005] The technical solution adopted by the present invention to solve its technical problem is: A novel polyurethane foam, comprising component A and component B, measured by weight: The A component includes the following components: 1-20 parts of MOFs material; 80-90 parts of polyether polyol; 5-10 parts of polymer polyol; 3-8 parts water; 0.1-0.5 parts of organic metal catalyst; 0.1-0.5 parts of amine catalyst; Silicone oil 0.1-0.5 parts; The B component is a polyisocyanate.

[0006] Optionally, the MOFs material is prepared according to the following method: using metal salts and organic ligand molecules as raw materials, and synthesizing the MOFs material by solvent thermal synthesis.

[0007] Optionally, the amine catalyst is selected from at least one of Dabco 33LV, DMAEE, A-300, and A-400.

[0008] 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.

[0009] Optionally, the mass ratio of the metal salt to the organic ligand molecule is 1:5-8.

[0010] Optionally, the MOFs material has photocatalytic activity.

[0011] 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 thiol group.

[0012] Another object of the present invention is to provide a method for preparing the novel polyurethane foam as described above, comprising the following steps: mixing component A and component B and foaming the mixture to obtain the polyurethane foam.

[0013] Optionally, the mass ratio of component A to component B is 1:1-1.2.

[0014] Another object of the present invention is to provide a novel polyurethane foam as described above for adsorption and catalytic degradation and removal of organic pollutants in water environments.

[0015] The present invention has the following beneficial effects: The novel MOFs polyurethane foam prepared by the present invention exhibits an excellent removal rate through photocatalytic MOF foaming technology, and can effectively adsorb and degrade water pollutants; its stable three-dimensional porous structure provides significant advantages for the foam: on the one hand, this structure greatly increases the specific surface area, so that water pollutants can fully contact with the active sites of MOFs, thereby improving the adsorption efficiency; on the other hand, it also optimizes the mass transfer efficiency, accelerates the adsorption and decomposition process of pollutants, thereby significantly improving the adsorption and degradation efficiency of environmental pollutants.

[0016] In addition, the inventors found through a large number of experimental studies that by precisely controlling the foaming process to achieve structuring, the material can be customized according to different environmental governance needs to meet 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

[0017] The present invention is now further described in detail. The embodiments described below are exemplary and intended to be used to explain the present invention, but cannot be understood as limiting the present invention. All other embodiments obtained by ordinary technicians in this field without creative work based on the embodiments of the present invention belong to the scope of protection of the present invention.

[0018] Polyurethane foam sponge is a good carrier with good flexibility, mechanical strength and porous structure. MOFs material is mixed with polyurethane resin to achieve one-step in-situ foaming, and MOFs polyurethane foam composite materials can be constructed at one time. The active groups in MOFs ligands can participate in the formation of polyurethane cross-linked networks to increase the bonding strength. The porous coating of polyurethane can increase the loading capacity of MOFs and increase its pollutant removal effect.

[0019] Therefore, in order to solve the problem that the supported MOFs composite materials in the prior art have poor stability and are difficult to be directly used for removing water pollutants, the present invention discloses a novel polyurethane foam, wherein the polyurethane foam comprises component A and component B, which are calculated by weight. Component A includes the following components: 1-20 parts of MOFs material; 80-90 parts of polyether polyol; 5-10 parts of polymer polyol; 3-8 parts water; 0.1-0.5 parts of organic metal catalyst; 0.1-0.5 parts of amine catalyst; Silicone oil 0.1-0.5 parts; Component B is polyisocyanate.

[0020] The novel MOFs polyurethane foam prepared by the present invention has a stable three-dimensional porous structure, which not only provides a larger specific surface area to promote the effective contact between pollutants and MOFs active sites, but also optimizes the mass transfer efficiency and accelerates the adsorption and decomposition process of pollutants, thereby significantly improving the adsorption and degradation efficiency of environmental pollutants.

[0021] Organic metal catalysts can promote the establishment of mechanical properties of foaming materials, while amine catalysts can promote foaming and form pores. Under the action of the two catalysts, the establishment of foam strength and porosity can be promoted.

[0022] Specifically, the preferred amine catalyst of the present invention is at least one selected from Dabco 33LV, DMAEE, A-300, and A-400.

[0023] Furthermore, the preferred amine catalyst is triethyleneimine.

[0024] In the present invention, the organometallic catalyst is preferably at least one selected from the group consisting of an organozinc catalyst, an organotin catalyst and an organobismuth catalyst.

[0025] Furthermore, the organic metal catalyst is preferably selected from at least one of zinc octoate, dibutyltin dilaurate, stannous octoate, dibutyltin diacetate, dibutyltin didodecylsulfide, dibutyltin bis(acetylacetonate), bismuth neodecanoate, bismuth laurate, bismuth isooctanoate, and bismuth cyclohexaneate.

[0026] The preferred polyether polyol of the present invention is at least one selected from EP330NG, MN-3050D, and MN-1000.

[0027] Furthermore, the preferred polyether polyol is MN-3050D.

[0028] The preferred polymer polyol of the present invention is at least one selected from POP36 / 28, POP93 / 28, HPOP40, and GPOP-2045.

[0029] Furthermore, the preferred polyether polyol is GPOP-2045.

[0030] In the present invention, the MOFs material is preferably prepared according to the following method: using metal salt and organic ligand molecules as raw materials, reacting in a methanol solution at 30-180° C. for 10-12 h, and centrifuging to obtain the MOFs material.

[0031] Furthermore, the present invention preferably selects MOFs materials with photocatalytic activity, so that the materials 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 costs; and preferably selects an average particle size of the MOFs material of 300-1000 nm; this particle size range is conducive to more uniform dispersion of the MOFs material in the polyurethane foam, reduces agglomeration, thereby increasing the available surface area of ​​the material and the number of active sites.

[0032] In the present invention, the mass ratio of the metal salt to the organic ligand molecule is preferably 1:5-8; further, the mass ratio of the metal salt to the organic ligand molecule is preferably 1:5.

[0033] The metal ion in the preferred metal salt of the present invention is selected from Zn 2+ , Fe 3+ , Ti 4+ , Zr 4+ At least one of .

[0034] In order to further enhance the adsorption and degradation capabilities of the material, the present invention preferably contains active groups in the organic ligand molecules, and the active groups are selected from at least one of hydroxyl, amino, and thiol.

[0035] Furthermore, in the present invention, the organic ligand molecule is preferably selected from at least one of hydroxyterephthalic acid, aminoterephthalic acid, mercaptoterephthalic acid and tetracarboxyphenylporphyrin.

[0036] Another object of the present invention is to provide a method for preparing the novel polyurethane foam as described above, comprising the following steps: S1: According to the formula, 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 50-60°C, and the reaction speed is stirred at 300-400 rpm for 50-60 minutes, and then the temperature is lowered to 35-40°C at 1°C / min to obtain a premixed base material; S2: Add deionized water to the premixed base material, then add silicone oil, organic metal catalyst and amine catalyst, stir and disperse for 40-50 minutes, then mix at a speed of 100-120 rpm in vacuum for 25-30 minutes to obtain component A; Component B is TDI; Component A and component B are mixed in a mass ratio of 1:1-1.2 and then foamed to obtain polyurethane foam.

[0037] By precisely controlling the foaming process to achieve structuring, the material can be customized according to different environmental governance needs to meet 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 adsorption and catalytic degradation and removal of organic pollutants in actual water environments.

[0038] Another object of the present invention is to provide an application of the novel polyurethane foam as described above in removing organic pollutants from water bodies.

[0039] The polyisocyanate of the present invention is preferably selected from at least one of HDI, HMDI, TDI, MDI, PM200, PM400 and PM700.

[0040] Furthermore, in the present invention, the preferred polyisocyanate is TDI.

[0041] In order to make the above-mentioned objects, features and advantages of the present invention more obvious and easy to understand, specific embodiments of the present invention are described in detail below.

[0042] Example 1 This embodiment provides a novel polyurethane foam, wherein the polyurethane foam comprises component A and component B, which are calculated by weight: The A component includes the following components: 2 parts of MOFs material; 86 parts of polyether polyol; 8 parts of polymer polyol; 5 parts water; 0.2 parts of stannous octoate; 0.25 parts of amine catalyst; 0.5 parts of silicone oil; The B component is a polyisocyanate.

[0043] Wherein, MOFs material is prepared according to the following method: Zinc nitrate and hydroxyterephthalic acid in a mass ratio of 1:5 were used as raw materials, reacted at 180°C for 12 hours in a methanol solution, and centrifuged to obtain MOFs materials; The preparation method of the novel polyurethane foam comprises the following steps: S1: According to the formula, polyether polyol, polymer polyol and MOFs material are added into a reactor and mixed and stirred until there are no obvious undispersed particles, then the temperature is raised to 50°C, stirred at 300 rpm for 60 min, and then the temperature is lowered to 35°C at 1°C / min to obtain a premixed base material; S2: Add deionized water to the premixed base material, then add silicone oil, organic metal catalyst and amine catalyst, stir and disperse for 40 minutes, and then mix at 120 rpm in vacuum for 30 minutes to obtain component A; S3: Component A and component B are mixed in a mass ratio of 1:1 and then foamed to obtain polyurethane foam.

[0044] Example 2 This embodiment provides a novel polyurethane foam, wherein the polyurethane foam comprises component A and component B, which are calculated by weight: The A component includes the following components: 20 parts of MOFs materials; 80 parts of polyether polyol; 5 parts of polymer polyol; 8 parts water; 0.5 part of zinc octoate; 0.1 part of amine catalyst; 0.3 parts of silicone oil; The B component is a polyisocyanate.

[0045] Wherein, MOFs material is prepared according to the following method: Using iron nitrate and aminoterephthalic acid in a mass ratio of 1:5 as raw materials, reacting at 120°C in a methanol solution for 10 hours, and centrifuging to obtain MOFs material; The preparation method of the novel polyurethane foam comprises the following steps: S1: According to the formula, polyether polyol, polymer polyol and MOFs material are added into a reactor and mixed and stirred until there are no obvious undispersed particles, then the temperature is raised to 60°C, stirred at 400 rpm for 50 min, and then the temperature is lowered to 40°C at 1°C / min to obtain a premixed base material; S2: Add deionized water to the premixed base material, then add silicone oil, organic metal catalyst and amine catalyst, stir and disperse for 50 minutes, and then mix at a speed of 100 rpm in vacuum for 25 minutes to obtain component A; S3: Component A and component B are mixed in a mass ratio of 1:1-1.2 and then foamed to obtain polyurethane foam.

[0046] Example 3 This embodiment provides a novel polyurethane foam, wherein the polyurethane foam comprises component A and component B, which are calculated by weight: The A component includes the following components: 10 parts of MOFs materials; 90 parts of polyether polyol; 10 parts of polymer polyol; 3 parts water; 0.1 part of bismuth isooctanoate; 0.5 parts of amine catalyst; 0.1 part of silicone oil; The B component is a polyisocyanate; Wherein, MOFs material is prepared according to the following method: Using titanium tetrachloride and mercaptoterephthalic acid in a mass ratio of 1:5 as raw materials, reacting them in a methanol solution at 100°C for 12 hours, and centrifuging to obtain MOFs materials; The preparation method of the novel polyurethane foam comprises the following steps: S1: According to the formula, polyether polyol, polymer polyol and MOFs material were added into the reaction kettle and mixed and stirred until there were no obvious undispersed particles, then the temperature was raised to 55°C, stirred at 350 rpm for 55 min, and then the temperature was lowered to 40°C at 1°C / min to obtain a premixed base material; S2: Add deionized water to the premixed base material, then add silicone oil, organic metal catalyst and amine catalyst, stir and disperse for 40 minutes, and then mix at 120 rpm in vacuum for 30 minutes to obtain component A; S3: Component A and component B are mixed in a mass ratio of 1:1.1 and then foamed to obtain polyurethane foam.

[0047] Example 4 This embodiment provides a novel polyurethane foam, wherein the polyurethane foam comprises component A and component B, which are calculated by weight: The A component includes the following components: MOFs material 5 parts; 84 parts of polyether polyol; 6 parts of polymer polyol; 6 parts water; 0.4 parts of dibutyltin dilaurate; 0.4 parts of amine catalyst; 0.5 parts of silicone oil; The B component is a polyisocyanate; Wherein, MOFs material is prepared according to the following method: Zirconium tetrachloride and hydroxyterephthalic acid in a mass ratio of 1:5 were used as raw materials, reacted at 180°C in a methanol solution for 12 hours, and centrifuged to obtain MOFs materials; The preparation method of the novel polyurethane foam comprises the following steps: S1: According to the formula, 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 60°C, stirred at 300 rpm for 50 min, and then the temperature is lowered to 35°C at 1°C / min to obtain a premixed base material; S2: Add deionized water to the premixed base material, then add silicone oil, organic metal catalyst and amine catalyst, stir and disperse for 40 minutes, and then mix at 120 rpm in vacuum for 30 minutes to obtain component A; S3: Component A and component B are mixed in a mass ratio of 1:1.2 and then foamed to obtain polyurethane foam.

[0048] Example 5 This embodiment provides a novel polyurethane foam, wherein the polyurethane foam comprises component A and component B, which are calculated by weight: The A component includes the following components: MOFs materials 15 parts; 85 parts of polyether polyol; 5 parts of polymer polyol; 5 parts water; 0.5 parts of bismuth neodecanoate; 0.1 part of amine catalyst; 0.3 parts of silicone oil; The B component is a polyisocyanate; Wherein, MOFs material is prepared according to the following method: Zinc nitrate and aminoterephthalic acid in a mass ratio of 1:5 were used as raw materials, reacted at 90°C for 12 h in a methanol solution, and centrifuged to obtain MOFs materials. The preparation method of the novel polyurethane foam comprises the following steps: S1: According to the formula, polyether polyol, polymer polyol and MOFs material were added into the reaction kettle and mixed and stirred until there were no obvious undispersed particles, then the temperature was raised to 55°C, stirred at 400 rpm for 55 min, and then the temperature was lowered to 40°C at 1°C / min to obtain a premixed base material; S2: Add deionized water to the premixed base material, then add silicone oil, organic metal catalyst and amine catalyst, stir and disperse for 45 minutes, and then mix at 120 rpm in vacuum for 30 minutes to obtain component A; S3: Component A and component B are mixed in a mass ratio of 1:1 and then foamed to obtain polyurethane foam.

[0049] The difference between Comparative Example 1 and Example 1 is that no MOFs material is added.

[0050] The difference between Comparative Example 2 and Example 1 is that the MOFs material is ZIF-8, and is prepared according to the following method: zinc sulfate and 2-methylimidazole in a mass ratio of 1:5 are mixed in deionized water, then allowed to stand at room temperature for 24 hours, and ZIF-8 is obtained after centrifugation, washing, and drying.

[0051] The difference between Comparative Example 3 and Example 1 is that no organic metal catalyst is added.

[0052] The difference between Comparative Example 4 and Example 1 is that the added amount of MOFs material is 25 parts.

[0053] The difference between Comparative Example 5 and Example 1 is that the average particle size of the MOFs material is 1200 nm.

[0054] According to the formula amount, the polyurethane foams prepared in the embodiments of the present invention and the comparative examples were tested for their removal effects after being applied to water pollutants. The specific test process is as follows: 1. Wastewater Sample Preparation Collect wastewater samples to be treated and record their initial chemical oxygen demand (COD) and phenol content as baseline data for subsequent testing.

[0055] 2. Catalytic degradation treatment The polyurethane foam prepared by the present invention is cut into samples of 50mm×50mm×10mm and placed in a catalytic degradation tank, and then the wastewater is preliminarily treated to remove impurities and then pumped into the catalytic degradation tank containing the polyurethane foam, and hydrogen peroxide with a mass concentration of 3% 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.

[0056] 3. Test results analysis After the treatment, the pollutant indicators such as COD and phenol content of the wastewater are measured again, compared with the initial data, and the removal rate is calculated.

[0057] The test results are shown in Table 1: It can be seen from the data in the above table that the new MOFs polyurethane foam prepared by the present invention shows an excellent removal rate through the photocatalytic MOF foaming technology, and can effectively adsorb and degrade water pollutants; its stable three-dimensional porous structure provides significant advantages for the foam: on the one hand, this structure greatly increases the specific surface area, so that water pollutants can fully contact with the active sites of MOFs, thereby improving the adsorption efficiency; on the other hand, it also optimizes the mass transfer efficiency, accelerates the adsorption and decomposition process of pollutants, thereby significantly improving the adsorption and degradation efficiency of environmental pollutants.

[0058] Based on the above ideal embodiments of the present invention, the relevant staff can make various changes and modifications without departing from the technical concept of the present invention through the above description. The technical scope of the present invention is not limited to the contents of the specification, and its technical scope must be determined according to the scope of the claims.

Claims

1. A novel polyurethane foam, characterized in that: The polyurethane foam comprises component A and component B, which are calculated by weight. The A component includes the following components: 1-20 parts of MOFs material; 80-90 parts of polyether polyol; 5-10 parts of polymer polyol; 3-8 parts water; 0.1-0.5 parts of organic metal catalyst; 0.1-0.5 parts of amine catalyst; Silicone oil 0.1-0.5 parts; The B component is a polyisocyanate.

2. The novel polyurethane foam according to claim 1, characterized in that: The MOFs material is prepared according to the following method: using metal salt and organic ligand molecules as raw materials, the MOFs material is synthesized by solvent thermal synthesis.

3. The novel polyurethane foam according to claim 1, characterized in that: The amine catalyst is selected from at least one of Dabco33LV, DMAEE, A-300 and A-400.

4. The novel polyurethane foam according to claim 1, characterized in that: The organic metal catalyst is selected from at least one of an organic zinc catalyst, an organic tin catalyst and an organic bismuth catalyst.

5. The novel polyurethane foam according to claim 2, characterized in that: The mass ratio of the metal salt to the organic ligand molecule is 1:5-8.

6. The novel polyurethane foam according to claim 2, characterized in that: The MOFs material has photocatalytic activity.

7. The novel polyurethane foam according to claim 5, characterized in that: 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 thiol group.

8. A method for preparing a novel polyurethane foam as claimed in any one of claims 1 to 7, characterized in that: The following steps are involved: The A component and the B component are mixed and foamed to obtain the polyurethane foam.

9. The method for preparing the novel polyurethane foam according to claim 8, characterized in that: The mass ratio of component A to component B is 1:1-1.

2.

10. Use of the novel polyurethane foam according to any one of claims 1 to 7 in removing organic pollutants from water.

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