Preparation method of quaternary ammonium modified polyurethane foam

Abstract

The quaternary ammonium group modified polyurethane foam provided by the invention can be applied to the field of water treatment, can improve the removal rate of degradation-resistant organic matters such as enoxacin, and can also be applied to the fields of buildings, home furnishing, automobiles, electronics, packaging and the like besides the field of water treatment.

Description

Technical Field

[0001] The present invention belongs to the technical field of polyurethane foam materials, and specifically relates to a method for preparing quaternary ammonium modified polyurethane foam, and the polyurethane foam prepared by the method, which can be used in the fields of adsorption, antibacterial, water treatment biofilm forming materials, etc. Background Art

[0002] Polyurethane foam is a common thermal insulation, fireproof, antibacterial and adsorbent polymer material widely used in fields such as thermal insulation, cushioning and adsorption, and has good application prospects in the construction, home furnishing, automobile, electronics, packaging and environmental protection industries. In the field of water treatment, polyurethane foam has become a common biofilm material in water treatment biological methods due to its high specific surface area and low cost. However, the functions of existing polyurethane foam materials are single and difficult to meet the higher requirements of antibacterial, adsorbent and ion exchange properties. Quaternary ammonium compounds are well-known for their excellent antibacterial and adsorbent properties. Materials containing quaternary ammonium structures have strong hydrophilicity, antibacterial properties and ion exchange functional characteristics. Therefore, introducing them into polyurethane foam can give the foam material new functions. In addition, the quaternary ammonium structure is conducive to the growth of some microorganisms on the carrier surface because of its positive charge. Introducing the quaternary ammonium structure into polyurethane foam fillers can generally promote the biofilm formation process.

[0003] Patent CN117339571A discloses a method for preparing a granular quaternary ammonium-modified polyurethane CO2 adsorbent. The method involves reacting an isocyanate with a composite polyether, hydrophilizing the polyurethane with glutaraldehyde and acrylic acid. The hydrophilic polyurethane is then reacted with isopropyl alcohol and an aqueous solution of 3-chloro-2-hydroxypropyltrimethylammonium chloride, followed by ion exchange with a sodium carbonate solution to yield the target product. Patent CN116574297A discloses a method for modifying the surface of a polyurethane material using sulfobetaine, a diquaternary ammonium cation, and an isocyanate-based crosslinker. Patent CN118165229A discloses a quaternary ammonium salt-based waterborne polyurethane and its preparation method. The method uses dihydroxy silicone oil and isocyanate as raw materials, with 3-dimethylamino-1,2-propylene glycol as a crosslinker. The quaternary ammonium salt-based waterborne polyurethane is then prepared through catalytic catalysis and quaternization of halogenated or brominated alkane. Although quaternary ammonium groups are introduced into the polyurethane structure, the modification process requires a variety of reagents, some of which are relatively expensive. Therefore, it is urgent to develop a method for preparing quaternary ammonium polyurethane foam that is simple to operate and low in cost. Summary of the Invention

[0004] The object of the present invention is to provide a method for preparing quaternary ammonium modified polyurethane foam on the basis of the prior art.

[0005] The second object of the present invention is to provide a quaternary ammonium modified polyurethane foam obtained by the above preparation method.

[0006] The technical solutions of the present invention are as follows:

[0007] A method for preparing a quaternary ammonium modified polyurethane foam comprises the following steps:

[0008] (1) soaking a polyurethane sponge filler in a methanol-water solution, adding a silane coupling agent I to the resulting mixture after soaking, mixing uniformly, adding an ammonia solution dropwise, adjusting the pH value to 9.0-12.0, continuing mixing, and performing solid-liquid separation;

[0009] (2) mixing the solid obtained in step (1) with a methanol-acetone-water mixed solution, adding a silane coupling agent II to the obtained mixed solution, and continuing mixing to perform solid-liquid separation again; wherein the silane coupling agent II is γ-glycidyloxypropyltriethoxysilane and / or γ-glycidyloxypropyltrimethoxysilane;

[0010] (3) mixing the solid obtained in step (2) with an aqueous solution of an aminating agent, carrying out a chemical reaction at 30-90° C., washing, and drying to obtain a quaternary ammonium-modified polyurethane foam.

[0011] In the present invention, the polyurethane sponge filler is an existing commercially available product, for example, it can be sourced from Henan Tianyi Environmental Protection Technology Co., Ltd., Henan Tiancheng Water Co., Ltd., Yixing Flanders Environmental Protection Equipment Co., Ltd., etc.

[0012] For the present invention, in step (1), the mass ratio of the polyurethane sponge filler to the methanol-water solution is 1:0.5-1:15.0, and can be but not limited to 1:0.5, 1:1.0, 1:1.5, 1:2.0, 1:2.5, 1:3.0, 1:3.5, 1:4.0, 1:4.5, 1:5.0, 1:5.5, 1:6.0, 1:6.5, 1:7.0, 1:7.5, 1:8.0, 1:8.5, 1:9.0, 1:9.5, 1:10.0, 1:10.5, 1:11.0, 1:12.0, 1:13.0, 1:14.0 or 1:15.0. In a preferred embodiment, the mass ratio of the polyurethane sponge filler to the methanol-water solution is 1:1-1:10.0.

[0013] In step (1), the mass concentration of methanol in the methanol-water solution is 25%-95%, and can be but not limited to 25%, 30%, 35%, 40%, 45%, 50%, 55%, 60%, 65%, 70%, 75%, 80%, 85%, 90% or 95%. In a preferred embodiment, the mass concentration of methanol in the methanol-water solution is 35%-90%.

[0014] In step (1), the silane coupling agent I is one or more of γ-aminopropyl triethoxysilane of the present invention, γ-aminopropyl trimethoxysilane, vinyl triethoxysilane, vinyl trimethoxysilane, γ-methacryloxypropyl trimethoxysilane, γ-methacryloxypropyl triethoxysilane, tetramethoxysilane or tetraethoxysilane.

[0015] In step (1), the mass of the silane coupling agent I is 0.05%-8.0% of the total mass of the methanol-water solution, and can be but not limited to 0.05%, 0.1%, 0.6%, 1.0%, 1.5%, 1.9%, 2.0%, 2.5%, 3.0%, 3.5%, 4.0%, 4.5%, 5.0%, 5.5%, 6.0%, 7.0% or 8.0%. In a preferred embodiment, the mass of the silane coupling agent I is 0.1%-5.0% of the total mass of the methanol-water solution.

[0016] In step (1), the soaking time is 0.5-8 hours, which can be but not limited to 0.5 hours, 1 hour, 1.5 hours, 2 hours, 2.5 hours, 3 hours, 3.5 hours, 4 hours, 4.5 hours, 5 hours, 5.5 hours, 6 hours, 7 hours or 15 hours. In a preferred embodiment, the soaking time is 1-5 hours.

[0017] In step (1), the mass concentration of the ammonia solution is 5%-35%, which can be but not limited to 5%, 10%, 15%, 18%, 20%, 25%, 28%, 30%, 33% or 35%. In a preferred embodiment, the mass concentration of the ammonia solution is 10%-28%.

[0018] In step (1), an ammonia solution is added dropwise to adjust the pH value to 9.0-12.0, which may be but not limited to 9.0, 9.5, 10.0, 10.5, 11.0, 11.3, 11.5 or 12.0. In a preferred embodiment, the pH value is adjusted to 9.5-11.5.

[0019] In step (1), the mixing time is continued for 1-15 hours, which can be but not limited to 1 hour, 2 hours, 3 hours, 4 hours, 5 hours, 6 hours, 7 hours, 8 hours, 9 hours, 10 hours, 11 hours, 12 hours, 13 hours, 14 hours or 15 hours. In a preferred embodiment, the mixing time is continued for 2-10 hours.

[0020] In the present invention, in step (2), the mass concentration of methanol in the methanol-acetone-water mixed solution is 30%-70%, and can be but not limited to 20%, 25%, 30%, 35%, 40%, 45%, 50%, 55%, 60%, 65% or 70%. In a preferred embodiment, the mass concentration of methanol in the methanol-acetone-water mixed solution is 30%-70%.

[0021] In step (2), the mass concentration of acetone in the methanol-acetone-water mixed solution is 1%-15%, which can be but not limited to 1%, 2%, 3%, 4%, 5%, 6%, 7%, 8%, 9%, 10%, 11%, 12%, 13%, 14% or 15%. In a preferred embodiment, the mass concentration of acetone in the methanol-acetone-water mixed solution is 2%-10%.

[0022] In step (2), the mass ratio of the polyurethane sponge filler to the methanol-acetone-water mixed solution is 1:0.1-1:6.0, and can be but not limited to 1:0.1, 1:0.5, 1:1.0, 1:1.5, 1:2.0, 1:2.5, 1:3.0, 1:3.5, 1:4.0, 1:4.5, 1:5.0, 1:5.5 or 1:6.0. In a preferred embodiment, the mass ratio of the polyurethane sponge filler to the methanol-acetone-water mixed solution is 1:0.5-1:4.0.

[0023] In step (2), the mass of the silane coupling agent II is 0.01%-5.0% of the total mass of the methanol-acetone-water mixed solution, and can be but not limited to 0.01%, 0.05%, 0.1%, 0.6%, 1.0%, 1.5%, 1.9%, 2.0%, 2.5%, 3.0%, 3.5%, 4.0%, 4.5% or 5.0%. In a preferred embodiment, the mass of the silane coupling agent II is 0.05%-3.0% of the total mass of the methanol-acetone-water mixed solution.

[0024] In step (2), the mixing time is 0.5-8 hours, which can be but not limited to 0.5 hours, 1 hour, 1.5 hours, 2 hours, 2.5 hours, 3 hours, 3.5 hours, 4 hours, 4.5 hours, 5 hours, 5.5 hours, 6 hours, 7 hours or 15 hours. In a preferred embodiment, the mixing time is 1-5 hours.

[0025] In step (2), the mixing time is continued for 1-15 hours, which can be but not limited to 1 hour, 2 hours, 3 hours, 4 hours, 5 hours, 6 hours, 7 hours, 8 hours, 9 hours, 10 hours, 11 hours, 12 hours, 13 hours, 14 hours or 15 hours. In a preferred embodiment, the mixing time is continued for 2-10 hours.

[0026] In the present invention, in step (3), the amination reagent is one or more of trimethylamine, triethylamine, tributylamine, tripropylamine, dimethylethanolamine, dimethylpropanolamine, methyldiethanolamine, dioctylethanolamine or their corresponding hydrochlorides. For example, the amination reagent is trimethylamine, trimethylamine hydrochloride, triethylamine, tributylamine, dimethylethanolamine hydrochloride or dimethylpropanolamine.

[0027] In step (3), the mass concentration of the aminating agent in the aqueous solution of the aminating agent is 20%-40%, and can be but not limited to 20%, 21%, 22%, 23%, 24%, 25%, 26%, 27%, 28%, 29%, 30%, 31%, 32%, 33%, 34%, 35%, 36%, 37%, 38%, 39% or 40%. In a preferred embodiment, the mass concentration of the aminating agent in the aqueous solution of the aminating agent is 30%-35%.

[0028] In step (3), the mass ratio of the aqueous solution of the amination reagent to the polyurethane sponge filler is 1.0-5.0:1, and can be but not limited to 1.0:1, 1.5:1, 2.0:1, 2.5:1, 3.0:1, 3.5:1, 4.0:1, 4.5:1 or 5.0:1. In a preferred embodiment, the mass ratio of the aqueous solution of the amination reagent to the polyurethane sponge filler is 2.0-3.0:1.

[0029] In step (3), the reaction temperature is 30°C-90°C, and can be but not limited to 30°C, 35°C, 40°C, 45°C, 50°C, 55°C, 60°C, 65°C, 70°C, 75°C, 80°C, 85°C or 90°C. In a preferred embodiment, the reaction temperature is 45°C-90°C.

[0030] In step (3), the reaction time is 2-24 hours, which can be but not limited to 2 hours, 3 hours, 4 hours, 5 hours, 6 hours, 7 hours, 8 hours, 9 hours, 10 hours, 11 hours, 12 hours, 13 hours, 14 hours, 15 hours, 16 hours, 17 hours, 18 hours, 19 hours, 20 hours, 21 hours, 22 hours, 23 hours or 24 hours. In a preferred embodiment, the reaction time is 4-20 hours.

[0031] Adopt the technical scheme of the present invention, the advantages are as follows:

[0032] The present invention provides a quaternary ammonium-modified polyurethane foam, which can be used in the field of water treatment and can improve the removal rate of enoxacin and other difficult-to-degrade organic matter. In addition to being used in the field of water treatment, it can also be used in the fields of construction, home furnishing, automobiles, electronics, packaging, etc. BRIEF DESCRIPTION OF THE DRAWINGS

[0033] Figure 1It is the removal rate of enoxacin by the samples in Examples 1-8 and Comparative Example 1. DETAILED DESCRIPTION

[0034] The present invention can be better understood according to the following examples. However, it is easy for those skilled in the art to understand that the contents described in the examples are only used to illustrate the present invention, and should not and will not limit the present invention described in detail in the claims.

[0035] Example 1

[0036] A method for preparing a quaternary ammonium modified polyurethane foam comprises the following steps:

[0037] (1) A polyurethane sponge filler (sourced from Henan Tianyi Environmental Protection Technology Co., Ltd.) was soaked in a 30% methanol-water solution for 1 hour. γ-aminopropyltriethoxysilane was added to the resulting mixture, mixed evenly, and then a 10% ammonia solution was added dropwise. The pH value was adjusted to 9.5, and mixing was continued for 2 hours before solid-liquid separation. The mass ratio of the polyurethane sponge filler to the methanol-water solution was 1:1; the mass of the γ-aminopropyltriethoxysilane was 0.1% of the total mass of the methanol-water solution.

[0038] (2) The solid obtained in step (1) is mixed with a methanol-acetone-water mixed solution for 1 hour. γ-glycidyloxypropyltriethoxysilane is added to the obtained mixed solution, and the mixing is continued for 5 hours, and solid-liquid separation is performed again; wherein the mass concentration of methanol in the methanol-acetone-water mixed solution is 30%, and the mass concentration of acetone is 2%; the mass ratio of the polyurethane sponge filler to the methanol-acetone-water mixed solution is 1:0.5; and the mass of γ-glycidyloxypropyltriethoxysilane is 0.05% of the total mass of the methanol-acetone-water mixed solution.

[0039] (3) mixing the solid obtained in step (2) with a trimethylamine aqueous solution having a mass concentration of 30%, reacting the mixture at 60° C. for 12 hours, washing the mixture with ethanol, and drying the mixture to obtain a quaternary ammonium-modified polyurethane foam; wherein the mass ratio of the polyurethane sponge filler to the trimethylamine aqueous solution is 1:3.0.

[0040] Example 2

[0041] A method for preparing a quaternary ammonium modified polyurethane foam comprises the following steps:

[0042] (1) A polyurethane sponge filler (sourced from Henan Tiancheng Water Co., Ltd.) was soaked in a 50% methanol-water solution for 2.5 hours. γ-aminopropyltrimethoxysilane was added to the resulting mixture, mixed evenly, and then a 15% ammonia solution was added dropwise. The pH value was adjusted to 10.0, and mixing was continued for 5 hours before solid-liquid separation. The mass ratio of the polyurethane sponge filler to the methanol-water solution was 1:3.5; the mass of γ-aminopropyltrimethoxysilane was 0.6% of the total mass of the methanol-water solution.

[0043] (2) The solid obtained in step (1) is mixed with a methanol-acetone-water mixed solution for 3 hours. γ-glycidyloxypropyltrimethoxysilane is added to the obtained mixed solution, and the mixing is continued for 8 hours, and solid-liquid separation is performed again; wherein the mass concentration of methanol in the methanol-acetone-water mixed solution is 40%, and the mass concentration of acetone is 5%; the mass ratio of the polyurethane sponge filler to the methanol-acetone-water mixed solution is 1:1.0; and the mass of γ-glycidyloxypropyltrimethoxysilane is 1% of the total mass of the methanol-acetone-water mixed solution.

[0044] (3) mixing the solid obtained in step (2) with a triethylamine aqueous solution having a mass concentration of 33%, reacting at 75° C. for 15 hours, washing with water, and drying to obtain a quaternary ammonium-modified polyurethane foam; wherein the mass ratio of the polyurethane sponge filler to the triethylamine aqueous solution is 1:2.5.

[0045] Example 3

[0046] A method for preparing a quaternary ammonium modified polyurethane foam comprises the following steps:

[0047] (1) Polyurethane sponge filler (sourced from Yixing Flanders Environmental Protection Equipment Co., Ltd.) was soaked in a 70% methanol-water solution for 4 hours. Vinyl triethoxysilane was added to the resulting mixture, mixed evenly, and then an 18% ammonia solution was added dropwise. The pH value was adjusted to 10.5, and mixing was continued for 10 hours before solid-liquid separation. The mass ratio of polyurethane sponge filler to methanol-water solution was 1:5.0; the mass of vinyl triethoxysilane was 1.9% of the total mass of the methanol-water solution.

[0048] (2) The solid obtained in step (1) is mixed with a methanol-acetone-water mixed solution for 5 hours, γ-glycidyloxypropyltrimethoxysilane and γ-glycidyloxypropyltriethoxysilane are added to the obtained mixed solution, the mixture is mixed again for 2 hours, and solid-liquid separation is performed again; wherein the mass concentration of methanol in the methanol-acetone-water mixed solution is 50%, and the mass concentration of acetone is 7%; the mass ratio of the polyurethane sponge filler to the methanol-acetone-water mixed solution is 1:2.0; the mass ratio of γ-glycidyloxypropyltrimethoxysilane to γ-glycidyloxypropyltriethoxysilane is 1:1; and the total mass of γ-glycidyloxypropyltrimethoxysilane and γ-glycidyloxypropyltriethoxysilane is 2% of the total mass of the methanol-acetone-water solution.

[0049] (3) mixing the solid obtained in step (2) with a tributylamine aqueous solution having a mass concentration of 30%, reacting the mixture at 90° C. for 4 hours, washing with acetone, and drying to obtain a quaternary ammonium-modified polyurethane foam; wherein the mass ratio of the polyurethane sponge filler to the tributylamine aqueous solution is 1:3.0.

[0050] Example 4

[0051] A method for preparing a quaternary ammonium modified polyurethane foam comprises the following steps:

[0052] (1) A polyurethane sponge filler (sourced from Henan Tiancheng Water Co., Ltd.) was soaked in a 90% methanol-water solution for 5 hours. Vinyltrimethoxysilane and tetramethoxysilane were added to the resulting mixture, mixed evenly, and then a 20% ammonia solution was added dropwise. The pH value was adjusted to 11.0, and mixing was continued for 3 hours before solid-liquid separation. The mass ratio of the polyurethane sponge filler to the methanol-water solution was 1:7; the mass ratio of vinyltrimethoxysilane to tetramethoxysilane was 1:1; and the total mass of vinyltrimethoxysilane and tetramethoxysilane was 4% of the total mass of the methanol-water solution.

[0053] (2) mixing the solid obtained in step (1) with a methanol-acetone-water mixed solution for 2 hours, adding γ-glycidyloxypropyltriethoxysilane to the obtained mixed solution, mixing again for 10 hours, and performing solid-liquid separation again; wherein the mass concentration of methanol in the methanol-acetone-water mixed solution is 60%, and the mass concentration of acetone is 10%; the mass ratio of the polyurethane sponge filler to the methanol-acetone-water mixed solution is 1:3.0; and the mass of the γ-glycidyloxypropyltrimethoxysilane is 0.1% of the total mass of the methanol-acetone-water mixed solution.

[0054] (3) mixing the solid obtained in step (2) with a 35% by mass concentration of a dimethylethanolamine hydrochloride aqueous solution, reacting the mixture at 45° C. for 20 hours, washing with methanol, and drying to obtain a quaternary ammonium modified polyurethane foam; wherein the mass ratio of the polyurethane sponge filler to the dimethylethanolamine hydrochloride aqueous solution is 1:2.0.

[0055] Example 5

[0056] A method for preparing a quaternary ammonium modified polyurethane foam comprises the following steps:

[0057] (1) A polyurethane sponge filler (sourced from Yixing Flanders Environmental Protection Equipment Co., Ltd.) was soaked in a 60% methanol-water solution for 1.5 hours. γ-methacryloxypropyltrimethoxysilane and tetraethoxysilane were added to the resulting mixture, mixed evenly, and then a 25% ammonia solution was added dropwise. The pH value was adjusted to 11.3, and the mixture was mixed for 8 hours before solid-liquid separation. The mass ratio of the polyurethane sponge filler to the methanol-water solution was 1:8.0; the mass ratio of γ-methacryloxypropyltrimethoxysilane to tetraethoxysilane was 1:1.0; and the total mass of γ-methacryloxypropyltrimethoxysilane and tetraethoxysilane was 4.5% of the total mass of the methanol-water solution.

[0058] (2) mixing the solid obtained in step (1) with a methanol-acetone-water mixed solution for 4 hours, adding γ-glycidyloxypropyltrimethoxysilane to the obtained mixed solution, mixing again for 6 hours, and performing solid-liquid separation again; wherein the mass concentration of methanol in the methanol-acetone-water mixed solution is 45%, and the mass concentration of acetone is 6%; the mass ratio of the polyurethane sponge filler to the methanol-acetone-water mixed solution is 1:4.0; and the mass of the γ-glycidyloxypropyltrimethoxysilane is 2.5% of the total mass of the methanol-acetone-water mixed solution.

[0059] (3) mixing the solid obtained in step (2) with a dimethylpropanolamine aqueous solution having a mass concentration of 30%, reacting the mixture at 80° C. for 8 hours, washing with ethyl acetate, and drying to obtain a quaternary ammonium modified polyurethane foam; wherein the mass ratio of the polyurethane sponge filler to the dimethylpropanolamine aqueous solution is 1:2.0.

[0060] Example 6

[0061] A method for preparing a quaternary ammonium modified polyurethane foam comprises the following steps:

[0062] (1) A polyurethane sponge filler (sourced from Henan Tiancheng Water Co., Ltd.) was soaked in a 90% methanol-water solution for 4 hours, and γ-methacryloxypropyl trimethoxysilane, γ-methacryloxypropyl triethoxysilane, and tetramethoxysilane were added to the resulting mixture. After mixing evenly, a 28% ammonia aqueous solution was added dropwise, and the pH value was adjusted to 11.5. Mixing was continued for 4 hours, and solid-liquid separation was performed. The mass ratio of the polyurethane sponge filler to the methanol-water solution was 1:10.0; the amount ratio of γ-methacryloxypropyl trimethoxysilane, γ-methacryloxypropyl triethoxysilane, and tetramethoxysilane was 1:1:1; and the total mass of γ-methacryloxypropyl trimethoxysilane, γ-methacryloxypropyl triethoxysilane, and tetramethoxysilane was 3% of the total mass of the methanol-water solution.

[0063] (2) The solid obtained in step (1) is mixed with a methanol-acetone-water mixed solution for 3 hours, γ-glycidyloxypropyltrimethoxysilane and γ-glycidyloxypropyltriethoxysilane are added to the obtained mixed solution, the mixture is mixed again for 4 hours, and solid-liquid separation is performed again; wherein the mass concentration of methanol in the methanol-acetone-water mixed solution is 55%, and the mass concentration of acetone is 8%; the mass ratio of the polyurethane sponge filler to the methanol-acetone-water mixed solution is 1:1.5; the mass ratio of γ-glycidyloxypropyltrimethoxysilane to γ-glycidyloxypropyltriethoxysilane is 1:1; and the total mass of γ-glycidyloxypropyltrimethoxysilane and γ-glycidyloxypropyltriethoxysilane is 3% of the total mass of the methanol-acetone-water solution.

[0064] (3) mixing the solid obtained in step (2) with a 30% by mass concentration trimethylamine aqueous solution, reacting at 55° C. for 10 hours, washing with ether, and drying to obtain a quaternary ammonium modified polyurethane foam; wherein the mass ratio of the polyurethane sponge filler to the trimethylamine aqueous solution is 1:2.0.

[0065] Example 7

[0066] A method for preparing a quaternary ammonium modified polyurethane foam comprises the following steps:

[0067] (1) A polyurethane sponge filler (sourced from Yixing Flanders Environmental Protection Equipment Co., Ltd.) was soaked in a 90% methanol-water solution for 5 hours, and γ-methacryloxypropyltrimethoxysilane, γ-aminopropyltrimethoxysilane, and tetramethoxysilane were added to the resulting mixture. After uniform mixing, a 28% ammonia aqueous solution was added dropwise, and the pH value was adjusted to 11.5. The mixture was mixed for another 4 hours, and solid-liquid separation was performed. The mass ratio of the polyurethane sponge filler to the methanol-water solution was 1:10.0; the amount ratio of γ-methacryloxypropyltrimethoxysilane, γ-aminopropyltrimethoxysilane, and tetramethoxysilane was 1:1:1; and the total mass of γ-methacryloxypropyltrimethoxysilane, γ-aminopropyltrimethoxysilane, and tetramethoxysilane was 3% of the total mass of the methanol-water solution.

[0068] (2) The solid obtained in step (1) is mixed with a methanol-acetone-water mixed solution for 3 hours, γ-glycidyloxypropyltrimethoxysilane and γ-glycidyloxypropyltriethoxysilane are added to the obtained mixed solution, the mixture is mixed again for 4 hours, and solid-liquid separation is performed again; wherein the mass concentration of methanol in the methanol-acetone-water mixed solution is 55%, and the mass concentration of acetone is 8%; the mass ratio of the polyurethane sponge filler to the methanol-acetone-water mixed solution is 1:1.5; the mass ratio of γ-glycidyloxypropyltrimethoxysilane to γ-glycidyloxypropyltriethoxysilane is 1:1; and the total mass of γ-glycidyloxypropyltrimethoxysilane and γ-glycidyloxypropyltriethoxysilane is 3% of the total mass of the methanol-acetone-water mixed solution.

[0069] (3) mixing the solid obtained in step (2) with a 30% by mass concentration trimethylamine aqueous solution, reacting at 50° C. for 10 hours, washing with ether, and drying to obtain a quaternary ammonium modified polyurethane foam; wherein the mass ratio of the polyurethane sponge filler to the trimethylamine aqueous solution is 1:3.0.

[0070] Example 8

[0071] A method for preparing a quaternary ammonium modified polyurethane foam comprises the following steps:

[0072] (1) A polyurethane sponge filler (Henan Tianyi Environmental Protection Technology Co., Ltd.) was soaked in a 60% methanol-water solution for 2 hours, and γ-methacryloxypropyltrimethoxysilane and tetramethoxysilane were added to the resulting mixture. After mixing evenly, a 25% ammonia aqueous solution was added dropwise, and the pH value was adjusted to 11.3. The mixture was mixed for another 4 hours, and solid-liquid separation was performed. The mass ratio of the polyurethane sponge filler to the methanol-water solution was 1:8.0; the mass ratio of γ-methacryloxypropyltrimethoxysilane to tetramethoxysilane was 1:1; and the total mass of γ-methacryloxypropyltrimethoxysilane and tetramethoxysilane was 4.5% of the total mass of the methanol-water solution.

[0073] (2) mixing the solid obtained in step (1) with a methanol-acetone-water mixed solution for 4 hours, adding γ-glycidyloxypropyltrimethoxysilane to the obtained mixed solution, mixing again for 6 hours, and performing solid-liquid separation again; wherein the mass concentration of methanol in the methanol-acetone-water mixed solution is 50%, and the mass concentration of acetone is 6%; the mass ratio of the polyurethane sponge filler to the methanol-acetone-water mixed solution is 1:4.0; and the mass of the γ-glycidyloxypropyltrimethoxysilane is 2.5% of the total mass of the methanol-acetone-water mixed solution.

[0074] (3) mixing the solid obtained in step (2) with a 35% by mass concentration of trimethylamine hydrochloride aqueous solution, reacting at 75° C. for 8 hours, washing with ethyl acetate, and drying to obtain a quaternary ammonium modified polyurethane foam; wherein the mass ratio of the polyurethane sponge filler to the trimethylamine hydrochloride aqueous solution is 1:2.0.

[0075] Comparative Example 1

[0076] Comparative Example 1: a polyurethane sponge filler (sourced from Henan Tianyi Environmental Protection Technology Co., Ltd.) was soaked in a 60% methanol-water solution for two hours, washed with pure water, and dried.

[0077] Performance Testing

[0078] The quaternary ammonium-modified polyurethane foams prepared in Examples 1-8 and the soaked polyurethane sponge filler in Comparative Example 1 were subjected to thermogravimetric testing and antibiotic removal experiments after microbial biofilm formation. The thermogravimetric testing was performed under a nitrogen atmosphere, heating from room temperature to 800°C at a heating rate of 10°C / min. Glucose was used as the carbon source during microbial biofilm formation, with a glucose concentration of 184 mg / L. The antibiotic selected was the quinolone antibiotic enoxacin. Antibiotic removal was measured after 10 days of incubation.

[0079] The thermogravimetric test results are shown in Table 1, and the antibiotic removal results are shown in Table 1. Figure 1 shown.

[0080] Table 1 Thermogravimetric test results of quaternary ammonium modified polyurethane foams of Examples 1 to 8 and Comparative Example 1

[0081] sample Residual mass ratio / % Example 1 2.67 Example 2 2.78 Example 3 3.42 Example 4 3.29 Example 5 4.12 Example 6 6.34 Example 7 10.37 Example 8 8.55 Comparative Example 1 0.62

[0082] As can be seen from Table 1, since Comparative Example 1 was not subjected to quaternary ammonium modification, its residual mass ratio at the end of the thermogravimetric test was lower than that of Examples 1-8.

[0083] Depend on Figure 1 It can be seen that since Comparative Example 1 was not modified by quaternization, the removal rate of enoxacin by microorganisms after biofilm formation was lower than that of Examples 1-8.

[0084] The above embodiments are only used to illustrate the technical solutions of the present invention, rather than to limit the same. Although the present invention has been described in detail with reference to the aforementioned embodiments, those skilled in the art should understand that it is still possible to modify the technical solutions described in the aforementioned embodiments, or to make equivalent replacements for some of the technical features therein. However, these modifications or replacements do not cause the essence of the corresponding technical solutions to deviate from the scope of the technical solutions of the embodiments of the present invention.

Claims

1. A method for preparing a quaternary ammonium modified polyurethane foam, characterized in that: The steps include: (1) soaking a polyurethane sponge filler in a methanol-water solution, adding a silane coupling agent I to the resulting mixture after soaking, mixing uniformly, adding an ammonia solution dropwise, adjusting the pH value to 9.0-12.0, continuing mixing, and performing solid-liquid separation; (2) mixing the solid obtained in step (1) with a methanol-acetone-water mixed solution, adding a silane coupling agent II to the obtained mixed solution, and continuing mixing to perform solid-liquid separation again; wherein the silane coupling agent II is γ-glycidyloxypropyltriethoxysilane and / or γ-glycidyloxypropyltrimethoxysilane; (3) mixing the solid obtained in step (2) with an aqueous solution of an aminating agent, carrying out an amination reaction at 30-90° C., washing, and drying to obtain a quaternary ammonium-modified polyurethane foam.

2. The method for preparing a quaternary ammonium modified polyurethane foam according to claim 1, wherein In step (1), the mass ratio of the polyurethane sponge filler to the methanol-water solution is 1:0.5-1:15.0, preferably 1:1.0-1:10.0; The mass concentration of methanol in the methanol-water solution is 25%-95%, preferably 30%-90%.

3. The preparation method of quaternary ammonium modified polyurethane foam according to claim 1, wherein In step (1), the silane coupling agent I is one or more of γ-aminopropyltriethoxysilane, γ-aminopropyltrimethoxysilane, vinyltriethoxysilane, vinyltrimethoxysilane, γ-methacryloxypropyltrimethoxysilane, γ-methacryloxypropyltriethoxysilane, tetramethoxysilane or tetraethoxysilane; the mass of the silane coupling agent I is 0.05%-8.0% of the total mass of the methanol-water solution, preferably 0.1%-5.0%.

4. The method for preparing the quaternary ammonium modified polyurethane foam according to claim 1, wherein In step (1), the soaking time is 0.5-8 hours, preferably 1-5 hours; the mass concentration of the ammonia solution is 5%-35%, preferably 10%-28%; the pH value is adjusted to 9.5-11.5; and the mixing time is continued for 1-15 hours, preferably 2-10 hours.

5. The method for preparing the quaternary ammonium modified polyurethane foam according to claim 1, wherein In step (1), the polyurethane sponge filler is a commercially available polyurethane sponge filler, preferably sourced from Henan Tianyi Environmental Protection Technology Co., Ltd., Henan Tiancheng Water Co., Ltd. or Yixing Flanders Environmental Protection Equipment Co., Ltd.

6. The method for preparing the quaternary ammonium modified polyurethane foam according to claim 1, wherein In step (2), the mass concentration of methanol in the methanol-acetone-water mixed solution is 20%-70%, preferably 30%-60%; the mass concentration of acetone in the methanol-acetone-water mixed solution is 1%-15%, preferably 2%-10%; the mass ratio of the polyurethane sponge filler to the methanol-acetone-water mixed solution is 1:0.1-1:6.0, preferably 1:0.5-1:4.

0.

7. The method for preparing the quaternary ammonium modified polyurethane foam according to claim 1, wherein In step (2), the mass of the silane coupling agent II is 0.01%-5.0%, preferably 0.05%-3.0%, of the total mass of the methanol-acetone-water mixed solution; the mixing time is 0.5-8 hours, preferably 1-5 hours; and the continued mixing time is 1-15 hours, preferably 2-10 hours.

8. The method for preparing the quaternary ammonium modified polyurethane foam according to claim 1, wherein In step (3), the aminating agent is one or more of trimethylamine, triethylamine, tributylamine, tripropylamine, dimethylethanolamine, dimethylpropanolamine, methyldiethanolamine, dioctylethanolamine or their corresponding hydrochlorides; the mass concentration of the aminating agent in the aqueous solution of the aminating agent is 20%-40%, preferably 30%-35%; the mass ratio of the aqueous solution of the aminating agent to the polyurethane sponge filler is 1.0-5.0:1, preferably 2.0-3.0:

1.

9. The method for preparing the quaternary ammonium modified polyurethane foam according to claim 1, wherein The reaction temperature is 45°C-90°C; the reaction time is 2-24 hours, preferably 4-20 hours.

10. The quaternary ammonium modified polyurethane foam obtained by the preparation method according to any one of claims 1 to 9.

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