A glass fiber-based composite material for rotary dehumidification and its preparation method

Abstract

The present invention relates to the field of glass fiber-based composite materials, and specifically to a glass fiber-based composite material for rotary dehumidification and its preparation method. By adding a composite filler and a modified resin to the raw materials for preparing silica gel, since the composite filler is prepared by impregnating a metal-organic framework with lithium chloride salt, the problem of insufficient moisture absorption performance of the existing glass fiber-based composite material for rotary dehumidification is solved. The modified resin is prepared by connecting cyclodextrin-wrapped silver nanoparticles with polyvinyl alcohol, and at the same time, its antibacterial performance is improved, avoiding health hazards caused by bacterial growth, and to a certain extent, improving the crosslinking density of silica gel. The combination of the two avoids the problem of short service life caused by insufficient mechanical properties of silica gel and low bonding strength with the rotary dehumidification matrix.

Description

Technical Field

[0001] The present invention relates to the field of glass fiber-based composite materials, and particularly to a glass fiber-based composite material for rotary dehumidification and a preparation method thereof. Background Art

[0002] With the improvement of modern people's living standards and industrial related requirements, the influence of air humidity on production and life is becoming more and more important. As a common dehumidification device, the core component of a rotary dehumidifier is the dehumidification rotor, and most dehumidification rotors are made of a composite of activated silica gel and glass fiber.

[0003] As an adsorption material for the dehumidification rotor, silica gel has the characteristics of stable properties and easy cleaning. However, silica gel as an adsorption material still has many deficiencies. For example, compared with lithium chloride, silica gel has a smaller moisture absorption capacity and a lower dehumidification efficiency. On the other hand, in a stronger working environment or working pressure, the bonding strength between silica gel itself and the dehumidification rotor matrix is not high, and in severe cases, pore collapse and air flow blockage will occur, resulting in a significant reduction in its dehumidification efficiency. At the same time, due to the dehumidification rotor being in a humid environment for a long time, bacteria will inevitably breed, and these bacteria are extremely easy to be discharged with the dried air, having a certain health hazard. Summary of the Invention

[0004] The purpose of the present invention is to provide a glass fiber-based composite material for rotary dehumidification and a preparation method thereof, which solves the problems of insufficient moisture absorption performance, mechanical properties, and low bonding strength with the dehumidification rotor matrix of the existing glass fiber-based composite material for rotary dehumidification, resulting in a short service life. At the same time, its antibacterial performance is also improved, avoiding health hazards caused by bacteria breeding.

[0005] The purpose of the present invention can be achieved by the following technical solutions: A preparation method of a glass fiber-based composite material for rotary dehumidification, comprising the following steps: Step S1: Weigh the following raw materials by weight percentage: 30-35% of sodium silicate, 6-8% of modified resin, 3-5% of composite filler, and 0.2-0.3% of glyoxal, and the balance is water. Mix sodium silicate, modified resin, composite filler, glyoxal, and water to obtain a mixed solution.

[0006] Step S2: Immerse the glass fiber base cloth in the mixed solution, impregnate for 5-10 min, dry it, and then immerse it in a sulfuric acid solution at a temperature of 50 °C for 4-5 h. The pH of the sulfuric acid solution is 6. Wash and dry it to obtain a glass fiber-based composite material for rotary dehumidification.

[0007] The composite filler is prepared by the following steps:

[0008] Step A1: Mix p-bromotoluene and diethyl ether, stir and add n-butyllithium at a stirring rate of 80 - 100 rpm and a temperature of 5°C, stir for 2 - 3 h, raise the temperature to room temperature and add trichlorosilane, react for 12 h to obtain Intermediate 1. Mix Intermediate 1, 3-vinylimidazole and tetrahydrofuran, stir and add Karstedt's catalyst at a stirring rate of 120 - 150 rpm and a temperature of 90°C, react for 3 - 4 h to obtain Intermediate 2;

[0009] The dosage ratio of p-bromotoluene, n-butyllithium and trichlorosilane is 0.02 - 0.022 mol : 8 - 10 mL : 0.005 - 0.006 mol, and the dosage ratio of Intermediate 1, 3-vinylimidazole and Karstedt's catalyst is 0.005 - 0.006 mol : 0.007 - 0.008 mol : 0.3 - 0.4 g;

[0010] During the reaction process, under the action of n-butyllithium as an initiator, trichlorosilane is first lithiated and then reacts with p-bromotoluene to form a carbon-silicon bond to obtain Intermediate 1. Then, under the action of Karstedt's catalyst, the silicon-hydrogen bond in Intermediate 1 undergoes a hydrosilylation reaction with the vinyl group in 3-vinylimidazole to obtain Intermediate 2;

[0011] Step A2: Mix Intermediate 2, pyridine and deionized water, stir and add potassium permanganate at a stirring rate of 80 - 120 rpm and a temperature of 80°C, react for 4 - 5 h to obtain Intermediate 3. Mix Intermediate 3, zirconium hydroxide, acetic acid and deionized water, react at a stirring rate of 150 - 180 rpm and a temperature of 95°C for 12 - 14 h, filter and dry to obtain Precursor 1;

[0012] The dosage ratio of Intermediate 2, pyridine, deionized water and potassium permanganate is 0.009 - 0.01 mol : 110 - 130 mL : 40 mL : 25 - 28 g, and the dosage ratio of Intermediate 3, zirconium hydroxide, acetic acid and deionized water is 0.009 - 0.01 mol : 2.8 - 3 g : 300 mL : 200 mL;

[0013] During the reaction process, using pyridine and deionized water as solvents and potassium permanganate as a catalyst, the methyl group in the benzyl group of Intermediate 2 is oxidized to a carboxyl group to obtain Intermediate 3. Then, through a solvothermal method, using zirconium hydroxide as a zirconium source and Intermediate 3 as a ligand, Precursor 1 with a metal-organic framework structure is obtained;

[0014] Step A3: Mix Precursor 1, 1,4-butanesultone and acetone, react at a stirring rate of 120 - 150 rpm and a temperature of 40°C for 24 h to obtain Precursor 2. Mix Precursor 2 and lithium chloride solution, let it stand at room temperature for 12 h, dry to obtain the composite filler;

[0015] The dosage ratio of precursor 1, 1,4-butanesultone and acetone is 3.5 - 3.8 g : 0.008 - 0.01 mol : 100 - 120 mL, the mass fraction of the lithium chloride solution is 15%, and the dosage ratio of precursor 2 and the lithium chloride solution is 3.5 - 3.8 g : 10 - 12 mL;

[0016] During the reaction process, in the acetone solvent, 1,4-butanesultone undergoes ring opening and reacts with the pyridine group in precursor 1 to form a quaternary ammonium structure, obtaining precursor 2. Then, through the impregnation method, lithium chloride is loaded into precursor 2 to obtain the composite filler;

[0017] The modified resin is prepared through the following steps:

[0018] Step B1: Mix polyvinyl alcohol, p-toluenesulfonic acid and dimethyl sulfoxide, and under the conditions of a stirring rate of 200 - 240 rpm and a temperature of 60 °C, stir and add vanillin, react for 2 - 3 h, then add glycidyl methacrylate and 4-dimethylaminopyridine, and continue to react for 6 - 8 h to obtain modified polyvinyl alcohol;

[0019] The dosage ratio of polyvinyl alcohol, p-toluenesulfonic acid, dimethyl sulfoxide, vanillin, glycidyl methacrylate and 4-dimethylaminopyridine is 3 - 3.4 g : 0.08 - 0.1 g : 30 - 35 mL : 0.018 - 0.02 mol : 0.018 - 0.02 mol : 0.08 - 0.1 g;

[0020] During the reaction process, the aldehyde group in vanillin undergoes an acetal reaction with the hydroxyl group in polyvinyl alcohol to introduce phenolic hydroxyl groups, and the phenolic hydroxyl groups then react with the epoxy groups in glycidyl methacrylate to introduce double bonds, obtaining modified polyvinyl alcohol;

[0021] Step B2: Mix β-cyclodextrin and deionized water, and under the conditions of a stirring rate of 50 - 60 rpm and room temperature, stir and add silver nitrate solution, stir for 2 - 3 h, then add sodium hydroxide solution to adjust the pH value to 10, and react for 3 - 4 h to obtain precursor a. Mix precursor a, 2-mercaptopropionic acid and deionized water, and under the conditions of a stirring rate of 120 - 150 rpm and a temperature of 40 °C, react for 3 - 4 h to obtain precursor b;

[0022] The molar concentration of the silver nitrate solution is 0.01 mol / L, the molar concentration of the sodium hydroxide solution is 1 mol / L, the dosage ratio of β-cyclodextrin and the silver nitrate solution is 11 - 12 g : 5 - 6 mL, and the dosage ratio of precursor a and 2-mercaptopropionic acid is 0.3 - 0.4 g : 0.003 - 0.0035 mol;

[0023] During the reaction process, using β-cyclodextrin as a reducing agent and a stabilizer, under alkaline conditions, an in-situ reduction method was adopted to prepare a precursor a with β-cyclodextrin-coated silver nanoparticles. Then, through the inclusion ability of β-cyclodextrin in the precursor a, 2-mercaptopropionic acid was included in the inner cavity of β-cyclodextrin to prepare a precursor b;

[0024] Step B3: Mix modified polyvinyl alcohol, precursor b, and deionized water. Under nitrogen protection, ultraviolet irradiation, with a stirring rate of 120 - 150 rpm, at room temperature, stir and add 2-hydroxy-4'-(2-hydroxyethoxy)-2-methylpropiophenone, and react for 10 - 15 min to obtain composite polyvinyl alcohol. Mix the composite polyvinyl alcohol, 3-glycidoxypropyltrimethoxysilane, and N,N-dimethylformamide. Under nitrogen protection, with a stirring rate of 120 - 150 rpm, at a temperature of 90 °C, react for 4 - 5 h to obtain a modified resin;

[0025] The dosage ratio of modified polyvinyl alcohol, precursor b, and 2-hydroxy-4'-(2-hydroxyethoxy)-2-methylpropiophenone is 3.2 - 3.5 g : 0.08 - 0.1 g : 0.03 g, and the dosage ratio of composite polyvinyl alcohol and 3-glycidoxypropyltrimethoxysilane is 3.2 - 3.5 g : 0.8 - 1 g;

[0026] During the reaction process, under the action of the initiator 2-hydroxy-4'-(2-hydroxyethoxy)-2-methylpropiophenone, a click reaction occurs between the double bond in modified polyvinyl alcohol and the mercapto group in precursor b to connect precursor b to modified polyvinyl alcohol to obtain composite polyvinyl alcohol. Then, the hydroxyl group in the composite polyvinyl alcohol reacts with the epoxy group in 3-glycidoxypropyltrimethoxysilane to obtain a modified resin;

[0027] Advantages of the present invention: The present invention discloses a glass fiber-based composite material for rotary dehumidification and its preparation method. By adding a composite filler and a modified resin to the raw materials for preparing silica gel, the problems of insufficient moisture absorption performance, mechanical performance, and low bonding strength with the rotary dehumidification matrix of the existing glass fiber-based composite material for rotary dehumidification, resulting in a short service life, are solved. At the same time, its antibacterial performance is also improved, avoiding health hazards caused by bacterial growth. Since the composite filler is based on a metal-organic framework and impregnated with lithium chloride by an impregnation method, and since the metal-organic framework itself has a special porous structure, and its metal element is zirconium element and pyridine and sulfonic acid groups are introduced at the same time, this makes the metal-organic framework itself have good water adsorption performance, and the lithium chloride impregnated in the metal-organic framework has a large water absorption capacity. Their combination makes the composite filler have excellent water absorption performance. At the same time, through the special structure of the metal-organic framework, the overflow of lithium chloride during the regeneration process of rotary dehumidification is avoided. The modified resin is based on polyvinyl alcohol and connected with precursor b and 3-glycidoxypropyltrimethoxysilane. During the gelation process of sodium silicate, since the methoxy groups in 3-glycidoxypropyltrimethoxysilane will also hydrolyze, the modified resin can participate in the formation process of silica gel on the glass fiber base cloth. And since polyvinyl alcohol has certain adhesive properties after aldehydeization, to a certain extent, the bonding ability between silica gel and the glass fiber base cloth is improved. At the same time, since glyoxal is introduced as a crosslinking agent, glyoxal can react with the active hydroxyl groups in the modified resin to increase the crosslinking density of silica gel, thereby improving the mechanical properties of silica gel itself. Since precursor b has a nano-silver core and β-cyclodextrin on the surface, and the special external hydrophilic and internal hydrophobic structure of cyclodextrin avoids its influence on the water absorption performance of silica gel itself, and at the same time enables nano-silver and quaternary ammonium groups to synergistically exert good antibacterial ability. Specific embodiments

[0028] The technical solutions in the embodiments of the present invention will be clearly and completely described below. Obviously, the described embodiments are only a part of the embodiments of the present invention, rather than all the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those of ordinary skill in the art without creative work shall fall within the protection scope of the present invention.

[0029] Example 1 A preparation method of a glass fiber-based composite material for rotary dehumidification, comprising the following steps: Step S1: Weigh the following raw materials by weight percentage: 30% of commercially available Nalme sodium silicate, 6% of modified resin, 3% of composite filler, and 0.3% of glyoxal, and the balance is water. Mix sodium silicate, modified resin, composite filler, glyoxal, and water to obtain a mixed solution;

[0030] Step S2: Immerse the commercially available Haozheng fiberglass base cloth into the mixed solution, impregnate for 5 min, dry it, then immerse it into the sulfuric acid solution at a temperature of 50 °C for 5 h. The pH of the sulfuric acid solution is 6. Wash it and dry it to obtain a fiberglass-based composite material for rotary dehumidification;

[0031] The composite filler is prepared through the following steps:

[0032] Step A1: Mix p-bromotoluene and diethyl ether, stir and add n-butyllithium at a stirring rate of 80 rpm and a temperature of 5 °C, stir for 2 h, raise the temperature to room temperature and add trichlorosilane, react for 12 h to obtain Intermediate 1. Mix Intermediate 1, 3-vinylimidazole and tetrahydrofuran, stir and add a Kaster catalyst at a stirring rate of 120 rpm and a temperature of 90 °C, react for 3 h to obtain Intermediate 2;

[0033] The dosage ratio of p-bromotoluene, n-butyllithium and trichlorosilane is 0.02 mol: 8 mL: 0.005 mol, and the dosage ratio of Intermediate 1, 3-vinylimidazole and Kaster catalyst is 0.005 mol: 0.007 mol: 0.3 g;

[0034] Step A2: Mix Intermediate 2, pyridine and deionized water, stir and add potassium permanganate at a stirring rate of 80 rpm and a temperature of 80 °C, react for 4 h to obtain Intermediate 3. Mix Intermediate 3, zirconium hydroxide, acetic acid and deionized water, react at a stirring rate of 150 rpm and a temperature of 95 °C for 12 h, filter and dry to obtain Precursor 1;

[0035] The dosage ratio of Intermediate 2, pyridine, deionized water and potassium permanganate is 0.009 mol: 110 mL: 40 mL: 25 g, and the dosage ratio of Intermediate 3, zirconium hydroxide, acetic acid and deionized water is 0.009 mol: 2.8 g: 300 mL: 200 mL;

[0036] Step A3: Mix Precursor 1, 1,4-butanesultone and acetone, react at a stirring rate of 120 rpm and a temperature of 40 °C for 24 h to obtain Precursor 2. Mix Precursor 2 and lithium chloride solution, let it stand for 12 h at room temperature, dry it to obtain the composite filler;

[0037] The dosage ratio of Precursor 1, 1,4-butanesultone and acetone is 3.5 g: 0.008 - 0.01 mol: 100 mL, the mass fraction of the lithium chloride solution is 15%, and the dosage ratio of Precursor 2 and lithium chloride solution is 3.5 g: 10 mL;

[0038] The modified resin is prepared through the following steps:

[0039] Step B1: Mix commercially available Xinqiao 2500 polyvinyl alcohol, p-toluenesulfonic acid, and dimethyl sulfoxide. Under the conditions of a stirring rate of 200 rpm and a temperature of 60 °C, stir and add vanillin, react for 2 h, then add glycidyl methacrylate and 4-dimethylaminopyridine, and continue to react for 6 h to obtain modified polyvinyl alcohol;

[0040] The dosage ratio of polyvinyl alcohol, p-toluenesulfonic acid, dimethyl sulfoxide, vanillin, glycidyl methacrylate, and 4-dimethylaminopyridine is 3 g: 0.08 g: 30 mL: 0.018 mol: 0.018 mol: 0.08 g;

[0041] Step B2: Mix β-cyclodextrin and deionized water. Under the conditions of a stirring rate of 50 rpm and room temperature, stir and add silver nitrate solution, stir for 2 - 3 h, then add sodium hydroxide solution to adjust the pH value to 10, and react for 3 h to obtain precursor a. Mix precursor a, 2-mercaptopropionic acid, and deionized water. Under the conditions of a stirring rate of 120 rpm and a temperature of 40 °C, react for 3 h to obtain precursor b;

[0042] The molar concentration of the silver nitrate solution is 0.01 mol / L, the molar concentration of the sodium hydroxide solution is 1 mol / L, the dosage ratio of β-cyclodextrin and the silver nitrate solution is 11 g: 5 mL, and the dosage ratio of precursor a and 2-mercaptopropionic acid is 0.3 g: 0.003 mol;

[0043] Step B3: Mix modified polyvinyl alcohol, precursor b, and deionized water. Under nitrogen protection, ultraviolet irradiation, and a stirring rate of 120 rpm at room temperature, stir and add 2-hydroxy-4'-(2-hydroxyethoxy)-2-methylpropiophenone, react for 10 min to obtain composite polyvinyl alcohol. Mix composite polyvinyl alcohol, 3-glycidoxypropyltrimethoxysilane, and N,N-dimethylformamide. Under nitrogen protection and a stirring rate of 120 rpm at a temperature of 90 °C, react for 4 h to obtain modified resin;

[0044] The dosage ratio of modified polyvinyl alcohol, precursor b, and 2-hydroxy-4'-(2-hydroxyethoxy)-2-methylpropiophenone is 3.2 g: 0.08 g: 0.03 g, and the dosage ratio of composite polyvinyl alcohol and 3-glycidoxypropyltrimethoxysilane is 3.2 g: 0.8 g.

[0045] Example 2 A preparation method of a glass fiber-based composite material for rotary dehumidification, comprising the following steps: Step S1: Weigh the following raw materials by weight percentage: 35% of commercially available Narme sodium silicate, 6% of modified resin, 5% of composite filler, and 0.2% of glyoxal, and the balance is water. Mix sodium silicate, modified resin, composite filler, glyoxal, and water to obtain a mixed solution;

[0046] Step S2: Immerse the commercially available Haozheng fiberglass base fabric in the mixed solution, impregnate for 5 min, dry it, and then immerse it in the sulfuric acid solution at a temperature of 50 °C for 4 h. The pH of the sulfuric acid solution is 6. Wash it and dry it to obtain a fiberglass-based composite material for rotary dehumidification;

[0047] The composite filler is prepared through the following steps:

[0048] Step A1: Mix p-bromotoluene and diethyl ether, stir and add n-butyllithium at a stirring rate of 100 rpm and a temperature of 5 °C, stir for 2 h, raise the temperature to room temperature and add trichlorosilane, and react for 12 h to obtain Intermediate 1. Mix Intermediate 1, 3-vinylimidazole and tetrahydrofuran, stir and add a Kaster catalyst at a stirring rate of 150 rpm and a temperature of 90 °C, and react for 3 h to obtain Intermediate 2;

[0049] The dosage ratio of p-bromotoluene, n-butyllithium and trichlorosilane is 0.02 mol: 10 mL: 0.006 mol, and the dosage ratio of Intermediate 1, 3-vinylimidazole and Kaster catalyst is 0.006 mol: 0.007 mol: 0.3 g;

[0050] Step A2: Mix Intermediate 2, pyridine and deionized water, stir and add potassium permanganate at a stirring rate of 120 rpm and a temperature of 80 °C, react for 4 h to obtain Intermediate 3. Mix Intermediate 3, zirconium hydroxide, acetic acid and deionized water, and react at a stirring rate of 180 rpm and a temperature of 95 °C for 12 h, filter and dry to obtain Precursory 1;

[0051] The dosage ratio of Intermediate 2, pyridine, deionized water and potassium permanganate is 0.01 mol: 110 mL: 40 mL: 28 g, and the dosage ratio of Intermediate 3, zirconium hydroxide, acetic acid and deionized water is 0.01 mol: 2.8 g: 300 mL: 200 mL;

[0052] Step A3: Mix Precursory 1, 1,4-butanesultone and acetone, react at a stirring rate of 120 rpm and a temperature of 40 °C for 24 h to obtain Precursory 2. Mix Precursory 2 and lithium chloride solution, let it stand for 12 h at room temperature, and dry it to obtain the composite filler;

[0053] The dosage ratio of Precursory 1, 1,4-butanesultone and acetone is 3.8 g: 0.008 mol: 120 mL, the mass fraction of the lithium chloride solution is 15%, and the dosage ratio of Precursory 2 and lithium chloride solution is 3.5 g: 12 mL;

[0054] The modified resin is prepared through the following steps:

[0055] Step B1: Mix commercially available Xinqiao 2500 polyvinyl alcohol, p-toluenesulfonic acid, and dimethyl sulfoxide. Under the conditions of a stirring rate of 240 rpm and a temperature of 60 °C, stir and add vanillin, react for 2 h, then add glycidyl methacrylate and 4-dimethylaminopyridine, and continue to react for 8 h to obtain modified polyvinyl alcohol;

[0056] The dosage ratio of polyvinyl alcohol, p-toluenesulfonic acid, dimethyl sulfoxide, vanillin, glycidyl methacrylate, and 4-dimethylaminopyridine is 3.4 g: 0.08 g: 30 mL: 0.02 mol: 0.018 mol: 0.1 g;

[0057] Step B2: Mix β-cyclodextrin and deionized water. Under the conditions of a stirring rate of 50 rpm and room temperature, stir and add silver nitrate solution, stir for 3 h, then add sodium hydroxide solution to adjust the pH value to 10, and react for 4 h to obtain precursor a. Mix precursor a, 2-mercaptopropionic acid, and deionized water. Under the conditions of a stirring rate of 150 rpm and a temperature of 40 °C, react for 3 h to obtain precursor b;

[0058] The molar concentration of the silver nitrate solution is 0.01 mol / L, the molar concentration of the sodium hydroxide solution is 1 mol / L, the dosage ratio of β-cyclodextrin and the silver nitrate solution is 12 g: 5 mL, and the dosage ratio of precursor a and 2-mercaptopropionic acid is 0.4 g: 0.003 mol;

[0059] Step B3: Mix modified polyvinyl alcohol, precursor b, and deionized water. Under the protection of nitrogen, ultraviolet irradiation, and a stirring rate of 150 rpm at room temperature, stir and add 2-hydroxy-4'-(2-hydroxyethoxy)-2-methylpropiophenone, react for 10 min to obtain composite polyvinyl alcohol. Mix composite polyvinyl alcohol, 3-glycidoxypropyltrimethoxysilane, and N,N-dimethylformamide. Under the protection of nitrogen and a stirring rate of 150 rpm at a temperature of 90 °C, react for 4 h to obtain modified resin;

[0060] The dosage ratio of modified polyvinyl alcohol, precursor b, and 2-hydroxy-4'-(2-hydroxyethoxy)-2-methylpropiophenone is 3.5 g: 0.08 g: 0.03 g, and the dosage ratio of composite polyvinyl alcohol and 3-glycidoxypropyltrimethoxysilane is 3.5 g: 0.8 g;

[0061] Example 3 A preparation method of a glass fiber-based composite material for rotary dehumidification, comprising the following steps: Step S1: Weigh the following raw materials by weight percentage: 35% of commercially available Narme sodium silicate, 8% of modified resin, 5% of composite filler, and 0.3% of glyoxal, with the balance being water. Mix sodium silicate, modified resin, composite filler, glyoxal, and water to obtain a mixed solution;

[0062] Step S2: Immerse the commercially available Haozheng fiberglass base fabric into the mixed solution, impregnate for 10 min, dry it, then immerse it into the sulfuric acid solution at a temperature of 50 °C for 5 h. The pH of the sulfuric acid solution is 6. Wash it and dry it to obtain a fiberglass-based composite material for rotary dehumidification;

[0063] The composite filler is prepared through the following steps:

[0064] Step A1: Mix p-bromotoluene and diethyl ether, stir and add n-butyllithium at a stirring rate of 100 rpm and a temperature of 5 °C, stir for 3 h, raise the temperature to room temperature and add trichlorosilane, react for 12 h to obtain Intermediate 1. Mix Intermediate 1, 3-vinylimidazole and tetrahydrofuran, stir and add a Kaster catalyst at a stirring rate of 150 rpm and a temperature of 90 °C, react for 4 h to obtain Intermediate 2;

[0065] The dosage ratio of p-bromotoluene, n-butyllithium and trichlorosilane is 0.022 mol: 10 mL: 0.006 mol, and the dosage ratio of Intermediate 1, 3-vinylimidazole and Kaster catalyst is 0.006 mol: 0.008 mol: 0.4 g;

[0066] Step A2: Mix Intermediate 2, pyridine and deionized water, stir and add potassium permanganate at a stirring rate of 120 rpm and a temperature of 80 °C, react for 5 h to obtain Intermediate 3. Mix Intermediate 3, zirconium hydroxide, acetic acid and deionized water, react at a stirring rate of 180 rpm and a temperature of 95 °C for 14 h, filter and dry to obtain Precursory Body 1;

[0067] The dosage ratio of Intermediate 2, pyridine, deionized water and potassium permanganate is 0.01 mol: 130 mL: 40 mL: 28 g, and the dosage ratio of Intermediate 3, zirconium hydroxide, acetic acid and deionized water is 0.01 mol: 3 g: 300 mL: 200 mL;

[0068] Step A3: Mix Precursory Body 1, 1,4-butanesultone and acetone, react at a stirring rate of 150 rpm and a temperature of 40 °C for 24 h to obtain Precursory Body 2. Mix Precursory Body 2 and lithium chloride solution, stand still at room temperature for 12 h, dry to obtain the composite filler;

[0069] The dosage ratio of Precursory Body 1, 1,4-butanesultone and acetone is 3.8 g: 0.01 mol: 120 mL, the mass fraction of the lithium chloride solution is 15%, and the dosage ratio of Precursory Body 2 and lithium chloride solution is 3.8 g: 12 mL;

[0070] The modified resin is prepared through the following steps:

[0071] Step B1: Mix commercially available Xinqiao 2500 polyvinyl alcohol, p-toluenesulfonic acid, and dimethyl sulfoxide. Under the conditions of a stirring rate of 240 rpm and a temperature of 60 °C, stir and add vanillin, react for 3 h, then add glycidyl methacrylate and 4-dimethylaminopyridine, and continue to react for 8 h to obtain modified polyvinyl alcohol;

[0072] The dosage ratio of polyvinyl alcohol, p-toluenesulfonic acid, dimethyl sulfoxide, vanillin, glycidyl methacrylate, and 4-dimethylaminopyridine is 3.4 g: 0.1 g: 35 mL: 0.02 mol: 0.02 mol: 0.1 g;

[0073] Step B2: Mix β-cyclodextrin and deionized water. Under the conditions of a stirring rate of 60 rpm and room temperature, stir and add silver nitrate solution, stir for 3 h, then add sodium hydroxide solution to adjust the pH value to 10, and react for 4 h to obtain precursor a. Mix precursor a, 2-mercaptopropionic acid, and deionized water. Under the conditions of a stirring rate of 120 - 150 rpm and a temperature of 40 °C, react for 4 h to obtain precursor b;

[0074] The molar concentration of the silver nitrate solution is 0.01 mol / L, the molar concentration of the sodium hydroxide solution is 1 mol / L, the dosage ratio of β-cyclodextrin and the silver nitrate solution is 12 g: 6 mL, and the dosage ratio of precursor a and 2-mercaptopropionic acid is 0.4 g: 0.0035 mol;

[0075] Step B3: Mix modified polyvinyl alcohol, precursor b, and deionized water. Under the protection of nitrogen, ultraviolet irradiation, and a stirring rate of 150 rpm at room temperature, stir and add 2-hydroxy-4'-(2-hydroxyethoxy)-2-methylpropiophenone, react for 15 min to obtain composite polyvinyl alcohol. Mix composite polyvinyl alcohol, 3-glycidoxypropyltrimethoxysilane, and N,N-dimethylformamide. Under the protection of nitrogen and a stirring rate of 150 rpm at a temperature of 90 °C, react for 5 h to obtain modified resin;

[0076] The dosage ratio of modified polyvinyl alcohol, precursor b, and 2-hydroxy-4'-(2-hydroxyethoxy)-2-methylpropiophenone is 3.5 g: 0.1 g: 0.03 g, and the dosage ratio of composite polyvinyl alcohol and 3-glycidoxypropyltrimethoxysilane is 3.5 g: 1 g.

[0077] Comparative Example 1 Compared with Example 3, in this comparative example, 1,4-butanesultone was removed during the preparation of the composite filler in Example 3, and other steps were the same.

[0078] Comparative Example 2 Compared with Example 3, in this comparative example, the lithium chloride solution was removed during the preparation of the composite filler in Example 3, and other steps were the same.

[0079] Comparative Example 3 This comparative example is compared with Example 3. In the preparation process of the modified resin in Example 3, precursor b is replaced with nano silver, and other steps are the same.

[0080] Comparative Example 4 This comparative example is compared with Example 3. In the preparation process of the modified resin in Example 3, 3-glycidoxypropyltrimethoxysilane is replaced with isopropyl glycidyl ether, and other steps are the same.

[0081] Take the glass fiber-based composite materials for rotary dehumidification prepared in Example 1, Example 2, Example 3, Comparative Example 1, Comparative Example 2, Comparative Example 3, and Comparative Example 4. Cut them into samples of the same size. Under the conditions of room temperature, humidity of 90%, and adsorption time of 1 h, test their adsorption capacity. Then, under the conditions of a temperature of 100 °C and a desorption time of 2 h, calculate their desorption rate. Under the conditions of room temperature, humidity of 90%, adsorption time of 4 h, temperature of 100 °C, and desorption time of 2 h, conduct a cyclic adsorption and desorption experiment on the samples for 28 cycles. Then, calculate their adsorption performance retention rate and desorption performance retention rate to evaluate their service life. Test the antibacterial performance by the oscillation method, and the test results are shown in Table 1 below:

[0082] Table 1 Test Results

[0083]

[0084] It can be seen from the test results in the table that when comparing Example 1, Example 2, and Example 3 with Comparative Example 1, Comparative Example 2, Comparative Example 3, and Comparative Example 4, in Comparative Example 1, 1,4-butanesultone in the preparation process of the composite filler in Example 3 is removed. Due to the lack of sulfonic acid groups and quaternary ammonium groups, its water absorption capacity and antibacterial capacity have decreased to a certain extent. In Comparative Example 2, the lithium chloride solution in the preparation process of the composite filler in Example 3 is removed. Due to the lack of lithium chloride impregnation, its water absorption capacity has decreased significantly. In Comparative Example 3, precursor b in the preparation process of the modified resin in Example 3 is replaced with nano silver. Due to the lack of cyclodextrin encapsulation, its antibacterial performance has decreased significantly. In Comparative Example 4, 3-glycidoxypropyltrimethoxysilane in the preparation process of the modified resin in Example 3 is replaced with isopropyl glycidyl ether. Due to the lack of silane methoxy groups, its binding ability and mechanical properties have decreased to a certain extent, thus affecting its service life.

[0085] In the description of the specification, the descriptions referring to terms such as "one embodiment", "example", "specific example", etc. mean that the specific features, structures, materials or characteristics described in connection with the embodiment or example are included in at least one embodiment or example of the present invention. In this specification, the schematic representations of the above terms do not necessarily refer to the same embodiment or example. Moreover, the specific features, structures, materials or characteristics described can be combined in any one or more embodiments or examples in a suitable manner.

[0086] The above content is only an example and illustration of the concept of the present invention. Those skilled in the art of the present technology can make various modifications or supplements to the described specific embodiments or use similar ways to substitute, as long as they do not deviate from the concept of the invention or exceed the scope defined by the claims of the present invention, they should all fall within the protection scope of the present invention.

Claims

1. A method for preparing a glass fiber-based composite material for a rotary dehumidification device, characterized in that: The method comprises the following steps: Step S1: weighing the following raw materials in weight percentage: 30-35% sodium water glass, 6-8% modified resin, 3-5% composite filler and 0.2-0.3% glyoxal, with the balance being water, and mixing the sodium water glass, modified resin, composite filler, glyoxal and water to prepare a mixed solution; Step S2: immersing the glass fiber base cloth in the mixed solution for 5-10 minutes, drying, and then immersing it in a sulfuric acid solution at a temperature of 50° C. for 4-5 hours, the pH value of the sulfuric acid solution is 6, washing, and drying to obtain a glass fiber-based composite material for a rotary dehumidification wheel; The composite filler is prepared by the following steps: Step A1: p-bromotoluene and ether are mixed, stirred at a stirring rate of 80-100 rpm and a temperature of 5°C, and n-butyl lithium is added, stirred for 2-3 hours, the temperature is raised to room temperature, trichlorosilane is added, and the reaction is carried out for 12 hours to obtain intermediate 1; intermediate 1, 3-vinylimidazole and tetrahydrofuran are mixed, stirred at a stirring rate of 120-150 rpm and a temperature of 90°C, and a Custer catalyst is added, and the reaction is carried out for 3-4 hours to obtain intermediate 2; Step A2: Mix intermediate 2, pyridine and deionized water, stir at a stirring rate of 80-120 rpm and a temperature of 80°C, add potassium permanganate, and react for 4-5 hours to obtain intermediate 3; mix intermediate 3, zirconium hydroxide, acetic acid and deionized water, stir at a stirring rate of 150-180 rpm and a temperature of 95°C, react for 12-14 hours, filter, and dry to obtain precursor 1; Step A3: Precursor 1, 1,4-butanesultone and acetone are mixed, and reacted for 24 hours at a stirring rate of 120-150 rpm and a temperature of 40° C. to obtain precursor 2, and precursor 2 is mixed with lithium chloride solution, and allowed to stand at room temperature for 12 hours, and dried to obtain a composite filler; The modified resin is prepared by the following steps: Step B1: polyvinyl alcohol, p-toluenesulfonic acid and dimethyl sulfoxide are mixed, stirred at a stirring rate of 200-240 rpm and a temperature of 60° C., and vanillin is added, reacted for 2-3 hours, and then glycidyl methacrylate and 4-dimethylaminopyridine are added, and the reaction is continued for 6-8 hours to obtain modified polyvinyl alcohol; Step B2: β-cyclodextrin and deionized water are mixed, stirred at a stirring rate of 50-60 rpm and room temperature, and silver nitrate solution is added, stirred for 2-3 hours, and then sodium hydroxide solution is added to adjust the pH value to 10, and the reaction is carried out for 3-4 hours to obtain precursor a. Precursor a, 2-mercaptopropionic acid and deionized water are mixed, stirred at a rate of 120-150 rpm and a temperature of 40° C., and the reaction is carried out for 3-4 hours to obtain precursor b; Step B3: Mix the modified polyvinyl alcohol, precursor b and deionized water, stir and add 2-hydroxy-4'-(2-hydroxyethoxy)-2-methylpropiophenone under nitrogen protection, ultraviolet irradiation, stirring rate of 120-150rpm, room temperature, and react for 10-15min to obtain composite polyvinyl alcohol; mix the composite polyvinyl alcohol, 3-glycidyloxypropyltrimethoxysilane and N,N-dimethylformamide, under nitrogen protection, stirring rate of 120-150rpm, temperature of 90°C, and react for 4-5h to obtain a modified resin.

2. The method for preparing a glass fiber-based composite material for a rotary dehumidification wheel according to claim 1, characterized in that: In step A1, the ratio of p-bromotoluene, n-butyl lithium and trichlorosilane is 0.02-0.022 mol: 8-10 mL: 0.005-0.006 mol, and the ratio of intermediate 1, 3-vinylimidazole and Custer catalyst is 0.005-0.006 mol: 0.007-0.008 mol: 0.3-0.4 g.

3. The method for preparing a glass fiber-based composite material for a rotary dehumidification wheel according to claim 1, characterized in that: In step A2: the usage ratio of intermediate 2, pyridine, deionized water and potassium permanganate is 0.009-0.01 mol: 110-130 mL: 40 mL: 25-28 g, and the usage ratio of intermediate 3, zirconium hydroxide, acetic acid and deionized water is 0.009-0.01 mol: 2.8-3 g: 300 mL: 200 mL.

4. The method for preparing a glass fiber-based composite material for a rotary dehumidification wheel according to claim 1, characterized in that: In step A3: the amount ratio of precursor 1, 1,4-butanesultone and acetone is 3.5-3.8 g: 0.008-0.01 mol: 100-120 mL, the mass fraction of lithium chloride solution is 15%, and the amount ratio of precursor 2 and lithium chloride solution is 3.5-3.8 g: 10-12 mL.

5. The method for preparing a glass fiber-based composite material for a rotary dehumidification wheel according to claim 1, characterized in that: In step B1, the amount ratio of polyvinyl alcohol, p-toluenesulfonic acid, dimethyl sulfoxide, vanillin, glycidyl methacrylate and 4-dimethylaminopyridine is 3-3.4 g: 0.08-0.1 g: 30-35 mL: 0.018-0.02 mol: 0.018-0.02 mol: 0.08-0.1 g.

6. The method for preparing a glass fiber-based composite material for a rotary dehumidification wheel according to claim 1, characterized in that: In step B2: the molar concentration of the silver nitrate solution is 0.01 mol / L, the molar concentration of the sodium hydroxide solution is 1 mol / L, the dosage ratio of β-cyclodextrin and the silver nitrate solution is 11-12 g: 5-6 mL, and the dosage ratio of the precursor a and 2-mercaptopropionic acid is 0.3-0.4 g: 0.003-0.0035 mol.

7. The method for preparing a glass fiber-based composite material for a rotary dehumidification wheel according to claim 1, characterized in that: In step B3: the ratio of modified polyvinyl alcohol, precursor b and 2-hydroxy-4'-(2-hydroxyethoxy)-2-methylpropiophenone is 3.2-3.5g:0.08-0.1g:0.03g, and the ratio of composite polyvinyl alcohol and 3-glycidyloxypropyltrimethoxysilane is 3.2-3.5g:0.8-1g.

8. A glass fiber-based composite material for a rotary dehumidifier, characterized in that: Prepared according to any one of claims 1 to 7.

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