Surface bonded quaternary ammonium cation and phenol ammonium zwitterionic glass and preparation method thereof
By bonding quaternary ammonium cations and phenolic ammonium zwitteriones on the surface of silicate glass, the problem of uneven functional layer in the prior art is solved, and the combination of high light transmittance and multifunctional performance of the glass is achieved.
Patent Information
- Application Number
- CN202411677128.1
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2024-11-22
- Publication Date
- 2025-02-07
AI Technical Summary
In the prior art, when the surface of silicate glass is functionalized, it is difficult to effectively combine quaternary ammonium cations and phenol ammonium zwitteriones, resulting in uneven functionalized layer and affecting the light transmittance and functional performance of the glass.
By preparing surface ammonized glass, surface quaternized glass, and bonding 5-chloromethyl salicylic aldehyde to its surface, surface bonded quaternary ammonium cation and phenol ammonium zwitterionic glass is formed. The method includes a multi-step reaction process to ensure effective binding of quaternary ammonium cations and phenolic ammonium zwitteriones.
The uniform distribution of the functionalized layer on the surface of the glass is achieved, the high light transmittance of the glass is maintained, and the multifunctional properties such as antibacterial, conductive, and antistatic are imparted to the glass.
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Abstract
Description
Technical Field
[0001] The invention belongs to the field of fine chemicals, and in particular relates to surface-bonded quaternary ammonium cation and phenol ammonium zwitterion glass and a preparation method thereof. Technical Background
[0002] The method of functionalizing the surface of silicate glass is to hydroxylate the glass surface with a "piranha solution", and then a silane coupling agent carrying a functional group undergoes a condensation reaction on the surface, thereby introducing functional groups such as -C=C, -NH2, -SH, -NCO or epoxy groups, and by means of the chemical reaction of these functional groups, polyethylene glycol, polyacrylic acid, polyacrylamide, capsaicin, chloramine, quaternary ammonium salt, carboxylic ammonium salt, phosphate ammonium salt or sulfonium ammonium salt can be grafted, polymerized or bonded to the glass surface. The hydrophilic substance can form a hydration layer on the glass surface, which can isolate and prevent dust or microorganisms in the air from depositing or adhering on the glass surface; or the bactericidal and antibacterial agent can kill or inhibit the reproduction and growth of microorganisms on the glass surface, forming the antibacterial, conductive, antistatic, hydrophilic, anti-fogging, biocompatible, self-cleaning and other properties of the glass surface. The bonding of quaternary ammonium salts on the surface of silicate glass is a kind of functionalization. The moisture absorption and hygroscopicity of some quaternary ammonium salts can not only significantly change the hydrophilicity of the glass surface, but also have the characteristics of stable properties, designable chemical structure, simple preparation method, and broad antibacterial spectrum. Therefore, it is meaningful to study and develop quaternary ammonium salts bonded to the surface of glass. Summary of the invention
[0003] The purpose of the present invention is to make up for the deficiencies of the prior art and provide a surface-bonded quaternary ammonium cation and phenol ammonium zwitterion glass and a preparation method thereof.
[0004] To achieve the above object, the technical solution adopted by the present invention is: a surface-bonded quaternary ammonium cation and phenol ammonium zwitterion glass, characterized in that the surface-bonded quaternary ammonium cation and phenol ammonium zwitterion glass has a structure shown in general formula (I):
[0005] In the general formula (I), R1, R2 and R3 are respectively C1-C18 hydrocarbon groups.
[0006] The surface-bonded quaternary ammonium cation and phenol ammonium zwitterion glass is prepared according to the following reaction formula:
[0007] The specific steps are as follows: Step 1: Preparation of surface ammoniated glass A mixed solution of 98% concentrated sulfuric acid and 30% hydrogen peroxide is added to a single surface of a cleaned and dried glass substrate, the temperature is controlled at 20-120° C., the treatment time is controlled at 0.5-50 hours, the glass sheet is taken out, and the surface of the glass sheet is cleaned with deionized water, and then the glass sheet is placed in a vacuum oven at 60-90° C. for drying to obtain a single-sided hydroxylated glass sheet; an aminosilane coupling agent solution is added to a single surface of the obtained hydroxylated glass sheet, and the sheet is placed in an oven at 30-130° C. for 0.5-20 hours, and then the sheet is taken out and cooled to obtain a surface ammoniated glass; Step 2: Preparation of surface quaternized glass Put the surface ammoniumized glass into a reactor, control the temperature at 25-75°C, slowly add the epoxypropyl ammonium chloride solution on the surface of the surface ammoniumized glass, control the reaction time at 0.5-20 hours, wash away the unreacted epoxypropyl ammonium chloride with water, and after drying, obtain the surface quaternized glass; Step 3: Preparation of surface-bound quaternary ammonium cation and phenol ammonium zwitterion glass A surface quaternized glass sheet is placed in a reactor, the temperature is controlled at 0-60°C, 5-chloromethyl salicylaldehyde solution is added to its surface, the reaction time is controlled at 0.5-50 hours, then the unreacted 5-chloromethyl salicylaldehyde on the glass sheet is removed and cleaned with acetone, and then the glass surface is cleaned with acetone and deionized water in turn. After drying, a surface-bonded quaternary ammonium cation and phenol ammonium zwitterion glass is obtained.
[0008] Furthermore, in step 1, the amount of the mixed solution is 2 to 200% of the mass of the glass substrate; the volume ratio of concentrated sulfuric acid and hydrogen peroxide in the mixed solution is 9:1 to 7:3; the mass ratio of aminosilane coupling agent: ethanol: water in the aminosilane coupling agent solution is 1 to 5:50 to 98:5 to 45; the amount of the aminosilane coupling agent solution is 2 to 200% of the mass of the glass substrate.
[0009] In step 2, the amount of the glycidyl ammonium chloride solution is 5-500% of the mass of the glass substrate; the mass ratio of glycidyl ammonium chloride to solvent in the glycidyl ammonium chloride solution is 0.1-0.5:1.
[0010] Furthermore, the glycidyl ammonium chloride has a structure shown in the general formula (II):
[0011] Wherein R1, R2 and R3 are C1-C18 hydrocarbon groups respectively.
[0012] Furthermore, in step three, the amount of the 5-chloromethyl salicylaldehyde solution is 2-200% of the mass of the glass substrate; and the mass ratio of 5-chloromethyl salicylaldehyde to organic solvent in the 5-chloromethyl salicylaldehyde solution is 0.01-0.5:1.
[0013] Further, in step 1, the aminosilane coupling agent is 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, N-(2-aminoethyl)-3-aminopropyltrimethoxysilane, N-(2-aminoethyl)-3-aminopropyltriethoxysilane, N-ethyl-3-aminopropyltrimethoxysilane, N-ethyl-3-aminopropyltriethoxysilane, 3-aminopropyldimethoxymethylsilane, 3-aminopropyldiethoxymethylsilane, or a mixture of any two thereof in any proportion.
[0014] In step 2, the solvent is one or more of water, methanol, ethanol, acetone, butanone, cyclohexanone, methyl acetate, ethyl acetate, chloroform, 1,2-dichloroethane, carbon tetrachloride, tetrahydrofuran, 1,4-dioxane, decahydronaphthalene, toluene, chlorobenzene, dimethyl sulfoxide or N,N-dimethylacetamide.
[0015] In step 3, the organic solvent is one or more of acetone, butanone, cyclohexanone, methyl acetate, ethyl acetate, chloroform, 1,2-dichloroethane, carbon tetrachloride, tetrahydrofuran, 1,4-dioxane, decahydronaphthalene, toluene, chlorobenzene, dimethyl sulfoxide or N,N-dimethylacetamide.
[0016] The invention has the following beneficial effects: the preparation technology is simple and easy to implement, the raw materials used are widely available and inexpensive, each step of the preparation process does not affect each other and the reaction efficiency of each step is high. The functionalized layers after the quaternary ammonium cations and the phenol ammonium zwitterions are bonded to the glass surface are all monomolecular layers, presenting a lattice distribution and high uniformity, so the light transmittance of the modified glass is not affected by the quaternary ammonium cations and the phenol ammonium zwitterions bonded to the surface. DETAILED DESCRIPTION
[0017] In order to further understand the present invention, the present invention is specifically described by way of examples, the purpose of which is to better understand the content of the present invention. Therefore, the glass with surface-bonded quaternary ammonium cations and phenol ammonium zwitterions not listed in the examples should not be regarded as limiting the scope of protection of the present invention. Example 1
[0018] The preparation method of the ion-rich glass sheet (1-a) comprises the following specific steps: Step 1: Clean and dry a flat glass sheet with a diameter of 6 cm and a thickness of 0.3 cm, add 5 grams of a mixed solution of concentrated sulfuric acid and hydrogen peroxide prepared in a volume ratio of 7:3 on the glass sheet, treat it at 60-70°C for 2 hours, rinse it with deionized water until it is weakly acidic, and put it in a vacuum oven at 60°C for drying; add 8 grams of 3-aminopropyltrimethoxysilane solution prepared in a mass ratio of 3-aminopropyltrimethoxysilane: ethanol: water of 2:90:8, put it in an oven at 80-90°C, after 1 hour, repeat the process several times, take it out and cool it to obtain a surface amino-treated glass sheet (1-a).
[0019] Step 2: Place the surface amino glass sheet (1-a) obtained in step 1 into a reactor at 45-55° C., slowly add 4.5 g of an aqueous solution containing 1.85 g of N,N,N-trimethyl-N-epoxypropylammonium chloride on the surface, react for 12 hours, take out, wash with deionized water, and dry to obtain a surface quaternized glass sheet (1-a).
[0020] Step 3: Place the surface quaternized glass sheet (1-a) obtained in step 2 into a reactor, control the temperature at 5-10°C, slowly add 6.5 g of 40% 5-chloromethyl salicylaldehyde acetone solution on the surface, take it out after 2 hours, rinse the glass surface with acetone and deionized water, and vacuum dry to obtain a glass sheet (1-a) with quaternary ammonium cations and phenol ammonium zwitterions bonded to the surface, the structural formula is:
[0021] According to GB / T 24368-2009, the contact angle measurement method for detecting hydrophobic contaminants on glass surfaces was used to measure the pure water contact angles of the ionized glass sheet (1-a), the glass substrate, and the hydroxylated glass sheet. The measurement results are shown in Table 1. Example 2
[0022] The preparation method of the ion-rich glass sheet (1-b) is the same as that of Example 1, except that the N,N,N-trimethyl-N-epoxypropylammonium chloride in step 2 is replaced with N,N-dimethyl-N-benzyl-N-epoxypropylammonium chloride. The structural formula of the surface-bound quaternary ammonium cation and phenol ammonium zwitterion glass sheet (1-b) is:
[0023] According to GB / T 24368-2009, the contact angle measurement method for detecting hydrophobic contaminants on glass surfaces was used to measure the pure water contact angle of the ionized glass sheet (1-b). The measurement results are shown in Table 1. Example 3
[0024] The preparation method of the ion-rich glass sheet (1-c) has the same specific steps as Example 1, except that the N,N,N-trimethyl-N-epoxypropylammonium chloride in step 2 is replaced with N,N-dimethyl-N-epoxypropyl-N-dodecylammonium chloride. The structural formula of the surface-bound quaternary ammonium cation and phenol ammonium zwitterion glass sheet (1-c) is:
[0025] According to GB / T 24368-2009, the contact angle measurement method for detecting hydrophobic contaminants on glass surfaces was used to measure the pure water contact angle of the ionized glass sheet (1-c). The measurement results are shown in Table 1.
[0026] Table 1
[0027] The test results show that after the glass substrate is treated with hydroxylation, the water contact angle decreases. After the quaternary ammonium cations and phenolic ammonium zwitterions are bonded to its surface, the water contact angle decreases to zero, indicating that the surface of the glass sheet has super hydrophilicity and that the quaternary ammonium cations and phenolic ammonium zwitterions have been successfully bonded to the surface of the glass sheet.
Claims
1. A surface-bonded quaternary ammonium cation and phenol ammonium zwitterion glass, characterized in that: The surface-bonded quaternary ammonium cation and phenol ammonium zwitterion glass has a structure shown in general formula (I): In the general formula (I), R1, R2 and R3 are respectively C1-C18 hydrocarbon groups.
2. The method for preparing the surface-bonded quaternary ammonium cation and phenol ammonium zwitterion glass according to claim 1, characterized in that: The specific steps are as follows: Step 1: Preparation of surface ammoniated glass A mixed solution of 98% concentrated sulfuric acid and 30% hydrogen peroxide is added to a single surface of a cleaned and dried glass substrate, the temperature is controlled at 20-120° C., the treatment time is controlled at 0.5-50 hours, the glass sheet is taken out, and the surface of the glass sheet is cleaned with deionized water, and then the glass sheet is placed in a vacuum oven at 60-90° C. for drying to obtain a single-sided hydroxylated glass sheet; an aminosilane coupling agent solution is added to a single surface of the obtained hydroxylated glass sheet, and the sheet is placed in an oven at 30-130° C. for 0.5-20 hours, and then the sheet is taken out and cooled to obtain a surface ammoniated glass; Step 2: Preparation of surface quaternized glass The surface ammoniumized glass is placed in a reactor, the temperature is controlled at 25-75° C., and the glycidyl ammonium chloride solution is slowly added to the surface of the surface ammoniumized glass. After the reaction time is controlled at 0.5-20 hours, the unreacted glycidyl ammonium chloride is washed away with water, and the surface quaternized glass is obtained after drying. Step 3: Preparation of surface-bound quaternary ammonium cation and phenol ammonium zwitterion glass The surface quaternized glass is placed in a reactor, the temperature is controlled at 0-60°C, 5-chloromethyl salicylaldehyde solution is added to its surface, the reaction time is controlled at 0.5-50 hours, then the unreacted 5-chloromethyl salicylaldehyde on the glass sheet is removed and cleaned with acetone, and then the glass surface is cleaned with acetone and deionized water in turn. After drying, surface-bonded quaternary ammonium cations and phenol ammonium zwitterionic glass are obtained.
3. The method for preparing the surface-bonded quaternary ammonium cation and phenol ammonium zwitterion glass according to claim 2, characterized in that: In step 1, the amount of the mixed solution is 2-200% of the mass of the glass substrate; the volume ratio of concentrated sulfuric acid and hydrogen peroxide in the mixed solution is 9:1-7:3; the mass ratio of aminosilane coupling agent: ethanol: water in the aminosilane coupling agent solution is 1-5:50-98:5-45; the amount of the aminosilane coupling agent solution is 2-200% of the mass of the glass substrate.
4. The method for preparing the surface-bonded quaternary ammonium cation and phenol ammonium zwitterion glass according to claim 2, characterized in that: In step 2, the amount of the glycidyl ammonium chloride solution is 5-500% of the mass of the glass substrate; the mass ratio of glycidyl ammonium chloride to solvent in the glycidyl ammonium chloride solution is 0.1-0.5:
1.
5. The method for preparing the surface-bonded quaternary ammonium cation and phenol ammonium zwitterion glass according to claim 2 or 4, characterized in that: The epoxypropyl ammonium chloride has a structure shown in the general formula (II): Wherein R1, R2 and R3 are C1-C18 hydrocarbon groups respectively.
6. The method for preparing the surface-bonded quaternary ammonium cation and phenol ammonium zwitterion glass according to claim 2, characterized in that: In step 3, the amount of the 5-chloromethyl salicylaldehyde solution is 2-200% of the mass of the glass substrate; the mass ratio of 5-chloromethyl salicylaldehyde to organic solvent in the 5-chloromethyl salicylaldehyde solution is 0.01-0.5:
1.
7. The method for preparing the surface-bonded quaternary ammonium cation and phenol ammonium zwitterion glass according to claim 2 or 3, characterized in that: In step 1, the aminosilane coupling agent is 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, N-(2-aminoethyl)-3-aminopropyltrimethoxysilane, N-(2-aminoethyl)-3-aminopropyltriethoxysilane, N-ethyl-3-aminopropyltrimethoxysilane, N-ethyl-3-aminopropyltriethoxysilane, 3-aminopropyldimethoxymethylsilane, 3-aminopropyldiethoxymethylsilane, or a mixture of any two of them in any proportion.
8. The method for preparing the surface-bonded quaternary ammonium cation and phenol ammonium zwitterion glass according to claim 4, characterized in that: In step 2, the solvent is one or more of water, methanol, ethanol, acetone, butanone, cyclohexanone, methyl acetate, ethyl acetate, chloroform, 1,2-dichloroethane, carbon tetrachloride, tetrahydrofuran, 1,4-dioxane, decahydronaphthalene, toluene, chlorobenzene, dimethyl sulfoxide or N,N-dimethylacetamide.
9. The method for preparing the surface-bonded quaternary ammonium cation and phenol ammonium zwitterion glass according to claim 6, characterized in that: In step 3, the organic solvent is one or more of acetone, butanone, cyclohexanone, methyl acetate, ethyl acetate, chloroform, 1,2-dichloroethane, carbon tetrachloride, tetrahydrofuran, 1,4-dioxane, decahydronaphthalene, toluene, chlorobenzene, dimethyl sulfoxide or N,N-dimethylacetamide.