Application of a bishydroxyaminopropylsilane coupling agent in glass surface modification

Abstract

The present invention provides an application of a bishydroxylamine propyl silane coupling agent in glass surface modification, particularly a modification method for grafting ammonium phenol zwitterions on glass surface, which is a condensation reaction of a bis(hydroxylamine)propyl silane coupling agent and a hydroxylated glass surface, followed by a quaternary ammonium salt reaction with 5-chloromethyl salicylaldehyde, to achieve a modification method for grafting ammonium phenol zwitterions on glass surface; the glass surface modification method provided by the present invention is simple and easy to implement, and the raw materials used are widely available, cheap, and each preparation step has a high reaction efficiency, and there is no mutual influence before and after the preparation process. The functionalized layer after the glass surface is bonded with quaternary ammonium cations and ammonium phenol zwitterions is a monolayer, presenting a lattice distribution, with high uniformity, so the modified glass has a high light transmittance and has super hydrophilicity.

Description

Technical Field

[0001] The invention relates to application of a bishydroxyaminopropylsilane coupling agent in glass surface modification, which is achieved by condensation reaction of the bishydroxyaminopropylsilane coupling agent with hydroxyl groups on the glass surface and then quaternization reaction with 5-chloromethyl salicylaldehyde to realize the modification application of grafting phenol ammonium zwitterions on the glass surface, belonging to the technical field of glass surface. Technical Background

[0002] Silicate glass is an isotropic amorphous inorganic material with high light transmittance, high hardness, high pressure resistance, wear resistance, and corrosion resistance. In view of its good processability, it has been widely made into household glass products, vehicle windshields, medical glass products, glass curtain walls, glass greenhouses, photovoltaic glass, glass optical windows of underwater equipment and instruments, etc. In particular, people have known that the high hydrophilicity and antibacterial function of optical window glass of underwater equipment and instruments are necessary conditions to ensure its effective use. For this reason, many CN201210442595.7, CN201410321560.7, CN201410145198.2, CN201410551397.3, CN201110155872.1, CN202210463398.7, etc. indicate that by carrying -C=C, -NH 2 The condensation reaction of -SH, -NCO or epoxy silane coupling agents on the surface of the hydroxylated glass can establish new chemical active centers, based on which graft copolymerization can be carried out to link polyethylene glycol, polyacrylic acid, polyacrylamide, quaternary ammonium carboxylic acid inner salt, quaternary ammonium phosphate inner salt or quaternary ammonium sulfonic acid inner salt, etc. These hydrophilic substances form a hydration layer on the glass surface, which can isolate and prevent suspended matter or microorganisms in the water from contacting or adhering to the glass surface; or some antibacterial agents such as capsaicin, chloramine, quaternary ammonium salts are introduced on the glass surface to kill or inhibit the reproduction and growth of microorganisms on the glass surface, thereby achieving the self-cleaning of the optical window glass. For this reason, it is of great significance to achieve super-hydrophilic modification of the glass surface with a simple method. Summary of the invention

[0003] The present invention provides an application of a bishydroxyaminopropyl silane coupling agent in glass surface modification, wherein the bishydroxyaminopropyl silane coupling agent is subjected to a condensation reaction with a hydroxyl group on the glass surface, followed by a quaternary ammonium salt reaction with 5-chloromethyl salicylaldehyde, to achieve the modification and application of grafting phenol ammonium zwitterions on the glass surface. The specific technical scheme is shown in the following reaction formula:

[0004]

[0005] Wherein R in the reaction formula is selected from H or methyl.

[0006] The specific scheme for realizing the application of a bishydroxyaminopropylsilane coupling agent of the present invention in glass surface modification is as follows:

[0007] Step 1: Add ethanol aqueous solution of dihydroxyaminopropylsilane coupling agent on the surface of the hydroxylated glass sheet, place it in an oven at 30-130° C., control the time for 0.5-20 hours, take it out and cool it, and use ethanol to clean the glass sheet. After drying, the surface hydroxylated glass sheet is obtained.

[0008] The hydroxylated glass sheet is prepared according to the following method: adding a piranha solution prepared by 98% by mass concentrated sulfuric acid and 30% by mass hydrogen peroxide in a volume ratio of 9:1 to 7:3 to the surface of a cleaned and dried glass substrate, controlling the temperature at 20 to 120° C. for 0.5 to 50 hours, then taking out the glass substrate, washing the surface of the glass sheet with deionized water, and then vacuum drying at 60 to 90° C. to obtain a surface hydroxylated glass sheet.

[0009] The amount of the piranha solution is 2-200% of the mass of the glass substrate.

[0010] The mass ratio of the bishydroxyaminopropylsilane coupling agent: ethanol: water in the bishydroxyaminopropylsilane coupling agent ethanol aqueous solution is 2-8: 85-95: 3-7, and the amount of the bishydroxyaminopropylsilane coupling agent ethanol aqueous solution is 5-500% of the mass of the hydroxylated glass sheet;

[0011] The bishydroxyaminopropyl silane coupling agent of the present invention has a chemical structure shown in the general formula (1):

[0012]

[0013] Wherein R in the general formula (1) 1 , R 2 and R 3 are selected from or substituted by C 1 ~C 18 Hydrocarbyl, R is selected from H or methyl.

[0014] The ethanol aqueous solution of the bishydroxyaminopropyl silane coupling agent is prepared by Michael addition reaction with aminosilane coupling agent and hydroxyethyl acrylate or hydroxyethyl methacrylate as raw materials. The specific preparation process is as follows: ethanol and aminosilane coupling agent are added into a synthesis reactor, the material temperature in the synthesis reactor is controlled at 10-60° C., hydroxyethyl acrylate or hydroxyethyl methacrylate is slowly added into the synthesis reactor under stirring, and after the addition is completed, the reaction is continued for 2-6 hours to prepare the ethanol solution of the bishydroxyaminopropyl silane coupling agent, and ethanol and water are added into the ethanol solution of the bishydroxyaminopropyl silane coupling agent so that the mass ratio of the bishydroxyaminopropyl silane coupling agent: ethanol: water in the ethanol aqueous solution of the bishydroxyaminopropyl silane coupling agent is 2-8: 85-95: 3-7, and the ethanol aqueous solution is used for standby use.

[0015] The aminosilane coupling agent refers to one or more of 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, N-(2-aminoethyl)-3-aminopropyltrimethoxysilane, N-(2-aminoethyl)-3-aminopropyltriethoxysilane, 3-aminopropyldimethoxymethylsilane, and 3-aminopropyldiethoxymethylsilane; the molar ratio of the aminosilane coupling agent to hydroxyethyl acrylate or hydroxyethyl methacrylate is 2.0 to 2.2.

[0016] Step 2: Add 5-chloromethyl salicylaldehyde solution to the surface of the hydroxylamine glass sheet obtained in step 1, place it in a reactor at 0-60°C, control the reaction time to 0.5-50 hours, then take it out and use acetone to wash and remove the unreacted 5-chloromethyl salicylaldehyde on the glass sheet, then use deionized water to rinse the glass sheet until it is neutral, and after drying, obtain a surface-grafted phenol ammonium zwitterionic glass sheet.

[0017] The mass ratio of 5-chloromethyl salicylaldehyde to organic solvent in the 5-chloromethyl salicylaldehyde solution is 0.01-0.5:1, and the amount of the 5-chloromethyl salicylaldehyde solution is 2-200% of the mass of the hydroxylated glass sheet.

[0018] The organic solvent refers to 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.

[0019] The beneficial effect of using a bishydroxyaminopropylsilane coupling agent provided by the present invention in glass surface modification is that the method for grafting phenol ammonium zwitterions on the glass surface provided by the present invention is simple in technology and easy to implement, the raw materials used are widely available and low in price, each preparation step has high reaction efficiency, and there is no mutual influence before and after the preparation process.

[0020] The functionalized layers after the glass surface is grafted with ammonium phenol zwitterions are all monomolecular layers, presenting a lattice distribution with high uniformity, so the light transmittance of the modified glass will not be affected by the ammonium phenol zwitterions grafted on its surface. DETAILED DESCRIPTION

[0021] In order to further understand the present invention, it is specifically described through examples, the purpose of which is to better understand the content of the present invention. Therefore, the application of the bishydroxyaminopropylsilane coupling agent in glass surface modification not listed in the examples should not be regarded as limiting the scope of protection of the present invention.

[0022] Example 1 Preparation of ammonium phenol zwitterionic glass sheet (1-a)

[0023]

[0024] Preparation of hydroxylated glass sheet: A 7.6*2.5*0.15 cm glass substrate (glass slide, Jiangsu Feizhou Glass Plastic Co., Ltd.) was cleaned and dried, 5 g of a mixed solution of concentrated sulfuric acid and hydrogen peroxide was prepared in a volume ratio of 7:3, and then poured on the glass sheet, treated at 60-70°C for 2 hours, rinsed with deionized water until neutral, and vacuum dried at 60°C to obtain a surface hydroxylated glass sheet (1-a).

[0025] Preparation of bishydroxyaminopropylsilane coupling agent: Add 3.60 g of 3-aminopropyltrimethoxysilane to the synthesis reactor, control the material temperature in the synthesis reactor at 20-30°C, slowly drop 2.66 g of hydroxyethyl methacrylate into the synthesis reactor under stirring, after the addition is completed, continue to keep warm and react for 4 hours, add 20 g of 5% water-ethanol solution by mass percentage, and prepare ethanol aqueous solution of bishydroxyaminopropylsilane coupling agent of formula (1-a), which is set aside.

[0026] Step 1: Add the ethanol aqueous solution of the dihydroxyaminopropylsilane coupling agent of formula (1-a) onto the surface of the hydroxylated glass sheet (1-a), put it into an oven at 80-90°C, take it out after 2 hours and cool it, wash the glass sheet with ethanol, and dry it to obtain the surface hydroxylated glass sheet (1-a).

[0027] Step 2: Place the surface hydroxylated glass sheet (1-a) obtained in step 1 into a reactor, control the temperature at 5-10°C, slowly add 5 g of 40% 5-chloromethyl salicylaldehyde acetone solution on the surface, take it out after 2 hours, and use acetone to clean and remove the unreacted 5-chloromethyl salicylaldehyde on the glass sheet, rinse the glass surface with ethanol and deionized water in turn, and obtain the surface grafted phenol ammonium zwitterionic glass sheet (1-a) after vacuum drying.

[0028] The glass substrate, hydroxylated glass sheet (1-a), hydroxylamination glass sheet (1-a) and phenol ammonium zwitterion glass sheet (1-a) were placed in anhydrous ethanol respectively. After soaking for 0.5 hours, infrared spectroscopy test was performed. There was a medium-intensity absorption peak at 1692nm, which is the typical characteristic absorption peak of aldehyde carbonyl C=O. There was also a medium-intensity absorption peak at 1734nm, which is the typical characteristic absorption peak of ester carbonyl C=O. The glass substrate and the hydroxylated glass sheet (1-a) did not show absorption peaks near 1700nm. It was confirmed that the actual preparation process of the surface-grafted phenol ammonium zwitterion glass sheet was completely consistent with the theoretical design scheme, indicating that the surface of the glass sheet had been successfully grafted with phenol ammonium zwitterions.

[0029] Example 2 Preparation of ammonium phenol zwitterion glass sheet (1-b)

[0030]

[0031] According to the method and operation steps of Example 1, the hydroxyethyl methacrylate in the bishydroxyaminopropylsilane coupling agent preparation in Example 1 was replaced with hydroxyethyl acrylate to prepare a glass sheet (1-b) with ammonium phenol zwitterions grafted on the surface.

[0032] Example 3 Characteristics of surface-grafted ammonium phenol zwitterionic glass sheets

[0033] According to GB / T 24368-2009 Detection of hydrophobic contaminants on glass surfaces: Contact angle measurement method, the pure water contact angles of the glass substrates, hydroxylated glass sheets and surface-grafted phenol ammonium zwitterionic glass sheets of Examples 1 to 2 were measured, as shown in Table 1.

[0034] Table 1 Pure water contact angle of glass slide

[0035] Sample No. 1-a 1-b Glass substrate Hydroxylated glass Water contact angle θ 0 0 53.2 41.4

[0036] The test results in Table 1 show that the water contact angle of the glass substrate decreases after hydroxylation treatment; after the surface is grafted with ammonium phenol zwitterions, the water contact angle decreases to 0, indicating that the surface of the glass sheet has super hydrophilicity and that the surface of the glass sheet has been successfully grafted with ammonium phenol zwitterions.

Claims

1. Application of a bishydroxyaminopropylsilane coupling agent in glass surface modification, characterized in that The following steps are involved: Step 1: Add an ethanol aqueous solution of a bishydroxyaminopropylsilane coupling agent to the surface of a hydroxylated glass sheet, place the sheet in an oven at 30 to 130° C., control the time for 0.5 to 20 hours, take the sheet out for cooling, and wash the sheet with ethanol. After drying, a surface hydroxylated glass sheet is obtained; The bishydroxyaminopropylsilane coupling agent in the ethanol aqueous solution of the bishydroxyaminopropylsilane coupling agent has a chemical structure shown in the general formula (1): Wherein R1, R2 and R3 in the general formula (1) are selected from substituted or substituted C1-C 18 Hydrocarbyl, R is selected from H or methyl; The hydroxylated glass sheet is prepared by the following method: adding a piranha solution prepared by 98% by mass concentrated sulfuric acid and 30% by mass hydrogen peroxide in a volume ratio of 9:1 to 7:3 to the surface of a cleaned and dried glass substrate, controlling the temperature at 20 to 120° C. for 0.5 to 50 hours, then taking out the glass substrate, washing the surface of the glass sheet with deionized water, and then vacuum drying at 60 to 90° C. to obtain a surface hydroxylated glass sheet; wherein the amount of the piranha solution used is 2 to 200% of the mass of the glass substrate; The bishydroxyaminopropylsilane coupling agent ethanol aqueous solution refers to a bishydroxyaminopropylsilane coupling agent: ethanol: water mass ratio of 2 to 8: 85 to 95: 3 to 7, and the amount of the bishydroxyaminopropylsilane coupling agent ethanol aqueous solution is 5 to 500% of the mass of the glass substrate; Step 2: Add 5-chloromethyl salicylaldehyde solution to the surface of the hydroxylamine glass sheet obtained in step 1, put it into a reactor at 0-60° C., control the reaction time to 0.5-50 hours, then take it out and use acetone to wash to remove the unreacted 5-chloromethyl salicylaldehyde on the glass sheet, then use deionized water to rinse the glass sheet until it is neutral, and after drying, obtain glass with ammonium phenol zwitterions grafted on the surface; The mass ratio of 5-chloromethyl salicylaldehyde to organic solvent in the 5-chloromethyl salicylaldehyde solution is 0.01-0.5:1, and the amount of the 5-chloromethyl salicylaldehyde solution is 2-200% of the mass of the hydroxylated glass sheet.

2. The use of a bishydroxyaminopropylsilane coupling agent in glass surface modification according to claim 1, characterized in that The preparation method of the ethanol aqueous solution of the bishydroxyaminopropyl silane coupling agent is as follows: ethanol and aminosilane coupling agent are added into a synthesis reactor, the material temperature in the synthesis reactor is controlled at 10-60° C., hydroxyethyl acrylate or hydroxyethyl methacrylate is slowly added into the synthesis reactor under stirring, and after the addition is completed, the reaction is continued for 2-6 hours to obtain the ethanol solution of the bishydroxyaminopropyl silane coupling agent, and then ethanol and water are added into the ethanol solution of the bishydroxyaminopropyl silane coupling agent, so that the mass ratio of the bishydroxyaminopropyl silane coupling agent: ethanol: water in the ethanol aqueous solution of the bishydroxyaminopropyl silane coupling agent is 2-8: 85-95: 3-7; The molar ratio of the bishydroxyaminopropylsilane coupling agent to hydroxyethyl acrylate or hydroxyethyl methacrylate is 2.0-2.

2.

3. The use of a bishydroxyaminopropylsilane coupling agent in glass surface modification according to claim 1, characterized in that The organic solvent refers to 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.

4. The use of a bishydroxyaminopropylsilane coupling agent in glass surface modification according to claim 2, characterized in that The aminosilane coupling agent refers to one or more of 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, N-(2-aminoethyl)-3-aminopropyltrimethoxysilane, N-(2-aminoethyl)-3-aminopropyltriethoxysilane, 3-aminopropyldimethoxymethylsilane, and 3-aminopropyldiethoxymethylsilane.

Images