CN105130206B - A kind of preparation method of super-hydrophobic automatic cleaning glass - Google Patents

Abstract

The invention relates to a method for preparing superhydrophobic self-cleaning glass, which comprises the following steps: taking ordinary glass and immersing it in a piranha solution to carry out surface hydroxylation treatment, then placing the glass obtained by surface hydroxylation treatment in toluene, adding terminal groups as bis The silane coupling agent of the bonded surface is treated with double bonds on the surface, and then the hydrophobic polymer is covalently grafted on the glass surface by in-situ polymerization or spraying method, and the superhydrophobic self-cleaning glass is obtained after cleaning and drying. The preparation method of the superhydrophobic self-cleaning coated glass of the present invention can form a uniform, chemically grafted polymer coating on the surface of ordinary glass, and the coating has good superhydrophobicity, stability, light transmittance and excellent self-cleaning cleanliness.

Description

A kind of preparation method of superhydrophobic self-cleaning glass

technical field

The invention relates to the technical field of glass manufacturing, in particular to a method for preparing superhydrophobic self-cleaning glass.

Background technique

Glass is widely used in construction, automobiles, etc. Problems such as air pollution make these glasses very easy to get dirty and lose their light transmittance. The cleaning work of glass also becomes difficult, especially for high-rise buildings, cleaning glass also has very high danger. A new type of self-cleaning glass has been extensively and intensively studied to address the above problems. The so-called self-cleaning glass refers to the unique physical and chemical properties of the surface of ordinary glass after special physical or chemical treatment, so that the glass itself keeps fresh automatically and has a long-lasting light transmittance to keep the glass as bright as new. status. It can make the glass no longer go through the traditional manual scrubbing method, but can be cleaned under the natural rainwater. Hydrophobic self-cleaning glass is coated with a layer of super-hydrophobic film on the surface of ordinary glass, so that the water on the glass surface cannot be adsorbed on the glass surface and become spherical water droplets to roll away, and hydrophilic stains and lipophilic stains cannot adhere to the glass surface, thus ensuring the self-cleaning property of the glass.

Hydrophobic self-cleaning glass mostly imitates the self-cleaning effect of lotus leaves, and is prepared by coating a layer of hydrophobic film on the glass surface. The hydrophobic film can be a super-hydrophobic organic polymer fluoride, silicide and other polymer films, or an inorganic metal oxide film with a certain roughness. The existing methods for preparing hydrophobic coatings mainly include: sol-gel method, phase separation and self-assembly method, one-step surface pulling method, hydrofluoric acid corrosion method, plasma etching method, chemical deposition method, template method, etc. Many superhydrophobic surfaces with excellent properties have been obtained by using these methods. However, the disadvantage of the hydrophobic coatings prepared by these methods is that the coatings are mostly combined with the glass substrate by non-bonding, and the coatings are unstable. Due to the poor timeliness of hydrophobic glass, the long-term service life of glass products as durable consumer goods cannot be guaranteed, so the true self-cleaning effect cannot be guaranteed. How to covalently graft hydrophobic polymers to the glass surface to enhance the binding force between the hydrophobic coating and the glass; on the other hand, how to develop a simple, economical and environmentally friendly preparation method is the focus and focus of the current research and development of hydrophobic self-cleaning glass. difficulty.

Contents of the invention

In order to solve the above technical problems, the present invention provides a method for preparing superhydrophobic self-cleaning glass, which solves the problem that the hydrophobic coating of the existing hydrophobic glass has weak bonding force with the glass substrate and the coating is easy to fall off.

The technical solution adopted by the present invention to solve the above problems is: a preparation method of superhydrophobic self-cleaning glass, comprising the following steps: taking ordinary glass and immersing it in piranha solution to carry out surface hydroxylation treatment, and then placing the glass obtained by surface hydroxylation treatment In toluene, add a silane coupling agent whose end group is a double bond to treat the surface end double bond, and then covalently graft the hydrophobic polymer on the glass surface by in-situ polymerization or spraying method, after cleaning and drying Prepared superhydrophobic self-cleaning glass.

As a further optimization of the preparation method of a superhydrophobic self-cleaning glass of the present invention, the preparation method comprises the following steps:

(1) Hydroxylation of ordinary glass surface: prepare piranha solution, control the temperature at 50-100°C, add cleaned ordinary glass, oxidize for 1-120 min, wash with deionized water and dry after oxidation;

(2) Double bond on the glass surface: put the glass obtained in step (1) in toluene, add a silane coupling agent with a double bond at the end group, stop the reaction after reflux for 5-30 h, take out the glass piece, and clean it ultrasonically After that, let it dry at room temperature;

(3) Glass-grafted polymers: Covalently graft hydrophobic polymers onto the glass surface by in-situ polymerization or spraying, ultrasonically clean with ethanol and water, and dry at room temperature to obtain superhydrophobic self-cleaning glass.

As a further optimization of the preparation method of the above-mentioned superhydrophobic self-cleaning glass: the silane coupling agent whose terminal group is a double bond is γ-methacryloxypropyl trimethoxysilane, γ-methacryloyl Oxypropyltriethoxysilane, Vinyltrimethoxysilane or Vinyltriethoxysilane.

As a further optimization of the preparation method of the above superhydrophobic self-cleaning glass: the hydrophobic polymer is polystyrene, polystyrene and polymethyl methacrylate copolymer or polytetrafluoroethylene.

As a further optimization of the preparation method of the above-mentioned super-hydrophobic self-cleaning glass: in the step (3), the specific steps of covalently grafting the hydrophobic polymer to the glass surface by in-situ polymerization method are as follows: in the reaction bottle, Add the double-bonded glass flakes prepared in step (2), the reaction medium is distilled water, and the polymerization temperature is 60-80°C; add styrene monomer or styrene-methyl methacrylate blend monomer, in N _2. Add the initiator (the amount of the monomer) under protection; stop the reaction after 5-20 h; take out the glass piece, clean it with ethanol and water ultrasonically, and dry it at room temperature.

As a further optimization of the preparation method of the above-mentioned superhydrophobic self-cleaning glass: the initiator is ammonium persulfate or azobisisobutyronitrile, and the amount of the initiator is 1% to 5% of the added weight of the monomer.

As a further optimization of the preparation method of the above-mentioned superhydrophobic self-cleaning glass: the molar ratio of styrene and methyl methacrylate monomer in the styrene and methyl methacrylate blend monomer is 20 to 10: 1 .

As a further optimization of the preparation method of the above-mentioned super-hydrophobic self-cleaning glass: in the step (3), the specific steps of covalently grafting the hydrophobic polymer on the glass surface by spraying method are: polystyrene, polystyrene Spray the emulsion of ethylene and polymethyl methacrylate copolymer or polytetrafluoroethylene on the surface of the double-bonded glass sheet prepared in step (2), dry it at room temperature, and then place it at a constant temperature of 300-400°C Plasticize in the furnace for 5-15 h.

Beneficial effect

1. The method for preparing superhydrophobic self-cleaning coated glass of the present invention can form a uniform, chemically grafted polymer coating on the surface of ordinary glass. The coating has good superhydrophobicity, stability, light transmittance and excellent self-cleaning property; at the same time, the preparation method of the present invention has simple process, no need for special equipment, low production cost, and is easy to realize industrialized production;

2. On the glass prepared by the present invention, the polymer superhydrophobic coating is covalently bonded to the glass, so the coating is not easy to fall off and has high stability.

Description of drawings

Fig. 1 is the scanning electron micrograph of common glass in the embodiment 1 of the present invention;

Fig. 2 is the scanning electron microscope picture of the glass after hydroxylation treatment in the embodiment 1 of the present invention;

Fig. 3 is the scanning electron micrograph of the glass modified by the double bond at the middle end in Example 1 of the present invention;

Fig. 4 is a scanning electron microscope image of self-cleaning glass in Example 1 of the present invention;

Figure 5 is an energy spectrum analysis diagram of ordinary glass in Example 1 of the present invention;

6 is an energy spectrum analysis diagram of glass after hydroxylation treatment in Example 1 of the present invention;

Fig. 7 is an energy spectrum analysis diagram of the glass modified by the double bond at the middle end in Example 1 of the present invention;

Figure 8 is an energy spectrum analysis diagram of self-cleaning glass in Example 1 of the present invention;

Fig. 9 is a wide-spectrum scanning diagram of common glass in Example 7 of the present invention;

Fig. 10 is a high-resolution scanning diagram of C1s of common glass in Example 7 of the present invention;

Figure 11 is a wide-spectrum scanning diagram of self-cleaning glass in Example 7 of the present invention;

Fig. 12 is a high-resolution scanning diagram of C1s of self-cleaning glass in Example 7 of the present invention;

Fig. 13 is a contact angle test diagram of ordinary glass in Example 10 of the present invention;

Fig. 14 is the contact angle test diagram of glass after hydroxylation treatment in Example 10 of the present invention;

Fig. 15 is a test diagram of the contact angle of the glass modified by the middle-end double bond in Example 10 of the present invention;

Fig. 16 is a contact angle test diagram of self-cleaning glass in Example 10 of the present invention;

Fig. 17 is the contact angle test diagram after the polymer is grafted on the surface of ordinary glass;

Figure 18 is a light transmittance test chart of ordinary glass and self-cleaning glass in Example 11 of the present invention;

Fig. 19 is a schematic diagram of the principle of the preparation method of the present invention.

Detailed ways

The present invention will be further described below in conjunction with specific embodiment:

Example 1:

A preparation method of superhydrophobic self-cleaning glass, comprising the following steps:

(1) Hydroxylation of ordinary glass surface: First, cut the ordinary glass sheet into 10*10 mm, and ultrasonically clean it; then configure piranha solution, control the temperature at 80°C, add clean ordinary glass, control the oxidation time at 60 min, and then stop Rinse with deionized water and dry;

(2) Double bond on the surface of the glass: put 10 pieces of hydroxylated glass on the surface in 100 mL of toluene, add 5 mL of γ-methacryloxypropyltrimethoxysilane, and stop after reflux for 24 h To react, take out the glass slide, clean it ultrasonically with ethanol and water, and dry it at room temperature;

(3) Glass-grafted polystyrene: In the reaction bottle, add 10 double-bonded glass sheets prepared in step 2, the reaction medium is distilled water, and the polymerization temperature is 70°C; add 10 mL of styrene monomer, Under the protection of N2, 0.27 g of ammonium persulfate was added as an initiator; the reaction was stopped after 10 h; the glass piece was taken out, cleaned ultrasonically with ethanol and water, and dried at room temperature to obtain a self-cleaning glass.

Example 2:

A preparation method of superhydrophobic self-cleaning glass, comprising the following steps:

(1) Hydroxylation of ordinary glass surface: firstly cut the ordinary glass sheet into 10*10 mm, ultrasonic cleaning; then prepare piranha solution, control the temperature at 500C, add clean ordinary glass, control the oxidation time at 120 min, stop using Rinse with deionized water and dry;

(2) Double bond on the surface of the glass: put 10 pieces of hydroxylated glass on the surface in 100 mL of toluene, add 10 mL of γ-methacryloxypropyltrimethoxysilane, and stop the reaction after refluxing for 5 h , take out the glass slide, clean it ultrasonically with ethanol and water, and dry it at room temperature;

(3) Glass-grafted polystyrene: In the reaction bottle, add 10 double-bonded glass sheets prepared in step 2, the reaction medium is distilled water, and the polymerization temperature is 60 °C; add 10 mL of styrene monomer, Under the protection of N2, 0.44 g of ammonium persulfate was added as an initiator; the reaction was stopped after 5 h; the glass piece was taken out, cleaned ultrasonically with ethanol and water, and dried at room temperature to obtain a self-cleaning glass.

Example 3:

A preparation method of superhydrophobic self-cleaning glass, comprising the following steps:

(1) Hydroxylation of ordinary glass surface: First, cut the ordinary glass sheet into 10*10 mm, ultrasonic cleaning; then prepare piranha solution, control the temperature at 1000C, add clean ordinary glass, control the oxidation time at 1 min, and use Rinse with deionized water and dry;

(2) Double bond on the surface of the glass: Put 10 glass slices with surface hydroxylation in 100 mL of toluene, add 1 mL of γ-methacryloxypropyltrimethoxysilane, and stop after reflux for 30 h To react, take out the glass slide, clean it ultrasonically with ethanol and water, and dry it at room temperature;

(3) Glass-grafted polystyrene: In the reaction flask, add 10 double-bonded glass pieces prepared in step 2, the reaction medium is distilled water, and the polymerization temperature is 80°C; add 10 mL of styrene monomer, Under the protection of N2, 0.09 g of ammonium persulfate was added as an initiator; the reaction was stopped after 20 h; the glass piece was taken out, cleaned ultrasonically with ethanol and water, and dried at room temperature to obtain a self-cleaning glass.

Example 4:

A preparation method of superhydrophobic self-cleaning glass, comprising the following steps:

(1) Hydroxylation of ordinary glass surface: firstly cut the ordinary glass piece into 10*10 mm, ultrasonic cleaning; then prepare piranha solution, control the temperature at 800C, add clean ordinary glass, control the oxidation time at 60 min, stop using Rinse with deionized water and dry;

(2) Double bond on the surface of the glass: put 10 pieces of hydroxylated glass on the surface in 100 mL of toluene, add 5 mL of γ-methacryloxypropyltriethoxysilane, and reflux for 18 h Stop the reaction, take out the glass slide, clean it ultrasonically with ethanol and water, and dry it at room temperature;

(3) Glass-grafted polystyrene: In the reaction bottle, add 10 double-bonded glass sheets prepared in step 2, the reaction medium is distilled water, and the polymerization temperature is 70°C; add 10 mL of styrene monomer, Under the protection of N2, 0.27 g of ammonium persulfate was added as an initiator; the reaction was stopped after 10 h; the glass piece was taken out, cleaned ultrasonically with ethanol and water, and dried at room temperature to obtain a self-cleaning glass.

Example 5:

A preparation method of superhydrophobic self-cleaning glass, comprising the following steps:

(1) Hydroxylation of ordinary glass surface: firstly cut the ordinary glass piece into 10*10 mm, ultrasonic cleaning; then prepare piranha solution, control the temperature at 800C, add clean ordinary glass, control the oxidation time at 60 min, stop using Rinse with deionized water and dry;

(2) Double bond on the surface of the glass: put 10 pieces of hydroxylated glass on the surface in 100 mL of toluene, add 5 mL of vinyltrimethoxysilane, and stop the reaction after reflux for 18 h, take out the glass pieces, and wash with ethanol , Ultrasonic cleaning with water, and drying at room temperature;

(3) Glass-grafted polystyrene: In the reaction bottle, add 10 double-bonded glass sheets prepared in step 2, the reaction medium is distilled water, and the polymerization temperature is 70°C; add 10 mL of styrene monomer, Under the protection of N2, 0.27 g of ammonium persulfate was added as an initiator; the reaction was stopped after 10 h; the glass piece was taken out, cleaned ultrasonically with ethanol and water, and dried at room temperature to obtain a self-cleaning glass.

Embodiment 6:

A preparation method of superhydrophobic self-cleaning glass, comprising the following steps:

(1) Hydroxylation of ordinary glass surface: firstly cut the ordinary glass piece into 10*10 mm, ultrasonic cleaning; then prepare piranha solution, control the temperature at 800C, add clean ordinary glass, control the oxidation time at 60 min, stop using Rinse with deionized water and dry;

(2) Double bond on the surface of the glass: put 10 pieces of hydroxylated glass on the surface in 100 mL of toluene, add 5 mL of vinyltriethoxysilane, reflux for 18 h to stop the reaction, take out the glass pieces, and use Ultrasonic cleaning with ethanol and water, and drying at room temperature;

(3) Glass-grafted polystyrene: In the reaction bottle, add 10 double-bonded glass sheets prepared in step 2, the reaction medium is distilled water, and the polymerization temperature is 70°C; add 10 mL of styrene monomer, Under the protection of N2, 0.27 g of ammonium persulfate was added as an initiator; the reaction was stopped after 10 h; the glass piece was taken out, cleaned ultrasonically with ethanol and water, and dried at room temperature to obtain a self-cleaning glass.

Embodiment 7:

A preparation method of superhydrophobic self-cleaning glass, comprising the following steps:

(1) Hydroxylation of ordinary glass surface: First, cut the ordinary glass sheet into 10*10 mm, and ultrasonically clean it; then configure piranha solution, control the temperature at 80°C, add clean ordinary glass, control the oxidation time at 60 min, and then stop Rinse with deionized water and dry;

(2) Double bond on the surface of the glass: put 10 pieces of hydroxylated glass on the surface in 100 mL of toluene, add 5 mL of γ-methacryloxypropyltrimethoxysilane, and stop after reflux for 18 h To react, take out the glass slide, clean it ultrasonically with ethanol and water, and dry it at room temperature;

(3) Glass-grafted polystyrene: In the reaction bottle, add 10 double-bonded glass sheets prepared in step 2, the reaction medium is distilled water, and the polymerization temperature is 70°C; add 10 mL of styrene monomer, Under the protection of N ₂ , an initiator of 0.27 g of azobisisobutylcyanide was added; the reaction was stopped after 10 h; the glass piece was taken out, cleaned ultrasonically with ethanol and water, and dried at room temperature to obtain a self-cleaning glass.

Embodiment 8:

A preparation method of superhydrophobic self-cleaning glass, comprising the following steps:

(1) Hydroxylation of ordinary glass surface: First, cut the ordinary glass sheet into 10*10 mm, and ultrasonically clean it; then configure piranha solution, control the temperature at 80°C, add clean ordinary glass, control the oxidation time at 60 min, and then stop Rinse with deionized water and dry;

(2) Double bond on the surface of the glass: put 10 pieces of hydroxylated glass on the surface in 100 mL of toluene, add 5 mL of γ-methacryloxypropyltrimethoxysilane, and stop after reflux for 18 h To react, take out the glass slide, clean it ultrasonically with ethanol and water, and dry it at room temperature;

(3) Glass-grafted polystyrene-polymethyl methacrylate copolymer: In the reaction bottle, add 10 double-bonded glass sheets prepared in step 2, the reaction medium is distilled water, and the polymerization temperature is 70 °C Add 9.6 mL of styrene monomer, 0.4 mL of methyl methacrylate, and add 0.27 g of ammonium persulfate as an initiator under the protection of N ₂ ; stop after 10 h of reaction; take out the glass sheet and clean it ultrasonically with ethanol and water, and let it dry at room temperature Dry to produce self-cleaning glass.

Embodiment 9:

A preparation method of superhydrophobic self-cleaning glass, comprising the following steps:

(1) Hydroxylation of ordinary glass surface: First, cut the ordinary glass sheet into 10*10 mm, and ultrasonically clean it; then configure piranha solution, control the temperature at 80°C, add clean ordinary glass, control the oxidation time at 60 min, and then stop Rinse with deionized water and dry;

(2) Double bond on the surface of the glass: put 10 pieces of hydroxylated glass on the surface in 100 mL of toluene, add 5 mL of γ-methacryloxypropyltrimethoxysilane, and stop after reflux for 18 h To react, take out the glass slide, clean it ultrasonically with ethanol and water, and dry it at room temperature;

(3) Glass-grafted polystyrene-polymethyl methacrylate copolymer: In the reaction bottle, add 10 double-bonded glass sheets prepared in step 2, the reaction medium is distilled water, and the polymerization temperature is 70 °C Add 9.2 mL of styrene monomer, 0.8 mL of methyl methacrylate, and add 0.27 g of ammonium persulfate as an initiator under the protection of N ₂ ; stop after 10 h of reaction; take out the glass sheet and clean it ultrasonically with ethanol and water, and let it dry at room temperature Dry to produce self-cleaning glass.

Example 10:

A preparation method of superhydrophobic self-cleaning glass, comprising the following steps:

(1) Hydroxylation of ordinary glass surface: First, cut the ordinary glass sheet into 10*10 mm, and ultrasonically clean it; then configure piranha solution, control the temperature at 80°C, add clean ordinary glass, control the oxidation time at 60 min, and then stop Rinse with deionized water and dry;

(2) Double bond on the surface of the glass: put 10 pieces of hydroxylated glass on the surface in 100 mL of toluene, add 5 mL of γ-methacryloxypropyltrimethoxysilane, and stop after reflux for 18 h To react, take out the glass slide, clean it ultrasonically with ethanol and water, and dry it at room temperature;

(3) Glass-grafted polystyrene-polymethyl methacrylate copolymer: In the reaction bottle, add 10 double-bonded glass sheets prepared in step 2, the reaction medium is distilled water, and the polymerization temperature is 70 °C ; Add 9.4 mL of styrene monomer, 0.6 mL of methyl methacrylate, and add 0.27 g of ammonium persulfate as an initiator under the protection of N ₂ ; stop after 10 h of reaction; take out the glass sheet and clean it ultrasonically with ethanol and water, and let it dry at room temperature Dry to produce self-cleaning glass.

Example 11:

A preparation method of superhydrophobic self-cleaning glass, comprising the following steps:

(1) Hydroxylation of ordinary glass surface: First, cut the ordinary glass sheet into 10*10 mm, and ultrasonically clean it; then configure piranha solution, control the temperature at 80°C, add clean ordinary glass, control the oxidation time at 60 min, and then stop Rinse with deionized water and dry;

(2) Double bond on the surface of the glass: put 10 pieces of hydroxylated glass on the surface in 100 mL of toluene, add 5 mL of γ-methacryloxypropyltrimethoxysilane, and stop after reflux for 18 h To react, take out the glass slide, clean it ultrasonically with ethanol and water, and dry it at room temperature;

(3) Glass-grafted polystyrene-polymethyl methacrylate copolymer: In the reaction bottle, add 10 double-bonded glass sheets prepared in step 2, the reaction medium is distilled water, and the polymerization temperature is 70 °C Add 9.4 mL of styrene monomer, 0.6 mL of methyl methacrylate, and add 0.27 g of initiator azobisisobutylcyanide under the protection of N ₂ ; stop after 10 h of reaction; take out the glass sheet and clean it ultrasonically with ethanol and water. Dry at room temperature to produce self-cleaning glass.

Example 12:

A preparation method of superhydrophobic self-cleaning glass, comprising the following steps:

(1) Hydroxylation of ordinary glass surface: First, cut the ordinary glass sheet into 10*10 mm, and ultrasonically clean it; then configure piranha solution, control the temperature at 80°C, add clean ordinary glass, control the oxidation time at 60 min, and then stop Rinse with deionized water and dry;

(2) Double bond on the surface of the glass: put 10 pieces of hydroxylated glass on the surface in 100 mL of toluene, add 5 mL of γ-methacryloxypropyltriethoxysilane, and reflux for 18 h Stop the reaction, take out the glass slide, clean it ultrasonically with ethanol and water, and dry it at room temperature;

(3) Glass-grafted polystyrene-polymethyl methacrylate copolymer: In the reaction bottle, add 10 double-bonded glass sheets prepared in step 2, the reaction medium is distilled water, and the polymerization temperature is 70 °C ; Add 9.4 mL of styrene monomer, 0.6 mL of methyl methacrylate, and add 0.27 g of ammonium persulfate as an initiator under the protection of N ₂ ; stop after 10 h of reaction; take out the glass sheet and clean it ultrasonically with ethanol and water, and let it dry at room temperature Dry to produce self-cleaning glass.

Example 13:

A preparation method of superhydrophobic self-cleaning glass, comprising the following steps:

(1) Hydroxylation of ordinary glass surface: First, cut the ordinary glass sheet into 10*10 mm, and ultrasonically clean it; then configure piranha solution, control the temperature at 80°C, add clean ordinary glass, control the oxidation time at 60 min, and then stop Rinse with deionized water and dry;

(2) Double bond on the surface of the glass: put 10 pieces of hydroxylated glass on the surface in 100 mL of toluene, add 5 mL of vinyltrimethoxysilane, and stop the reaction after reflux for 18 h, take out the glass pieces, and wash with ethanol , Ultrasonic cleaning with water, and drying at room temperature;

(3) Glass-grafted polystyrene-polymethyl methacrylate copolymer: In the reaction bottle, add 10 double-bonded glass sheets prepared in step 2, the reaction medium is distilled water, and the polymerization temperature is 70 °C ; Add 9.4 mL of styrene monomer, 0.6 mL of methyl methacrylate, and add 0.27 g of ammonium persulfate as an initiator under the protection of N ₂ ; stop after 10 h of reaction; take out the glass sheet and clean it ultrasonically with ethanol and water, and let it dry at room temperature Dry to produce self-cleaning glass.

Example 14:

A preparation method of superhydrophobic self-cleaning glass, comprising the following steps:

(1) Hydroxylation of ordinary glass surface: First, cut the ordinary glass sheet into 10*10 mm, and ultrasonically clean it; then configure piranha solution, control the temperature at 80°C, add clean ordinary glass, control the oxidation time at 60 min, and then stop Rinse with deionized water and dry;

(2) Double bond on the surface of the glass: put 10 pieces of hydroxylated glass on the surface in 100 mL of toluene, add 5 mL of γ-methacryloxypropyltrimethoxysilane, and stop after reflux for 18 h To react, take out the glass slide, clean it ultrasonically with ethanol and water, and dry it at room temperature;

(3) Glass-grafted polytetrafluoroethylene: use a spray gun to spray a homogeneous polytetrafluoroethylene emulsion on the surface of the double-bonded glass sheet prepared in step 2, and dry it at room temperature; then place it in a constant temperature oven at 300 ° C for molding After 15 h, the self-cleaning glass was obtained.

Example 15:

A preparation method of superhydrophobic self-cleaning glass, comprising the following steps:

(1) Hydroxylation of ordinary glass surface: First, cut the ordinary glass sheet into 10*10 mm, and ultrasonically clean it; then configure piranha solution, control the temperature at 80°C, add clean ordinary glass, control the oxidation time at 60 min, and then stop Rinse with deionized water and dry;

(2) Double bond on the surface of the glass: put 10 pieces of hydroxylated glass on the surface in 100 mL of toluene, add 5 mL of γ-methacryloxypropyltrimethoxysilane, and stop after reflux for 18 h To react, take out the glass slide, clean it ultrasonically with ethanol and water, and dry it at room temperature;

(3) Glass-grafted PTFE: Use a spray gun to spray a uniform polytetrafluoroethylene emulsion on the surface of the double-bonded glass sheet prepared in step 2, and dry it at room temperature; then place it in a constant temperature furnace at 400 ° C After 5 h, self-cleaning glass was obtained.

Example 16:

A preparation method of superhydrophobic self-cleaning glass, comprising the following steps:

(1) Hydroxylation of ordinary glass surface: First, cut the ordinary glass sheet into 10*10 mm, and ultrasonically clean it; then configure piranha solution, control the temperature at 80°C, add clean ordinary glass, control the oxidation time at 60 min, and then stop Rinse with deionized water and dry;

(2) Double bond on the surface of the glass: put 10 pieces of hydroxylated glass on the surface in 100 mL of toluene, add 5 mL of γ-methacryloxypropyltrimethoxysilane, and stop after reflux for 18 h To react, take out the glass slide, clean it ultrasonically with ethanol and water, and dry it at room temperature;

(3) Glass-grafted PTFE: Use a spray gun to spray a uniform polytetrafluoroethylene emulsion on the surface of the double-bonded glass sheet prepared in step 2, and dry it at room temperature; then place it in a constant temperature oven at 350°C for plastic After 10 h, self-cleaning glass was obtained.

Example 17:

A preparation method of superhydrophobic self-cleaning glass, comprising the following steps:

(1) Hydroxylation of ordinary glass surface: First, cut the ordinary glass sheet into 10*10 mm, and ultrasonically clean it; then configure piranha solution, control the temperature at 80°C, add clean ordinary glass, control the oxidation time at 60 min, and then stop Rinse with deionized water and dry;

(2) Double bond on the surface of the glass: put 10 pieces of hydroxylated glass on the surface in 100 mL of toluene, add 5 mL of γ-methacryloxypropyltrimethoxysilane, and stop after reflux for 18 h To react, take out the glass slide, clean it ultrasonically with ethanol and water, and dry it at room temperature;

(3) Glass-grafted PTFE: Use a spray gun to evenly spray the polystyrene suspension on the surface of the double-bonded glass sheet prepared in step 2, and dry it at room temperature; then place it in a constant temperature oven at 350°C After 10 h, self-cleaning glass was obtained.

Example 18:

A preparation method of superhydrophobic self-cleaning glass, comprising the following steps:

(1) Hydroxylation of ordinary glass surface: First, cut the ordinary glass sheet into 10*10 mm, and ultrasonically clean it; then configure piranha solution, control the temperature at 80°C, add clean ordinary glass, control the oxidation time at 60 min, and then stop Rinse with deionized water and dry;

(2) Double bond on the surface of the glass: put 10 pieces of hydroxylated glass on the surface in 100 mL of toluene, add 5 mL of γ-methacryloxypropyltrimethoxysilane, and stop after reflux for 18 h To react, take out the glass slide, clean it ultrasonically with ethanol and water, and dry it at room temperature;

(3) Glass-grafted polytetrafluoroethylene: use a spray gun to evenly spray the polystyrene-polymethyl methacrylate copolymer suspension on the surface of the double-bonded glass sheet prepared in step 2, and dry it at room temperature; then Placed in a constant temperature oven at 350 °C for 10 h to make self-cleaning glass.

Example 19:

(1) Hydroxylation of ordinary glass surface: First, cut the ordinary glass sheet into 10*10 mm, and ultrasonically clean it; then configure piranha solution, control the temperature at 80°C, add clean ordinary glass, control the oxidation time at 60 min, and then stop Rinse with deionized water and dry;

(2) Double bond on the surface of the glass: put 10 pieces of hydroxylated glass on the surface in 100 mL of toluene, add 5 mL of γ-methacryloxypropyltriethoxysilane, and reflux for 18 h Stop the reaction, take out the glass slide, clean it ultrasonically with ethanol and water, and dry it at room temperature;

(3) Glass-grafted polytetrafluoroethylene: use a spray gun to spray a homogeneous polytetrafluoroethylene emulsion on the surface of the double-bonded glass sheet prepared in step 2, and dry it at room temperature; then place it in a constant temperature oven at 300 ° C for molding After 15 h, the self-cleaning glass was obtained.

Example 20:

(1) Hydroxylation of ordinary glass surface: First, cut the ordinary glass sheet into 10*10 mm, and ultrasonically clean it; then configure piranha solution, control the temperature at 80°C, add clean ordinary glass, control the oxidation time at 60 min, and then stop Rinse with deionized water and dry;

(2) Double bond on the surface of the glass: put 10 pieces of hydroxylated glass on the surface in 100 mL of toluene, add 5 mL of vinyltriethoxysilane, reflux for 18 h to stop the reaction, take out the glass pieces, and use Ultrasonic cleaning with ethanol and water, and drying at room temperature;

(3) Glass-grafted polytetrafluoroethylene: use a spray gun to spray a homogeneous polytetrafluoroethylene emulsion on the surface of the double-bonded glass sheet prepared in step 2, and dry it at room temperature; then place it in a constant temperature oven at 300 ° C for molding After 15 h, the self-cleaning glass was obtained.

Test Data

(1) Scanning electron microscope observation

Figures 1-4 are scanning electron micrographs of common glass, hydroxylated glass, terminal double bond modified glass and self-cleaning glass used in Example 1, wherein Figure 1 is common glass, Figure 2 is hydroxylated glass, and Figure 3 It is a double-bond modified glass at the end, and Figure 4 is a self-cleaning glass.

It can be seen from the figure that the surface of ordinary glass is smooth and flat; after surface oxidation, the surface of glass becomes obviously rough, indicating that the oxidation effect is obvious; and after further silane coupling of oxidized glass, the large area of rough surface morphology disappears and becomes The morphologies of small white bumps appeared one by one, indicating that the silane coupling agent was successfully introduced into the glass surface; when polystyrene was further introduced into the coupled glass surface through in-situ polymerization, more silane coupling agents appeared on the surface. The bumps are smaller and more uniform, which can be attributed to the successful grafting of polystyrene onto the surface of the modified glass.

(2) Energy Spectrum Test

Fig. 5-8 is that common glass, hydroxylated glass, terminal double bond modified glass and self-cleaning glass used in embodiment 1 have carried out corresponding energy spectrum test;

Among them, Figure 5 is ordinary glass, and the data are as follows:

Figure 6 is hydroxylated glass, the data are as follows:

Figure 7 shows the modified glass with terminal double bonds, and the data are as follows:

Figure 10 is self-cleaning glass, the data is as follows:

It can be seen from the figure and data that after the ordinary glass is oxidized, the oxygen content increases from 18.33 wt% (mass content) of the ordinary glass to 22.92 wt%, which may be due to the oxidation, which introduces more hydroxyl groups on the surface of the ordinary glass. and when the oxidized glass was further coupled, the silicon content increased from 32.43 wt% of the oxidized glass to 49.95 wt%, indicating that the silane coupling agent molecules were successfully introduced to the glass surface; and when polystyrene was grafted onto the glass After surface treatment, the carbon content on the glass surface increased from 20.08 wt% to 34.15 wt%, which further proved the successful grafting of polystyrene. From the energy spectrum test results, combined with the scanning electron microscope analysis, it can be seen that using our process, polystyrene was successfully grafted to the surface of the modified glass, and polystyrene superhydrophobic self-cleaning glass was obtained.

(3) X-ray photoelectron spectroscopy analysis

In order to further understand the changes in the structure and composition of the glass surface before and after modification, X-ray photoelectron spectroscopy tests were carried out on the glass before and after modification. Among them, Figure 9 is a wide-spectrum scan of ordinary glass, Figure 10 is a high-resolution scan of ordinary glass C1s, Figure 11 is a wide-spectrum scan of polystyrene superhydrophobic self-cleaning glass, and Figure 12 is a high-resolution scan of polystyrene superhydrophobic self-cleaning glass C1s resolution scan.

Comparing Figure 9 and Figure 11, we found that, first, many element peaks such as C, Na, Si, Ca, and O appeared on the surface of ordinary glass, while only C, O, and A small amount of Si element; Second, the C/O peak of ordinary glass is much smaller than the C/O peak of polystyrene superhydrophobic self-cleaning coating; this shows that we have successfully realized polystyrene Grafting on glass surface to prepare polystyrene superhydrophobic coating. From the further C1s high-resolution comparison results, we found that there are many C1s peaks on the surface of ordinary glass, but only two peaks appear on the glass surface modified by polystyrene grafting, one C=C peak attributed to the benzene ring (284.8 eV), and the other is assigned to the C-C peak (291.5 eV), which is exactly consistent with the polystyrene structure, further illustrating the successful grafting of polystyrene.

(4) Contact angle test

The contact angle is very sensitive to the change of the surface properties of the modified sample, so the modification information of the material surface can be reflected by the test of the contact angle. In this experimental example, the contact angles of the ordinary glass, hydroxylated glass, terminal double bond modified glass and self-cleaning glass of Example 10 were tested. Among them, Fig. 13 is ordinary glass, Fig. 14 is hydroxylated glass, Fig. 15 is terminal double bond modified glass, Fig. 15 is self-cleaning glass with polystyrene-polymethyl methacrylate copolymer hydrophobic coating, Fig. 16 is in Self-cleaning glass with polystyrene-polymethyl methacrylate copolymerized hydrophobic coating directly grafted on the unoxidized glass surface.

It can be seen from the figure that the contact angle of the oxidized glass increases from 4° of the ordinary glass sheet to 35° of the oxidized glass sheet compared with the contact angle of the clean ordinary glass sheet; it is generally believed that the surface contains oxygen The contact angle will decrease with the increase of the amount of oxidized glass, but combined with the scanning electron microscope analysis results of oxidized glass and ordinary glass, the contact angle of the surface of the oxidized glass increases, which can be attributed to the rough surface of the oxidized glass. ; And compared with the oxidized glass flakes, the contact angle of the double-bonded glass formed by coupling with the silane coupling agent increases significantly; from 35° of the oxidized glass flakes to that of the coupled glass flakes 85°, which can be attributed to the introduction of terminal double bonds on the glass surface through silane coupling, resulting in a larger contact angle, indicating the success of silane coupling, which is consistent with the results of scanning electron microscopy; After the grafting of the methyl acrylate copolymer, the contact angle on the surface of the glass sheet increased significantly from 85° to 150°. This is due to the introduction of hydrophobic polymers, which introduced hydrophobic groups on the surface of the glass sheet, making Its hydrophobicity is enhanced; in addition, the roughness of the surface is also increased, which all lead to an increase of its contact angle. At the same time, we also did a comparative experiment, using the same process to graft polystyrene-polymethyl methacrylate copolymerized hydrophobic coating directly on the surface of unoxidized glass. We found that the contact angle was only about 85°, It is significantly smaller than the contact angle of the superhydrophobic self-cleaning coating prepared by our oxidation-coupling-polymerization process. This is because the oxidation process greatly increases the hydroxyl content on the glass surface and improves the efficiency of the surface-grafted hydrophobic coating. If the polymer is directly grafted, due to the low content of surface hydroxyl groups, the amount of grafted polymer is very small, which cannot reach the degree of hydrophobicity. Can further prove from contact angle test result, utilize the method provided by the invention to be able to successfully realize the chemical grafting of polystyrene-polymethyl methacrylate copolymer on common glass surface, consistent with scanning electron microscope result; And this coating has Good hydrophobicity.

(5) Light transmission analysis

After a series of modification and grafting on the glass surface, whether the light transmittance of the glass is reduced was tested with a UV-Vis spectrophotometer. In this experimental example, the contact angles of the common glass and the self-cleaning glass of Example 11 were tested. Figure 18 is the UV-Vis transmission spectrum, where (a) is ordinary glass, (b) is hydroxylated glass, (c) is terminal double bond modified glass, (d) is polystyrene-polymethyl methacrylate Copolymerized hydrophobic coating self-cleaning glass.

It can be seen from the figure that after a series of modification and surface grafting of the hydrophobic glass prepared by this process, the light transmittance of the self-cleaning glass grafted with polystyrene-polymethyl methacrylate copolymer is comparable to that of ordinary glass. Compared with glass, the light transmittance is slightly reduced, but still maintains more than 95% of ordinary glass. It shows that the hydrophobic coating of polystyrene-polymethylmethacrylate copolymer does not affect the light transmission of glass, which is due to the superior light transparency of polystyrene and polymethylmethacrylate. The test results of the ultraviolet-visible spectrophotometer show that we have successfully obtained a new type of super-hydrophobic self-cleaning glass with excellent light transmission.

(6) Self-cleaning performance

The results of contact angle test, scanning electron microscope and energy spectrum test show that the oxidation-coupling-grafting process on the glass surface has successfully achieved the covalent grafting of polymers on the glass surface, and the light transmission is good. But after the oxidation-coupling-grafting process, does the prepared hydrophobic coating have self-cleaning properties? We tested the surface pollution of ordinary glass and self-cleaning glass with polytetrafluoroethylene hydrophobic coating prepared by this process after different time outdoors, and artificial water washing was used to simulate the natural rain washing effect. In this experimental example, the self-cleaning properties of the ordinary glass used in Example 18 and the glass with a polytetrafluoroethylene hydrophobic coating were tested, and the results are shown in the table below.

"+": represents the degree of pollution of the glass, the more + signs, the more serious the pollution;

"-": Represents the cleanliness of the glass, the more - signs, the cleaner.

It can be seen from the table that the surface of ordinary glass will become more and more dirty when it is placed outdoors; however, the surface of glass with Teflon hydrophobic coating is hardly polluted after being placed for 20 days. After one month, the surface of the glass is partially polluted, but not all of the surface is polluted by dust, which may be caused by the uneven surface. The self-cleaning performance test shows that the glass modified by PTFE hydrophobic coating has a significant self-cleaning performance compared with ordinary glass, indicating that the oxidation-coupling-spraying polymer process proposed by us is a very effective method for preparing new hydrophobic materials. A method of self-cleaning glass.

The above description is only a preferred embodiment of the present invention, and does not limit the present invention in any form. Although the present invention has been disclosed as above with preferred embodiments, it is not intended to limit the present invention. Anyone familiar with this field Those skilled in the art, without departing from the scope of the technical solution of the present invention, may use the technical content disclosed above to make some changes or modify equivalent embodiments with equivalent changes, but if they do not depart from the technical solution of the present invention, the Any simple modifications, equivalent changes and modifications made to the above embodiments by the technical essence still belong to the scope of the technical solutions of the present invention.

Claims (2)

1. a preparation method of superhydrophobic self-cleaning glass, is characterized in that: comprise the following steps: (1) Hydroxylation of ordinary glass surface: prepare piranha solution, control the temperature at 50-100°C, add cleaned ordinary glass, oxidize for 1-120min, wash and dry with deionized water after oxidation; (2) Double bond on the glass surface: put the glass obtained in step (1) in toluene, add a silane coupling agent with a double bond at the end group, stop the reaction after refluxing for 5-30 hours, take out the glass piece, and clean it ultrasonically Let dry at room temperature; (3) Glass-grafted polymer: In the reaction bottle, add the double-bonded glass flakes prepared in step (2), the reaction medium is distilled water, and the polymerization temperature is 60-80°C; add styrene and methacrylic acid Methyl ester blend monomer, the molar ratio of styrene and methyl methacrylate monomer in the blend monomer is 20-10:1, add initiator ammonium persulfate under _N protection, the consumption of initiator is unit Add 1-5% of the weight of the body, and stop after 5-20 hours of reaction; take out the glass sheet, wash it with ethanol and water ultrasonically, and dry it at room temperature to obtain a superhydrophobic self-cleaning glass. 2. the preparation method of a kind of superhydrophobic self-cleaning glass as claimed in claim 1 is characterized in that: the silane coupling agent that the described end group is a double bond is gamma-methacryloyloxypropyltrimethoxy Silane, γ-methacryloxypropyltriethoxysilane, vinyltrimethoxysilane or vinyltriethoxysilane.