CN115637104A - Preparation method and application of tetraethoxysilane-siloxane-surfactant hybrid material - Google Patents

Abstract

The invention relates to a preparation method and application of tetraethyl orthosilicate-siloxane-surfactant hybrid material. In the method, siloxane and catalyst are added to tetraethyl orthosilicate (TEOS) for pre-mixing, Obtain dispersion solution a; Add absolute ethanol and surfactant to dispersion solution a, disperse evenly, obtain orthosilicate-siloxane-surfactant hybrid material, the hybrid material that makes is transparent Solution, has good permeability, easy to form film on the surface of ceramic cultural relics, fast film formation, high strength, good toughness, good thermal stability and optical properties after film formation, and has good hydrophobicity, which can meet the protection needs of pottery .

Description

A kind of preparation method of ethyl orthosilicate-siloxane-surfactant hybrid material and application

technical field

The invention relates to a preparation method and application of a tetraethyl orthosilicate-siloxane-surfactant hybrid material, belonging to the technical field of pottery protection materials.

Background technique

Due to natural factors (stone aging), human factors and other reasons, ceramic cultural relics may suffer damage to varying degrees. Therefore, effective measures should be taken as soon as possible to protect these historical heritages. The most widely used in these measures is the reinforcement material, which can be roughly divided into three categories: inorganic materials, organic materials and silicon composite materials. Inorganic materials are used to fill the micro-pores of the stone, creating a barrier or replacement layer. At present, commonly used inorganic materials are: lime water, barium hydroxide, etc. Its reinforcement mechanism is similar, that is, it reacts with carbon dioxide in the air, and the generated calcium carbonate (or barium carbonate) fills the pores of stone cultural relics, playing the role of reinforcement and protection. In later studies, it was found that these reinforcement materials mainly act on the surface layer, and have relatively little protection effect on the interior of the cultural relics. In addition, cement and alkaline earth silicate will eventually decompose to generate salt harmful to cultural relics, which limits their application in cultural relics reinforcement. Organic materials are currently the most widely used reinforcement materials in my country. After it is mixed with curing agent, it can be cured under specific conditions, and the curing shrinkage rate is low. At present, commercial products such as Paraloid-72 (copolymer of acrylate and methacrylate), PrimalAC33, WD10, and Primal SF are widely used, but the organic materials themselves have poor heat resistance, light aging resistance, and easy yellowing Issues such as brittleness make the protected cultural relics unable to resist the irradiation of ultraviolet light.

From this, it can be found that neither a single organic material nor a single inorganic material can meet the requirements for the reinforcement and protection of cultural relics. Later, it was found that the alkoxysilane material has a semi-organic and semi-inorganic structure with a Si-O bond as its skeleton and an alkyl group as its side chain. It has the advantages of strong adhesion, good waterproof and air permeability, and is the same silicon-based material as the protected cultural relics, which has good compatibility and is suitable for the requirements of cultural relics protection materials, such as orthoethyl silicate (TEOS) , which has the advantages of low viscosity and high chemical stability. However, the silica gel formed by hydrolysis of TEOS is easy to crack under dry conditions, which has a negative impact on the reinforcement effect.

Hybrid materials are a special kind of organic-inorganic composite materials, whose organic and inorganic components interact at the molecular level. The advantages of each component, give full play to the excellent properties of each component, so that the mechanical properties of hybrid materials are significantly better than conventional materials. However, the existing hybrid materials have the following disadvantages: the preparation method is complex, the amount of organic solvent used is large, the environmental protection is poor, the energy consumption is high, and the stability is poor.

For example, Chinese patent document CN113717387B (application number: CN202110826119.4) discloses a cage type POSS-linear siloxane hybrid material suitable for the protection of sandstone cultural relics, its preparation method and application. Dissolve POSS into a mixed solution of acetone and absolute ethanol to obtain a cage-type octaglycidyl POSS dispersion solution; then add a catalytic ring-opening agent and linear amino PDMS, stir and heat for ring-opening reaction, and obtain a cage-type POSS line Type siloxane hybrid material, which endows the hybrid material with good hardness. Another example: Chinese patent document CN113354444B (application number: CN202110728546.9) discloses a modified bentonite-based hydrogel precursor solution, preparation method and use method for the protection of silicate cultural relics, and solves the problem of weathering and shedding of cultural relics. protected.

Therefore, it is of great significance to study pottery cultural relics protection materials with good integrity, excellent performance, eco-friendliness, convenient operation and wide use in the field of cultural relics protection.

Contents of the invention

Aiming at the technical problems existing in the prior art, especially the problems of complicated preparation methods, poor environmental protection and poor stability, the present invention provides a kind of tetraethyl orthosilicate-siloxane-surfactant hybrid material Preparation method and application.

The hybrid material obtained by the invention has high strength, good toughness, good thermal stability and optical properties after film formation, and has good hydrophobicity, which can meet the protection requirements of pottery.

Terminology Explanation:

Tyloxapol: It is a high-molecular non-ionic surfactant, which contains benzene rings in the molecule, has π-π stacking effect, and has fluorescence phenomenon. The average degree of polymerization is 7 and the relative molecular mass is 4611.

The present invention is achieved through the following technical solutions:

A preparation method of tetraethyl orthosilicate-siloxane-surfactant hybrid material, comprising steps as follows:

1) At room temperature, the siloxane and the catalyst were added to tetraethyl orthosilicate (TEOS) for pre-mixing, and then ultrasonically dispersed until the solution was colorless, transparent and uniform, to obtain dispersion solution a;

2) adding absolute ethanol and a surfactant into the dispersion solution a, and dispersing evenly to obtain a tetraethyl orthosilicate-siloxane-surfactant hybrid material.

According to the present invention, preferably, in step 1), the siloxane is hydroxyl-terminated polydimethylsiloxane (PDMS-OH), and the mass of the siloxane is 0.1-20% of the mass of the dispersion solution a.

According to the present invention, preferably, in step 1), the mass of siloxane is 10-20% of the mass of dispersion solution a.

Most preferably, in step 1), the mass of siloxane is 15-20% of the mass of dispersion solution a.

According to the present invention, preferably, in step 1), the catalyst is dibutyltin dilaurate (DBTL), and the mass of the catalyst is 0.5-2% of the mass of the dispersion solution a.

According to the present invention, preferably, in step 1), the ultrasonic frequency of ultrasonic dispersion is 60-80 Hz, the ultrasonic power is 60 W, the ultrasonic time is 2-2.5 h, and the ultrasonic temperature is 25°C.

According to the present invention, preferably, in step 2), the surfactant is Tyloxapol, and the molar ratio of the surfactant to tetraethyl orthosilicate (TEOS) is 0.0005˜0.001:1.

According to the present invention, preferably, in step 2), the molar ratio of absolute ethanol to tetraethyl orthosilicate (TEOS) is 0.5˜1:1.

According to the present invention, preferably, in step 2), the uniform dispersion is specifically: firstly add absolute ethanol and Tyloxapol dropwise at room temperature and pre-mix in a vortex shaker, and then ultrasonically disperse until the solution is colorless Transparent and uniform state

Further, preferably, in step 2), the ultrasonic frequency of ultrasonic dispersion is 60-80 Hz, the ultrasonic power is 60 W, the ultrasonic time is 1-1.5 h, and the ultrasonic temperature is 25°C.

A tetraethyl orthosilicate-siloxane-surfactant hybrid material is prepared by the above-mentioned method.

The present invention also provides the application of the above-mentioned tetraethyl orthosilicate-siloxane-surfactant hybrid material.

Application of tetraethyl orthosilicate-siloxane-surfactant hybrid materials for pottery protection.

Preferably according to the present invention, specific application method is as follows:

Coating tetraethyl orthosilicate-siloxane-surfactant hybrid material on the part of pottery to be protected, wetting it evenly and then drying it naturally at room temperature for 48 hours, so as to form a uniform and dense protective film on pottery, Realize the reinforcement and protection of pottery.

The invention adopts ethyl orthosilicate, siloxane, and surfactant as raw materials to prepare hybrid materials. During the preparation process, ethyl orthosilicate TEOS is hydrolyzed and condensed to form a network structure composed of Si-O-Si, which endows hetero Chemical materials have good thermal stability, optical properties, heat resistance, elasticity and toughness. In PDMS-OH, the Si-O bond faces the helical axis, and the -CH ₃ is outside the plane, shielding the Si-O bond. In this structure, the bond angle of the Si-O bond is close to 150°, which is prone to internal rotation, so that the obtained The hybrid material has excellent mechanical properties. At the same time, -CH3 in PDMS-OH is a hydrophobic group, which endows the hybrid material with good hydrophobic properties; the hybridization of tetraethyl orthosilicate, siloxane, and surfactant is equivalent to A strong "bridge" is introduced into the network structure composed of Si-O-Si, so the hybrid material has high strength, good toughness, good thermal stability and good optical properties after film formation, and at the same time, the strong flexibility of PDMS-OH makes it The sol can resist the force of drying shrinkage, making the film more smooth, and the surfactant makes the film have microscopic and nanostructured surface protrusions, as well as overall changes in surface morphology and roughness, thereby preventing cracking during the drying process , therefore, the stability is strong.

The hydrolytic condensation of ethyl orthosilicate forms a network structure composed of Si-O-Si, and the reaction process is as follows:

Hydrolysis reaction (A) and water loss/alcohol loss reaction (B):

A

B

Compared with the prior art, it has the following beneficial effects:

1. The present invention uses tetraethyl orthosilicate, siloxane, and surfactant as raw materials to prepare the hybrid material, which is a transparent solution with good permeability, easy to form a film on the surface of ceramic cultural relics, and the film is fast. Does not affect the surface gloss and feel of ceramic cultural relics.

2. After forming a film, the hybrid material prepared by the present invention has high strength, good toughness, good thermal stability and optical properties, smooth film formation, no cracking in the drying process, and strong stability.

3. The preparation method of the hybrid material of the present invention is convenient, the raw materials are easy to obtain, and the product does not need post-processing, which is economical and environmentally friendly, and has high operability.

Description of drawings

Fig. 1 is when not adding surfactant Tyloxapol, the infrared spectrogram of the hybrid material that comparative example 1-5 makes;

Fig. 2 is when no surfactant Tyloxapol is added, the hybrid material prepared in Comparative Examples 1-5 forms a film in a petri dish; A is Comparative Example 1, B is Comparative Example 2, C is Comparative Example 3, D Is Comparative Example 4, E is Comparative Example 5;

Fig. 3 is when not adding surfactant Tyloxapol, the scanning electron micrograph of the film that the hybrid material that comparative example 1-5 makes forms in culture dish; A is comparative example 1, B is comparative example 2, C is comparative example 3, D is comparative example 4, E is comparative example 5;

Fig. 4 is when not adding surfactant Tyloxapol, the X-ray photoelectron energy spectrum (XPS) analysis figure of the film that the hybrid material that comparative example 5 makes forms in petri dish; A is XPS total spectrogram, and B is XPS- Si2p spectrum, C is XPS-C1s spectrum;

Fig. 5 is when not adding surfactant Tyloxapol, the static water contact angle figure of the hybrid material that comparative example 5 makes in the culture dish that forms film;

Fig. 6 is after adding surfactant Tyloxapol, the scanning electron micrograph of the film that the hybrid material that embodiment 1-4 makes forms in petri dish; A is embodiment 1, and B is embodiment 2, and C is embodiment 3, D is embodiment 4;

Fig. 7 is after adding surfactant Tyloxapol, the static water contact angle figure of the film that the hybrid material that embodiment 1-4 makes forms in petri dish; A is embodiment 1, and B is embodiment 2, and C is embodiment Example 3, D is embodiment 4;

Figure 8 is the static water contact angle diagram of pottery surfaces with different treatments, A is the pottery without reinforcement protection, B is the pottery protected by the hybrid material prepared in Comparative Example 5, and C is the hybrid material protected by Example 1. pottery;

Figure 9 is a scanning electron microscope image of pottery surfaces with different treatments, A is the pottery without reinforcement protection, B is the pottery protected by the hybrid material prepared in Comparative Example 5, and C is the pottery protected by the hybrid material prepared in Example 1 .

Detailed ways

In order to make the purpose, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions of the present invention will be clearly and completely described below in conjunction with the accompanying drawings. Obviously, the described embodiments are part of the embodiments of the present invention, not all of them. the embodiment. Based on the embodiments of the present invention, all other embodiments obtained by persons of ordinary skill in the art without making creative efforts belong to the protection scope of the present invention.

The preparation method of a kind of tetraethyl orthosilicate-siloxane-surfactant hybrid material of the present invention comprises the following steps:

Step 1: At room temperature, PDMS-OH and dibutyltin dilaurate (DBTL) were added dropwise to tetraethyl orthosilicate (TEOS) and pre-mixed in a vortex shaker, and then ultrasonically dispersed until the solution was free. The color is transparent and uniform, and the dispersion is uniform, and the dispersion solution a is obtained.

Preferably, the mass of PDMS-OH is 0.1-20% of the mass of dispersion solution a, the mass of dibutyltin dilaurate (DBTL) is 0.5-2% of the mass of dispersion solution a; the ultrasonic frequency of ultrasonic dispersion is 60-80Hz, The ultrasonic power is 60W, the ultrasonic time is 2-2.5h, and the ultrasonic temperature is 25°C

Step 2: Dissolve absolute ethanol and surfactant Tyloxapol into the dispersion solution a in step 1 at room temperature, first pre-mix it in a vortex shaker, and then perform ultrasonic dispersion until the solution is colorless, transparent and uniform state, and finally the prepared hybrid material

Preferably, the molar ratio of absolute ethanol to TEOS is 0.5˜1:1. The molar ratio of surfactant Tyloxapol to TEOS is 0.0005-0.001:1. The ultrasonic frequency of ultrasonic dispersion is 60-80Hz, the ultrasonic power is 60W, the ultrasonic time is 1-1.5h, and the ultrasonic temperature is 25°C.

Example 1:

A preparation method of tetraethyl orthosilicate-siloxane-surfactant hybrid material, the steps are as follows:

1) At room temperature, first add PDMS-OH and dibutyltin dilaurate (DBTL) to tetraethyl orthosilicate (TEOS) dropwise, pre-mix in a vortex shaker, and then ultrasonically disperse until the solution is colorless In a transparent and uniform state, the dispersion is uniform, and the dispersion solution a is obtained;

Among them, the quality of PDMS-OH is 20% of the mass of dispersion solution a, the quality of dibutyltin dilaurate (DBTL) is 1% of the mass of dispersion solution a; the ultrasonic frequency of ultrasonic dispersion is 70Hz, the ultrasonic power is 60W, and the ultrasonic time 2h, the ultrasonic temperature is 25°C;

2) Dissolve absolute ethanol and surfactant Tyloxapol into the dispersion solution a in step 1) at room temperature, first pre-mix it in a vortex shaker, and then ultrasonically disperse until the solution is colorless, transparent and uniform state, and finally the prepared hybrid material is obtained.

Among them, the molar ratio of absolute ethanol to TEOS is 0.5:1, the molar ratio of surfactant Tyloxapol to TEOS is 0.0005:1, the ultrasonic frequency of ultrasonic dispersion is 70Hz, the ultrasonic power is 60W, the ultrasonic time is 1h, and the ultrasonic temperature is 25°C.

The prepared hybrid material was poured into a plastic Petri dish (d = 3.5 cm), allowed to gel and dry for 48 h at room temperature until reaching a constant weight and forming a uniform film on the Petri dish.

Example 2:

A preparation method of tetraethyl orthosilicate-siloxane-surfactant hybrid material, the steps are as follows:

1) At room temperature, first add PDMS-OH and dibutyltin dilaurate (DBTL) to tetraethyl orthosilicate (TEOS) dropwise, pre-mix in a vortex shaker, and then ultrasonically disperse until the solution is colorless In a transparent and uniform state, the dispersion is uniform, and the dispersion solution a is obtained;

Among them, the quality of PDMS-OH is 20% of the mass of dispersion solution a, the quality of dibutyltin dilaurate (DBTL) is 1% of the mass of dispersion solution a; the ultrasonic frequency of ultrasonic dispersion is 70Hz, the ultrasonic power is 60W, and the ultrasonic time 2h, the ultrasonic temperature is 25°C;

2) Dissolve absolute ethanol and surfactant Tyloxapol into the dispersion solution a in step 1) at room temperature, first pre-mix it in a vortex shaker, and then ultrasonically disperse until the solution is colorless, transparent and uniform state, and finally the prepared hybrid material is obtained.

Among them, the molar ratio of absolute ethanol to TEOS is 1:1, the molar ratio of surfactant Tyloxapol to TEOS is 0.0005:1, the ultrasonic frequency of ultrasonic dispersion is 70Hz, the ultrasonic power is 60W, the ultrasonic time is 1h, and the ultrasonic temperature is 25°C.

The prepared hybrid material was poured into a plastic Petri dish (d = 3.5 cm), allowed to gel and dry for 48 h at room temperature until reaching a constant weight and forming a uniform film on the Petri dish.

Example 3:

A preparation method of tetraethyl orthosilicate-siloxane-surfactant hybrid material, the steps are as follows:

1) At room temperature, first add PDMS-OH and dibutyltin dilaurate (DBTL) to tetraethyl orthosilicate (TEOS) dropwise, pre-mix in a vortex shaker, and then ultrasonically disperse until the solution is colorless In a transparent and uniform state, the dispersion is uniform, and the dispersion solution a is obtained;

Among them, the quality of PDMS-OH is 20% of the mass of dispersion solution a, the quality of dibutyltin dilaurate (DBTL) is 1% of the mass of dispersion solution a; the ultrasonic frequency of ultrasonic dispersion is 70Hz, the ultrasonic power is 60W, and the ultrasonic time 2h, the ultrasonic temperature is 25°C;

2) Dissolve absolute ethanol and surfactant Tyloxapol into the dispersion solution a in step 1) at room temperature, first pre-mix it in a vortex shaker, and then ultrasonically disperse until the solution is colorless, transparent and uniform state, and finally the prepared hybrid material is obtained.

Among them, the molar ratio of absolute ethanol to TEOS is 0.5:1, the molar ratio of surfactant Tyloxapol to TEOS is 0.001:1, the ultrasonic frequency of ultrasonic dispersion is 70Hz, the ultrasonic power is 60W, the ultrasonic time is 1h, and the ultrasonic temperature is 25°C.

The prepared hybrid material was poured into a plastic Petri dish (d = 3.5 cm), allowed to gel and dry for 48 h at room temperature until reaching a constant weight and forming a uniform film on the Petri dish.

Example 4:

A preparation method of tetraethyl orthosilicate-siloxane-surfactant hybrid material, the steps are as follows:

1) At room temperature, first add PDMS-OH and dibutyltin dilaurate (DBTL) to tetraethyl orthosilicate (TEOS) dropwise, pre-mix in a vortex shaker, and then ultrasonically disperse until the solution is colorless In a transparent and uniform state, the dispersion is uniform, and the dispersion solution a is obtained;

Among them, the quality of PDMS-OH is 20% of the mass of dispersion solution a, the quality of dibutyltin dilaurate (DBTL) is 1% of the mass of dispersion solution a; the ultrasonic frequency of ultrasonic dispersion is 70Hz, the ultrasonic power is 60W, and the ultrasonic time 2h, the ultrasonic temperature is 25°C;

2) Dissolve absolute ethanol and surfactant Tyloxapol into the dispersion solution a in step 1) at room temperature, first pre-mix it in a vortex shaker, and then ultrasonically disperse until the solution is colorless, transparent and uniform state, and finally the prepared hybrid material is obtained.

Among them, the molar ratio of absolute ethanol to TEOS is 1:1, the molar ratio of surfactant Tyloxapol to TEOS is 0.001:1, the ultrasonic frequency of ultrasonic dispersion is 70Hz, the ultrasonic power is 60W, the ultrasonic time is 1h, and the ultrasonic temperature is 25°C.

The prepared hybrid material was poured into a plastic Petri dish (d = 3.5 cm), allowed to gel and dry for 48 h at room temperature until reaching a constant weight and forming a uniform film on the Petri dish.

Comparative example 1:

With the method described in embodiment 1, difference is:

Step 1: At room temperature, first add PDMS-OH and DBTL to TEOS dropwise, pre-mix in a vortex shaker, and then ultrasonically disperse until the solution is colorless, transparent and uniform, and the dispersion is uniform to obtain a hybrid material.

The quality of PDMS-OH is 0% of the mass of dispersion solution a, the quality of dibutyltin dilaurate (DBTL) is 1% of the mass of dispersion solution a; the ultrasonic frequency of ultrasonic dispersion is 70Hz, the ultrasonic power is 60W, and the ultrasonic time is 2h , the ultrasonic temperature was 25°C.

Step 2: The prepared hybrid material was poured into a plastic petri dish (d=3.5 cm), allowed to gel and dry for 48 hours at room temperature until reaching a constant weight and forming a uniform film on the petri dish.

Comparative example 2:

With the method described in embodiment 1, difference is:

Step 1: At room temperature, first add PDMS-OH and DBTL to TEOS dropwise, pre-mix in a vortex shaker, and then ultrasonically disperse until the solution is colorless, transparent and uniform, and the dispersion is uniform to obtain a hybrid material.

The quality of PDMS-OH is 5% of the mass of dispersion solution a, the quality of dibutyltin dilaurate (DBTL) is 1% of the mass of dispersion solution a; the ultrasonic frequency of ultrasonic dispersion is 70Hz, the ultrasonic power is 60W, and the ultrasonic time is 2h , the ultrasonic temperature was 25°C.

Step 2: The prepared hybrid material was poured into a plastic petri dish (d=3.5 cm), allowed to gel and dry for 48 hours at room temperature until reaching a constant weight and forming a uniform film on the petri dish.

Comparative example 3:

With the method described in embodiment 1, difference is:

Step 1: At room temperature, first add PDMS-OH and DBTL to TEOS dropwise, pre-mix in a vortex shaker, and then ultrasonically disperse until the solution is colorless, transparent and uniform, and the dispersion is uniform to obtain a hybrid material.

The quality of PDMS-OH is 10% of the mass of dispersion solution a, the quality of dibutyltin dilaurate (DBTL) is 1% of the mass of dispersion solution a; the ultrasonic frequency of ultrasonic dispersion is 70Hz, the ultrasonic power is 60W, and the ultrasonic time is 2h , the ultrasonic temperature was 25°C.

Step 2: The prepared hybrid material was poured into a plastic petri dish (d=3.5 cm), allowed to gel and dry for 48 hours at room temperature until reaching a constant weight and forming a uniform film on the petri dish.

Comparative example 4:

With the method described in embodiment 1, difference is:

Step 1: At room temperature, first add PDMS-OH and DBTL to TEOS dropwise, pre-mix in a vortex shaker, and then ultrasonically disperse until the solution is colorless, transparent and uniform, and the dispersion is uniform to obtain a hybrid material.

The quality of PDMS-OH is 15% of the mass of dispersion solution a, the quality of dibutyltin dilaurate (DBTL) is 1% of the mass of dispersion solution a; the ultrasonic frequency of ultrasonic dispersion is 70Hz, the ultrasonic power is 60W, and the ultrasonic time is 2h , the ultrasonic temperature was 25°C.

Step 2: The prepared hybrid material was poured into a plastic petri dish (d=3.5 cm), allowed to gel and dry for 48 hours at room temperature until reaching a constant weight and forming a uniform film on the petri dish.

Comparative example 5:

With the method described in embodiment 1, difference is:

Step 1: At room temperature, first add PDMS-OH and DBTL to TEOS dropwise, pre-mix in a vortex shaker, and then ultrasonically disperse until the solution is colorless, transparent and uniform, and the dispersion is uniform to obtain a hybrid material.

The quality of PDMS-OH is 20% of the mass of dispersion solution a, the quality of dibutyltin dilaurate (DBTL) is 1% of the mass of dispersion solution a; the ultrasonic frequency of ultrasonic dispersion is 70Hz, the ultrasonic power is 60W, and the ultrasonic time is 2h , the ultrasonic temperature was 25°C.

Step 2: Pour the prepared hybrid material into a plastic petri dish (d=3.5cm), let it gel and dry for 4-8h at room temperature, until reaching a constant weight and forming a uniform film on the petri dish.

Experimental example 1:

Evaluate the hybrid materials of Comparative Examples 1-5:

Evaluation 1: The prepared hybrid material was transferred to a Petri dish (d=3.5 cm), allowed to gel and dry for 48 hours at room temperature until reaching a constant weight, and formed a thin film after curing for 48 hours. As shown in Figure 1, the infrared spectrum shows the formation of its silicon network.

Evaluation 2: Transfer the prepared hybrid material to a petri dish (d=3.5 cm), let it gel and dry for 48 hours at room temperature until reaching a constant weight, and form a thin film after curing for 48 hours. Figure 2 shows the film-forming property in the petri dish. With the gradual increase of PDMS-OH content, the film in the petri dish becomes flat gradually.

Evaluation 3: Transfer the prepared hybrid material to a Petri dish (d=3.5 cm), let it gel and dry for 48 hours at room temperature until reaching a constant weight, and form a film after curing for 48 hours. The scanning electron microscope picture shown in Figure 3 shows that as the content of PDMS-OH increases, the coating surface becomes gradually smooth and uniform, because PDMS-OH has a low surface energy, which reduces the stress during the drying shrinkage process, thereby Make the surface of the hybrid material film uniform and smooth. Combining Figure 2 and Figure 3, it proves that the strong flexibility of PDMS-OH enables the sol to resist the force of drying shrinkage, making the film more smooth.

Evaluation 4: The hybrid material prepared in Comparative Example 5 was transferred to a Petri dish (d=3.5 cm), allowed to gel and dry for 48 hours at room temperature until reaching a constant weight, and formed a film after curing for 48 hours. As shown in the X-ray photoelectron spectroscopy (XPS) analysis diagram shown in Figure 4, the formation of the silicon network is further proved, and it is proved that PDMS-OH acts as a bridge to connect SiO2.

Evaluation 5: Transfer the hybrid material prepared in Comparative Example 5 to a Petri dish (d=3.5cm), let it gel and dry for 48 hours at room temperature until it reaches a constant weight, and form a film after curing for 48 hours . The static water contact angle diagram shown in Figure 5 proves that the hybrid material has a certain hydrophobic effect due to the presence of -CH3 in PDMS-OH.

Experimental example 2:

The hybrid materials of Examples 1-4 were evaluated:

Evaluation 1: The solution prepared in Examples 1-4 was transferred to a petri dish, and a thin film was formed after curing for 48 hours. Compared with Comparative Examples 1-5 by the scanning electron microscope picture shown in Figure 6, it can be seen that the coating surface uniformity increases, and this is because the adding of surfactant further reduces the capillary pressure in the drying shrinkage process; Simultaneously with Compared with Comparative Examples 1-5, small bumps are formed on the surface, which increases the roughness of the surface and prevents cracking during drying.

Evaluation 2: The solution prepared in Examples 1-4 was transferred to a petri dish, and a thin film was formed after curing for 48 hours. The static water contact angle diagram shown in Figure 7 proves that compared with Comparative Example 5, the water contact angle is much larger than that of Comparative Example 5, indicating that the hydrophobicity of the hybrid material is further enhanced.

Experimental example 3:

Apply the hybrid material obtained in Example 4 and the hybrid material obtained in Comparative Example 5 to the part of the pottery to be protected, wet it evenly, and then dry it naturally at room temperature for 48 hours, thereby forming a uniform protective film on the pottery , to achieve reinforcement and protection of pottery.

As shown in Figures 8 and 9, the hybrid material obtained in Example 4 forms a dense protective film on pottery. The static water contact angle of the pottery reinforced and protected by the hybrid material increases. It can be seen that the hybrid material increases the hydrophobicity, anti-fouling and durability of the pottery.

Claims (10)

1. a preparation method of tetraethyl orthosilicate-siloxane-surfactant hybrid material, comprising steps as follows: 1) At room temperature, the siloxane and the catalyst were added to tetraethyl orthosilicate (TEOS) for pre-mixing, and then ultrasonically dispersed until the solution was colorless, transparent and uniform, to obtain dispersion solution a; 2) adding absolute ethanol and a surfactant into the dispersion solution a, and dispersing evenly to obtain a tetraethyl orthosilicate-siloxane-surfactant hybrid material. 2. The preparation method according to claim 1, wherein the siloxane is hydroxyl-terminated polydimethylsiloxane (PDMS-OH), and the quality of the siloxane is 0.1% of the quality of the dispersion solution a. ~20%. 3. The preparation method according to claim 1, characterized in that, in step 1), the mass of siloxane is 10-20% of the mass of dispersion solution a. 4. The preparation method according to claim 1, characterized in that, in step 1), the mass of siloxane is 15-20% of the mass of dispersion solution a. 5. preparation method according to claim 1 is characterized in that, in step 1), described catalyzer is dibutyltin dilaurate (DBTL), and the quality of catalyzer is 0.5～2% of dispersion solution a quality; Step 1 ), the ultrasonic frequency of ultrasonic dispersion is 60-80 Hz, the ultrasonic power is 60 W, the ultrasonic time is 2-2.5 h, and the ultrasonic temperature is 25°C. 6. The preparation method according to claim 1, characterized in that, in step 2), the surfactant is Tyloxapol, and the molar ratio of the surfactant to tetraethyl orthosilicate (TEOS) is 0.0005-0.001:1 . 7. The preparation method according to claim 1, characterized in that, in step 2), the molar ratio of absolute ethanol to tetraethyl orthosilicate (TEOS) is 0.5-1:1. 8. The preparation method according to claim 1, characterized in that, in step 2), the uniform dispersion is specifically: at room temperature, first add absolute ethanol and Tyloxapol dropwise and pre-mix in a vortex shaker, Then perform ultrasonic dispersion until the solution is colorless, transparent and uniform; the ultrasonic frequency of ultrasonic dispersion is 60-80 Hz, the ultrasonic power is 60 W, the ultrasonic time is 1-1.5 h, and the ultrasonic temperature is 25°C. 9. A tetraethyl orthosilicate-siloxane-surfactant hybrid material, prepared by the method according to any one of claims 1-8. 10. the application of tetraethyl orthosilicate-siloxane-surfactant hybrid material described in claim 9, is used for pottery protection; The specific application method is as follows: Coating tetraethyl orthosilicate-siloxane-surfactant hybrid material on the part of pottery to be protected, wetting it evenly and then drying it naturally at room temperature for 48 hours, so as to form a uniform and dense protective film on pottery, Realize the reinforcement and protection of pottery.

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