CN109266211B - Organopolysiloxane super-hydrophobic coating and preparation method thereof - Google Patents

Abstract

The invention relates to the field of chemical industry, and discloses an organopolysiloxane superhydrophobic coating and a preparation method thereof. The molecular formula of an organosilane precursor in the coating is: R ₃ Si-X-SiR ₃ , and X in the formula is C _n H _2n carbon chain group, where n is 2, 4, 6, 8, 10 or 12, and R is Cl, OCH ₃ or OCH ₂ CH ₃ . The preparation method includes the following steps, including the following steps: at room temperature, after mixing a certain proportion of an organosilane precursor with a molecular formula of R ₃ Si-X-SiR ₃ and polydimethylsiloxane evenly, adding a photoacid generator, After stirring and dissolving, spraying on the substrate to form a film; placing it under a light-emitting diode lamp for 10-60 min to obtain the organopolysiloxane superhydrophobic coating. Compared with the existing super-hydrophobic coating preparation technology, the method has the advantages of simple operation, fast polymerization speed, no need to use organic solvents, energy saving and environmental protection, and has broad market prospects.

Description

Organopolysiloxane superhydrophobic coating and preparation method thereof

technical field

The invention relates to the technical field of coating preparation, in particular to an organopolysiloxane superhydrophobic coating and a preparation method thereof.

Background technique

Superhydrophobic coating materials have attracted widespread attention due to their special surface non-wettability, and have broad application prospects in the fields of self-cleaning, antifouling, anti-icing, anti-corrosion, and drag reduction.

At present, there are many preparation methods for superhydrophobic coatings, and a large number of different types of superhydrophobic coatings have been prepared. However, for practical applications, most of the reported preparation methods require special equipment and complicated processes, and a large number of organic volatile solvents are used in the preparation process, which makes them only suitable for laboratory research. In addition, traditional polymer coatings tend to lose their superhydrophobic properties when heated and applied outdoors, resulting in poor material stability and difficulty in industrial application.

SUMMARY OF THE INVENTION

Purpose of the invention: In view of the problems existing in the prior art, the present invention provides an organopolysiloxane superhydrophobic coating and a preparation method thereof. The main chain of the polysiloxane is not easily decomposed by ultraviolet light and ozone, and has good thermal stability. In addition, the method has the advantages of simple operation, fast polymerization speed, no need to use any solvent, energy saving and environmental protection.

Technical solution: The present invention provides an organopolysiloxane super-hydrophobic coating. The molecular formula of the organosilane precursor in the coating is: R ₃ Si-X-SiR ₃ , where X in the formula is a carbon of C _n H _2n chain group where n is 2, 4, 6, 8, 10 or 12 and R is _Cl , _OCH3 or _OCH2CH3 .

The invention also provides a preparation method of an organopolysiloxane superhydrophobic coating, comprising the following steps: at room temperature, a certain proportion of an organosilane precursor whose molecular formula is R ₃ Si-X-SiR ₃ is mixed with polydimethyl Siloxane is mixed, after stirring and mixing evenly, adding a photoacid generator, after stirring and dissolving, spraying on the substrate to form a film; placing it under a lamp for a preset time to obtain the organopolysiloxane superhydrophobic coating; In the organosilane precursor whose molecular formula is R ₃ Si-X-SiR ₃ , X in the formula is a carbon chain group of C _n H _2n , wherein n is 2, 4, 6, 8, 10 or 12, and R is _Cl , _OCH3 or _OCH2CH3 .

Preferably, the mass ratio between the organosilane precursor and the polydimethylsiloxane is 2-10:1.

Preferably, the mass ratio between the organosilane precursor, the polydimethylsiloxane and the photoacid generator is 1-10:1:0.05-0.5.

Preferably, the polydimethylsiloxane is end-capped with methoxy OCH ₃ and has an average molecular weight of 550 g/mol.

Preferably, the lamp is a light emitting diode with a specific wavelength, and the wavelength is 320 nm, 365 nm or 405 nm.

Preferably, the power of the light-emitting diode is 0.1-20 mW/cm ² ; preferably 0.5 mW/cm ² , 2 mW/cm ² , 5 mW/cm ² , and 10 mW/cm ² .

Preferably, the photoacid generator is diphenyl iodonium hexafluorophosphate (DH), 4-isobutylphenyl-4'-methylphenyl iodonium hexafluorophosphate (I250), 2- Methyl-α-[2-[[propanesulfonyl]imide]-3(2H)-thienylidene-phenylacetonitrile (PAG103), diphenyl-(4-phenylthio)phenylsulfonium hexafluoro Phosphate (UV6992) or 4-octoxydiphenyl iodonium hexafluoroantimonate (OPHA).

Preferably, the substrate is glass, silicon wafer, tinplate, aluminum alloy, polycarbonate, filter paper or woven cloth.

Preferably, the preset time for irradiation under the lamp is 10-60 min, preferably 15 min, 30 min, 45 min or 60 min.

Beneficial effects: in the present invention, the organosilane precursor, polydimethylsiloxane and the photoacid generator are directly mixed and stirred evenly, and then sprayed onto the substrate to obtain an organosilicon liquid coating; The super acid initiates the hydrolysis and condensation reaction of Si-Cl, SiOCH ₃ or SiOCH ₂ CH ₃ in the organosilane precursor to obtain the organopolysiloxane superhydrophobic coating. Among them, polydimethylsiloxane exists in the organopolysiloxane skeleton through the hydrolysis copolycondensation reaction of the end-capped _SiOCH3 group with Si _{- Cl} , _SiOCH3 or SiOCH2CH3 in the organosilane precursor. Its low surface energy characteristics, combined with the rough structure of the coating surface, make the resulting organopolysiloxanes have superhydrophobic properties.

Compared with the prior art, the preparation method provided by the invention only needs to simply mix the organosilane precursor and the photoacid generator without using a solvent, and the formula solution is very stable in the absence of light; the preparation of the coating only needs to be simple Lighting for 10~60min, it has the advantages of green environmental protection, simple and efficient, and can be widely used in substrates of different materials; the superhydrophobic coating in the present invention has excellent heat resistance and weather resistance, and is suitable for self-cleaning materials, anti-corrosion coatings, etc. with broadly application foreground.

Description of drawings

1 is a scanning electron microscope image and a water contact angle image of the coating surface in Example 2.

Detailed ways

The present invention will be described in detail below with reference to specific embodiments.

Embodiment 1:

9 g of 1,6-bis(trichlorosilyl)hexane (Cl ₃ Si-C ₆ H ₁₂ -SiCl ₃ ) and 1 g of polydimethylsilane were stirred and mixed uniformly, and then 4-isobutylphenyl-4 was added. '-Methylphenyliodohexafluorophosphate (I250) 0.2g, which was completely dissolved and sprayed on the substrate to form a film, illuminated with a 320nm LED light for 10min, and the LED power was 20 mW/cm ² to obtain an organopolysiloxane Superhydrophobic coating, the results are shown in Table 1.

Embodiment 2:

7.5 g of 1,6-bis(trimethoxysilyl)hexane[(CH ₃ O) ₃ Si-C ₆ H ₁₂ -Si(OCH ₃ ) ₃ ] and 2.5 g of polydimethylsilane were stirred and mixed uniformly, and then Add 0.05g of 2-methyl-α-[2-[[propanesulfonyl]imide]-3(2H)-thiophene methylene-phenylacetonitrile (PAG103), and spray it on the substrate to form a film, 405nm after complete dissolution The LED light was illuminated for 30 min, and the power of the LED was 0.5 mW/cm ² , and the organopolysiloxane superhydrophobic coating was obtained. The results are shown in Table 1. The scanning electron microscope image and water contact angle image of the coating surface of the coating are shown in Figure 1. It can be seen that the surface of the obtained organopolysiloxane superhydrophobic coating is rough, and the water contact angle is 156°.

Embodiment 3:

8 g of 1,2-bis(trimethoxysilyl)ethane [(CH ₃ O) ₃ Si-C ₂ H ₄ -Si(OCH ₃ ) ₃ ] and 2 g of polydimethylsilane were stirred and mixed uniformly, and then 4 g was added. -Octyloxydiphenyliodonium hexafluoroantimonate (OPHA) 0.1g, after it was completely dissolved, it was sprayed on the substrate to form a film, 365nm LED light was illuminated for 30min, the power of the LED was 2 mW/cm ² , and the organic polymer was obtained. Siloxane superhydrophobic coating, the results are shown in Table 1.

Embodiment 4:

1,8-bis(trimethoxysilyl)octane [(CH ₃ O) ₃ Si-C ₈ H ₁₆ -Si(OCH ₃ ) ₃ ] 7g and polydimethylsilane 3g were stirred and mixed uniformly, and then 2 -Methyl-α-[2-[[propanesulfonyl]imide]-3(2H)-thiophene-methylene-phenylacetonitrile (PAG103) 0.1g, completely dissolved and sprayed on the substrate to form a film, 405nm LED The light was illuminated for 30 min, the power of the LED was 0.5 mW/cm ² , and the organopolysiloxane superhydrophobic coating was obtained. The results are shown in Table 1.

Embodiment 5:

6 g of 1,10-bis(trimethoxysilyl)decane[(CH ₃ O) ₃ Si-C ₁₀ H ₂₀ -Si(OCH ₃ ) ₃ ] and 4 g of polydimethylsilane were stirred and mixed uniformly, and then 2 -Methyl-α-[2-[[propanesulfonyl]imide]-3(2H)-thiophene methylene-phenylacetonitrile (PAG103) 0.2g, completely dissolved and sprayed on the substrate to form a film, 405nm LED The light was illuminated for 30 min, and the power of the LED was 5 mW/cm ² to obtain an organopolysiloxane superhydrophobic coating. The results are shown in Table 1.

Embodiment 6:

Combine 1,12-bis(triethoxysilyl)dodecane[ _{( CH3CH2O ) 3Si} - _C12H24 -Si( _{OCH2CH3 ) 3} ] 6.5g with polydimethylsilane 3.5g g Stir and mix evenly, then add 0.5 g of 2-methyl-α-[2-[[propanesulfonyl]imide]-3(2H)-thiophene methylene-phenylacetonitrile (PAG103), and then add 0.5 g to the base A film was formed by spraying on the top, and the LED light of 405 nm was illuminated for 60 min, and the power of the LED was 10 mW/cm ² , and an organopolysiloxane superhydrophobic coating was obtained. The results are shown in Table 1.

Table 1 Test results of water contact angle of organopolysiloxane superhydrophobic coating

Note: The contact angle test adopts DSA25 automatic video contact angle measuring instrument produced by Krüss Company in Germany, and the average value of three parallel tests is taken.

The above-mentioned embodiments are only intended to illustrate the technical concept and features of the present invention, and the purpose is to enable those who are familiar with the art to understand the content of the present invention and implement it accordingly, and cannot limit the protection scope of the present invention. All equivalent transformations or modifications made according to the spirit of the present invention should be covered within the protection scope of the present invention.

Claims (9)

1. a preparation method of organopolysiloxane super-hydrophobic coating, is characterized in that, comprises the following steps: At room temperature, a certain proportion of an organosilane precursor with a molecular formula of R ₃ Si-X-SiR ₃ is mixed with polydimethylsiloxane, and after stirring and mixing uniformly, a photoacid generator is added, and after stirring and dissolving, it is placed on the substrate. spraying to form a film; placing it under a lamp for a preset time to obtain the organopolysiloxane superhydrophobic coating; In the organosilane precursor whose molecular formula is R ₃ Si-X-SiR ₃ , X in the formula is a carbon chain group of C _n H _2n , wherein n is 2, 4, 6, 8, 10 or 12, R is Cl, OCH ₃ or OCH ₂ CH ₃ . 2. the preparation method of organopolysiloxane superhydrophobic coating according to claim 1, is characterized in that, the mass ratio between described organosilane precursor and described polydimethylsiloxane is 2～10 :1. 3. the preparation method of organopolysiloxane superhydrophobic coating according to claim 1, is characterized in that, between described organosilane precursor, described polydimethylsiloxane and described photoacid generator The mass ratio of 1~10:1:0.05~0.5. 4. The preparation method of organopolysiloxane superhydrophobic coating according to claim 1, wherein the polydimethylsiloxane is methoxy OCH end _- capping, and the average molecular weight is 550 g/mol. 5. The preparation method of organopolysiloxane superhydrophobic coating according to claim 1, wherein the lamp is a light-emitting diode with a specific wavelength, and the wavelength is 320 nm, 365 nm or 405 nm. 6 . The method for preparing an organopolysiloxane superhydrophobic coating according to claim 5 , wherein the power of the light-emitting diode is 0.1-20 mW/cm ² . 7 . 7. according to the preparation method of the organopolysiloxane superhydrophobic coating described in any one in claim 1 to 6, it is characterized in that, described photoacid generator is diphenyliodonium hexafluorophosphate, 4 -Isobutylphenyl-4'-methylphenyliodohexafluorophosphate, 2-methyl-α-[2-[[propanesulfonyl]imide]-3(2H)-thiophene methylene- Benzylacetonitrile, diphenyl-(4-phenylthio)phenylsulfonium hexafluorophosphate or 4-octoxydiphenyliodonium hexafluoroantimonate. 8. according to the preparation method of the organopolysiloxane superhydrophobic coating described in any one of claim 1 to 6, it is characterized in that, described substrate is glass, silicon wafer, tinplate, aluminum alloy, polycarbonate, filter paper or weaving. 9. The preparation method of the organopolysiloxane superhydrophobic coating according to any one of claims 1 to 6, wherein the preset time for irradiating under the lamp is 10 to 60 min.

Images