CN111978861A

CN111978861A - Preparation method of phenyl polysiloxane super-hydrophobic coating

Info

Publication number: CN111978861A
Application number: CN202010905418.2A
Authority: CN
Inventors: 倪伶俐; 刘永涛; 徐成鹏; 杨昌佑; 郑菲; 蔡鹏�; 姜孝武
Original assignee: Huaiyin Institute of Technology
Current assignee: Huaiyin Institute of Technology
Priority date: 2020-09-01
Filing date: 2020-09-01
Publication date: 2020-11-24
Anticipated expiration: 2040-09-01
Also published as: CN111978861B

Abstract

The invention relates to the field of coatings, and discloses a preparation method of phenyl polysiloxane super-hydrophobic coating, which comprises the steps of adding a certain proportion of diphenyl dihydroxy silane solid precursor and a photobase generator into a certain amount of organic solvent at room temperature, mixing and stirring uniformly, and spraying and coating on a substrate; and (3) after the substrate coated with the sample is illuminated under an ultraviolet lamp for a preset time, putting the substrate into an oven for drying to obtain the phenyl polysiloxane super-hydrophobic coating. Compared with the existing super-hydrophobic coating preparation technology, the method is simple to operate, the obtained coating is uniform, the shrinkage rate is low, and the method has a wide market prospect.

Description

Preparation method of phenyl polysiloxane super-hydrophobic coating

Technical Field

The invention relates to the technical field of paint preparation, and particularly relates to a preparation method of phenyl polysiloxane super-hydrophobic paint.

Background

In recent years, due to the special wettability and potential application value of the surface of the super-hydrophobic coating, the super-hydrophobic coating attracts wide attention in the industry. However, the raw materials for preparing the super-hydrophobic coating are basically fluorine-containing compounds or organosilane with complex structure and high price, and special equipment, harsh environment and other conditions are needed for preparing the coating. In addition, the mechanical strength and durability of the surface of the prepared super-hydrophobic coating can not meet the requirements of practical application. The above factors limit the application of superhydrophobic coatings in the fields of self-cleaning, corrosion prevention, drag reduction, and the like.

Disclosure of Invention

The purpose of the invention is as follows: aiming at the problems in the prior art, the invention provides a preparation method of phenyl polysiloxane super-hydrophobic coating, and the prepared phenyl polysiloxane super-hydrophobic coating has the advantages of good wear resistance, high usable temperature and the like.

The technical scheme is as follows: the invention provides a phenyl organopolysiloxane super-hydrophobic coating,

at room temperature, adding a certain proportion of diphenyl dihydroxy silane solid precursor and a photobase generator into a certain amount of organic solvent, mixing and stirring uniformly, and spraying and coating on a substrate; and (3) after the substrate coated with the sample is illuminated under an ultraviolet lamp for a preset time, putting the substrate into an oven for drying to obtain the phenyl polysiloxane super-hydrophobic coating.

Preferably, the mass ratio of the diphenyl dihydroxysilane solid precursor to the photobase generator is 1: 0.02-0.10.

Preferably, the photobase generator is 2-methyl-1- (4-methylthiophenyl) -2-morpholinyl-1-propanone, 2-phenylbenzyl-2-dimethylamine-1- (4-morpholinylbenzyl) butanone or 2- (4-methylbenzyl) -2- (dimethylamino) -1- (4-morpholinylphenyl) -1-butanone.

Preferably, the organic solvent is ethanol, tetrahydrofuran, toluene, chloroform or acetonitrile.

Preferably, the preset time is 20-60 min. Preferably, the temperature of the oven is 60-120 deg.C^oC. Preferably 80 to 100^oC。

Preferably, the drying time is 24-288 h. Preferably, the drying time is 48-144 h.

Preferably, the power of the ultraviolet lamp is 0.1-20 mW/cm²Preferably 0.5-5 mW/cm²。

Preferably, the wavelength of the ultraviolet lamp is 240nm or 320 nm.

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

Has the advantages that: in the invention, diphenyl dihydroxy silane and a photobase generator are added into a small amount of organic solvent, and after being mixed and stirred uniformly, the mixture is sprayed on a substrate to obtain a liquid coating; and then placing the mixture under an ultraviolet lamp for illumination for 20-60min to generate organic quaternary ammonium base to initiate the condensation polymerization of SiOH groups in the silane precursor, wherein the diphenyl polysiloxane has super-hydrophobic performance due to the hydrophobic characteristic provided by phenyl functional groups in the silane and the combination of the rough structure on the surface of the coating. Based on the mechanism of silicon hydroxyl condensation polymerization reaction, different from the traditional siloxane condensation catalyzed by acid, the condensation reaction of siloxane catalyzed by alkali can lead the coating to obtain higher polymerization degree (condensation degree), thereby further improving the mechanical strength and hydrophobic property (reduction of Si-OH groups) of the coating.

The invention introduces the photobase generator, generates base through illumination to catalyze the polycondensation reaction of the silane precursor, and compared with the traditional scheme of directly adding the base catalyst, the solution of the formula is very stable in the environment without ultraviolet light; can be sealed and placed for more than 1 year. Meanwhile, in the super-hydrophobic coating, the polysiloxane main chain has high mechanical strength and good wear resistance, and phenyl polysiloxane is easy to self-assemble and crystallize by combining the pi-pi conjugation effect among benzene ring groups, so that the super-hydrophobic performance of the coating has good thermal stability, the situations of poor wear resistance, short service time and poor use effect of the existing super-hydrophobic coating are effectively overcome, and the preparation method is simple to operate.

Drawings

Fig. 1 is a polarization microscope photograph of the phenyl polysiloxane superhydrophobic coating prepared in embodiment 5.

Detailed Description

The present invention will be described in detail with reference to the accompanying drawings.

Embodiment 1:

adding 1g of diphenyl dihydroxy silane and 0.02g of 2-methyl-1- (4-methylthiophenyl) -2-morpholinyl-1-acetone into 5mL of ethanol, uniformly mixing under magnetic stirring, spraying on a substrate to form a film, and placing at the power of 0.1mW/cm²And irradiating the mixture for reaction for 48 hours in an oven at 120 ℃ under an ultraviolet lamp with the wavelength of 240nm for 60min to obtain the phenyl polysiloxane super-hydrophobic coating, wherein the results are shown in Table 1.

Embodiment 2:

adding 1g of diphenyl dihydroxy silane and 0.02g of 2-methyl-1- (4-methylthiophenyl) -2-morpholinyl-1-acetone into 2mL of trichloromethane, uniformly mixing under magnetic stirring, spraying on a substrate to form a film, and placing at the power of 0.5mW/cm²And irradiating the mixture for reaction for 72 hours in an oven at 100 ℃ for 40 min under an ultraviolet lamp with the wavelength of 2400nm to obtain the phenyl polysiloxane super-hydrophobic coating, wherein the results are shown in Table 1.

Embodiment 3:

adding 1g of diphenyl dihydroxy silane and 0.04g of 2-methyl-1- (4-methylthiophenyl) -2-morpholinyl-1-acetone into 3mL of tetrahydrofuran, uniformly mixing under magnetic stirring, spraying on a substrate to form a film, and placing at a power of 2mW/cm²And the phenyl polysiloxane super-hydrophobic coating is obtained by the reaction of the phenyl polysiloxane super-hydrophobic coating in an oven with the wavelength of 240nm and the illumination time of 30 min at 100 ℃, and the result is shown in the table 1.

Embodiment 4:

adding 1g of diphenyl dihydroxy silane and 0.02g of 2-methyl-1- (4-methylthiophenyl) -2-morpholinyl-1-acetone into 2mL of acetonitrile, uniformly mixing under magnetic stirring, spraying on a substrate to form a film, and placing at a power of 20mW/cm²Irradiating under an ultraviolet lamp with a wavelength of 240nm for 20 min in an oven at 80 ℃ for 144h to obtain the phenyl polysiloxaneHydrophobic coating, results are shown in table 1.

Embodiment 5:

adding 1g of diphenyl dihydroxy silane and 0.04g of 2-phenyl benzyl-2-dimethylamine-1- (4-morpholine benzyl phenyl) butanone into 5mL of ethanol, uniformly mixing under magnetic stirring, spraying on a substrate to form a film, and placing at a power of 5mW/cm²And the reaction is carried out for 288h in an oven at 60 ℃ under an ultraviolet lamp with the wavelength of 320nm for 60min to obtain the phenyl polysiloxane super-hydrophobic coating, and the result is shown in table 1. Fig. 1 is a polarization microscope photograph of the phenyl polysiloxane superhydrophobic coating prepared in the present embodiment, and phenyl polysiloxane exists in the coating layer in a form of spherulites due to pi-pi conjugation between benzene rings, thereby providing surface roughness and excellent wear resistance, and good superhydrophobic thermal stability.

Embodiment 6:

adding 1g of diphenyl dihydroxy silane and 0.06g of 2- (4-methylbenzyl) -2- (dimethylamino) -1- (4-morpholinyl phenyl) -1-butanone into 3mL of tetrahydrofuran, uniformly mixing under magnetic stirring, spraying on a substrate to form a film, and placing at a power of 10mW/cm²And irradiating the coating for 60min under an ultraviolet lamp with the wavelength of 320nm for 144h in an oven at 100 ℃ to obtain the phenyl polysiloxane super-hydrophobic coating, wherein the results are shown in Table 1.

Comparative example:

diphenyldihydroxysilane (1g) was dissolved in tetrahydrofuran (3 mL), 0.16mL of a sodium hydroxide aqueous solution (1 mol/L) of sodium hydroxide was added, magnetic stirring was performed at 40 ℃ in a sealed state for 72 hours, and then the resulting transparent liquid was sprayed on a substrate to form a film, which was placed in an oven at 100 ℃ for 144 hours to obtain a phenyl polysiloxane coating, the results of which are shown in Table 1.

Table 1 results of water contact angle test of super-hydrophobic coatings of phenylpolysiloxanes prepared in embodiments 1 to 6

Sample (I)	Water contact Angle (°)	Rolling angle (°)
			Embodiment mode 1	142	12
Embodiment mode 2	152	5
			Embodiment 3	152	6
Embodiment 4	156	2
			Embodiment 5	150	7
Embodiment 6	151	7
			Comparative example	107	-

Note: the contact angle was measured by using a DSA25 model full-automatic video contact angle measuring instrument manufactured by Kruss company, Germany, and the average value of three parallel tests was obtained.

Table 1 shows that the phenyl polysiloxane superhydrophobic coatings prepared by the methods of embodiments 1 to 6 all have high superhydrophobic performance and small rolling angles, which indicates that the coatings have great application prospects in the fields of self-cleaning coatings, antifogging coatings and the like; the phenyl polysiloxane coating prepared by the traditional classical sol-gel method has insufficient surface roughness, and cannot have super-hydrophobic performance.

The above embodiments are merely illustrative of the technical concepts and features of the present invention, and the purpose of the embodiments is to enable those skilled in the art to understand the contents of the present invention and implement the present invention, and not to limit the protection scope of the present invention. All equivalent changes and modifications made according to the spirit of the present invention should be covered within the protection scope of the present invention.

Claims

1. A preparation method of phenyl polysiloxane super-hydrophobic coating is characterized in that diphenyl dihydroxy silane solid precursor and photobase generator in a certain proportion are added into a certain amount of organic solvent at room temperature, and after being mixed and stirred uniformly, the mixture is sprayed and coated on a substrate; and (3) after the substrate coated with the sample is illuminated under an ultraviolet lamp for a preset time, putting the substrate into an oven for drying to obtain the phenyl polysiloxane super-hydrophobic coating.

2. The method for preparing the phenyl polysiloxane super-hydrophobic coating according to claim 1, wherein the mass ratio of the diphenyl dihydroxy silane solid precursor to the photobase generator is 1: 0.02-0.10.

3. The method for preparing phenyl polysiloxane super-hydrophobic coating according to claim 1, wherein the photobase generator is 2-methyl-1- (4-methylthiophenyl) -2-morpholinyl-1-propanone, 2-phenylbenzyl-2-dimethylamine-1- (4-morpholinyl benzyl) butanone or 2- (4-methylbenzyl) -2- (dimethylamino) -1- (4-morpholinyl phenyl) -1-butanone.

4. The method for preparing phenyl polysiloxane super-hydrophobic coating according to claim 1, wherein the organic solvent is ethanol, tetrahydrofuran, toluene, chloroform or acetonitrile.

5. The method for preparing a phenyl polysiloxane super-hydrophobic coating according to any one of claims 1 to 4, wherein the preset time is 20-60 min.

6. Method for preparing a phenylpolysiloxane superhydrophobic coating according to any of claims 1 to 4, characterized in that the temperature of the oven is 60-120 deg^oC。

7. The method for preparing phenyl polysiloxane super-hydrophobic coating according to any one of claims 1 to 4, wherein the drying time is 24-288 h.

8. The method for preparing phenyl polysiloxane super-hydrophobic coating according to any one of claims 1 to 4, wherein the power of the ultraviolet lamp is 0.1-20 mW/cm²。

9. The method for preparing phenyl polysiloxane super-hydrophobic coating according to any one of claims 1 to 4, wherein the wavelength of the ultraviolet lamp is 240nm or 320 nm.

10. The phenylpolysiloxane superhydrophobic coating according to any of claims 1 to 4, characterized in that the substrate is glass, filter paper, silicon wafer, aluminum alloy, tinplate or polycarbonate.