CN111978861B - Preparation method of phenyl polysiloxane super-hydrophobic coating - Google Patents

Preparation method of phenyl polysiloxane super-hydrophobic coating Download PDF

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CN111978861B
CN111978861B CN202010905418.2A CN202010905418A CN111978861B CN 111978861 B CN111978861 B CN 111978861B CN 202010905418 A CN202010905418 A CN 202010905418A CN 111978861 B CN111978861 B CN 111978861B
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hydrophobic coating
phenyl polysiloxane
super
coating according
preparing
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CN111978861A (en
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倪伶俐
刘永涛
徐成鹏
杨昌佑
郑菲
蔡鹏�
姜孝武
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Huaiyin Institute of Technology
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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D183/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Coating compositions based on derivatives of such polymers
    • C09D183/04—Polysiloxanes
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D4/00—Coating compositions, e.g. paints, varnishes or lacquers, based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; Coating compositions, based on monomers of macromolecular compounds of groups C09D183/00 - C09D183/16
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/04—Polysiloxanes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/80—Siloxanes having aromatic substituents, e.g. phenyl side groups

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  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Wood Science & Technology (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Application Of Or Painting With Fluid Materials (AREA)
  • Paints Or Removers (AREA)

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.CoC. Preferably 80 to 100oC。
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:
1g of diphenyl dihydroxy silane and 0.02g of 2-methyl-1- (4-methylthiophenyl) -2-morpholinyl-1-propanone are added into 2mL of trichloromethane, and after the materials are uniformly mixed under magnetic stirring,spraying on a substrate to form a film, and placing the film at a 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/cm2And (3) irradiating the mixture for 20 min under an ultraviolet lamp with the wavelength of 240nm and reacting the mixture for 144h in an oven at 80 ℃ to obtain the phenyl polysiloxane super-hydrophobic coating, wherein the 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:
1g of diphenyldihydroxysilane and 0.06g of 2- (4-methylbenzyl) -2- (dimethylamino) -1- (4-morpholinophenyl) -1-butanone are added to 3mL of tetrahydrofuran, and the mixture is uniformly mixed under magnetic stirringThen spraying on the substrate to form a film, and placing the film 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 (10)

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 degoC。
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 0.1~20mW/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 method for preparing phenyl polysiloxane super-hydrophobic coating according to any one of claims 1 to 4, wherein the substrate is glass, filter paper, silicon wafer, aluminum alloy, tinplate or polycarbonate.
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CN103043919A (en) * 2012-11-07 2013-04-17 北京化工大学 Method for preparing waterproof and antifogging surface modified glass
CN108384443A (en) * 2018-01-11 2018-08-10 淮阴工学院 Hybrid super hydrophobic coating and its preparation method and application
CN109266211A (en) * 2018-08-28 2019-01-25 淮阴工学院 Organopolysiloxane super hydrophobic coating and preparation method thereof

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KR101992594B1 (en) * 2011-11-29 2019-06-25 메르크 파텐트 게엠베하 Negative-type photosensitive siloxane composition
CN104513607B (en) * 2014-12-24 2016-09-28 浙江佑谦特种材料有限公司 A kind of wear-resisting anti-fog coating of photocuring and construction method thereof

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103043919A (en) * 2012-11-07 2013-04-17 北京化工大学 Method for preparing waterproof and antifogging surface modified glass
CN108384443A (en) * 2018-01-11 2018-08-10 淮阴工学院 Hybrid super hydrophobic coating and its preparation method and application
CN109266211A (en) * 2018-08-28 2019-01-25 淮阴工学院 Organopolysiloxane super hydrophobic coating and preparation method thereof

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