CN112080167A - Preparation method of polyacrylate super-hydrophobic coating - Google Patents

Preparation method of polyacrylate super-hydrophobic coating Download PDF

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CN112080167A
CN112080167A CN202010905849.9A CN202010905849A CN112080167A CN 112080167 A CN112080167 A CN 112080167A CN 202010905849 A CN202010905849 A CN 202010905849A CN 112080167 A CN112080167 A CN 112080167A
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polyacrylate
fluorine
coating according
hydrophobic coating
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CN112080167B (en
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蔡鹏�
刘永涛
李姗姗
倪伶俐
姜孝武
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Dragon Totem Technology Hefei Co ltd
Ningbo Mingyuan Packaging Co ltd
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Huaiyin Institute of Technology
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Abstract

The invention relates to the technical field of high polymer coating materials, and discloses a preparation method of a polyacrylate super-hydrophobic coating, which is characterized in that the polyacrylate super-hydrophobic coating is prepared by mixing the components in a mass ratio of 1: 0.01-0.05: and 0.02-0.05 of a fluorine-free acrylate monomer, a fluorine-containing acrylate monomer and a free radical photoinitiator, uniformly stirring, spraying on the surface of a substrate, and placing under an ultraviolet lamp for irradiating for a preset time to obtain the polyacrylate super-hydrophobic coating. The super-hydrophobic coating has the advantages of performance, no need of using organic solvent and solid particle filler, simple preparation process, suitability for various substrates and large-scale production, and wide market prospect.

Description

Preparation method of polyacrylate super-hydrophobic coating
Technical Field
The invention belongs to the technical field of high polymer coating materials, and relates to a preparation method of a polyacrylate super-hydrophobic coating.
Background
The super-hydrophobic coating is widely concerned by people due to the special surface non-wettability, and has good application prospects in the fields of self-cleaning, corrosion prevention, ice coating prevention, drag reduction and the like.
Numerous studies have shown that the wettability of solid surfaces is determined by their chemical composition and their microscopic geometry.
In recent years, a number of techniques for preparing superhydrophobic surfaces have been developed, such as sol-gel methods, chemical vapor deposition methods, electrochemical deposition methods, plasma methods, chemical etching methods, electrostatic spinning methods, and the like. However, these methods require special processing equipment such as plasma processing equipment or complicated processes, and use a large amount of organic volatile solvents in the preparation process, and thus are difficult to industrially produce.
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 a polyacrylate super-hydrophobic coating, which has excellent heat resistance and self-cleaning performance, does not need to use organic solvent and solid particle filler, has simple preparation process, and can be suitable for various substrates and large-scale production.
The technical scheme is as follows: the invention provides a preparation method of a polyacrylate super-hydrophobic coating, which comprises the following steps of: 0.01-0.05: and 0.02-0.05 of a fluorine-free acrylate monomer, a fluorine-containing acrylate monomer and a free radical photoinitiator, uniformly stirring, spraying on the surface of a substrate, and placing under an ultraviolet lamp for irradiating for a preset time to obtain the polyacrylate super-hydrophobic coating.
Preferably, the fluorine-free acrylate monomer is any one of the following: 1, 12-dodecanediol dimethacrylate, 1, 10-decandiol dimethacrylate, 1, 6-hexanediol dimethacrylate.
Preferably, the fluorine-containing acrylate monomer is any one of the following monomers: 1H,1H,2H, 2H-perfluorooctanol acrylate, 1H,2H, 2H-perfluorodecyl acrylate, 2-perfluorodecyl ethyl acrylate, 2- (perfluorooctyl) ethyl methacrylate, 2- (perfluorohexyl) ethyl methacrylate, 2- (perfluorobutyl) ethyl methacrylate.
Preferably, the free radical photoinitiator is any one of: 2-hydroxy-2-methylphenylacetone (1173), Methyl Benzoylformate (MBF), benzoin bis methyl ether (BDK), (2,4, 6-trimethylbenzoyl) diphenylphosphine oxide (TPO), 1-hydroxy-cyclohexyl-phenyl-methanone (184).
Preferably, the wavelength of the ultraviolet lamp is 250-400 nm. The preferred wavelength is 254nm or 365 nm.
Preferably, the power of the ultraviolet lamp is 5-40 mW/cm2. Preferably 10mW/cm2、15mW/cm2、20mW/cm2And 30mW/cm2。
Preferably, the preset time is 5-60 min. Preferably 10min, 20min, 30min and 40 min.
Preferably, the substrate is glass, silicon wafer, tinplate, aluminum alloy, polycarbonate, filter paper or woven fabric.
Has the advantages that: in the invention, acrylic resin without fluorine, fluorine-containing acrylic resin and free radical photoinitiator are uniformly stirred and mixed and then sprayed on a substrate to obtain an acrylic resin liquid coating; then, irradiating the photolysis free radical initiator to generate free radicals, initiating the polymerization of carbon-carbon double bond free radicals in the acrylic resin, forming a macromolecular chain, and then carrying out phase separation to obtain micron-sized particles, thereby forming a micro-nano coarse structure; in the copolymerization process of the fluorine-containing acrylic resin, the surface energy of the fluorine-containing carbon chain is lower than that of the alkyl carbon chain and is similar to that of a surfactant, and the fluorine-containing carbon chain can migrate to the surface of polyacrylate particles, so that the free energy of the surface of the coarse structure is extremely high, and finally the polyacrylate super-hydrophobic coating is obtained.
Compared with the prior art, the preparation method provided by the invention has the advantages that the polymerization is initiated only by the acrylic resin body, micron-sized polyacrylate particles are generated due to the phase separation effect of the formed polyacrylate in the polymerization process, and thus the rough surface of the coating is generated; meanwhile, the low surface energy of the fluorine-containing carbon chain in the fluorine-containing acrylic resin is combined, and the low surface energy migrates to the surface of the polyacrylate particle in the polymerization process, so that the surface of the coating has good intrinsic hydrophobic property, the polyacrylate super-hydrophobic coating is finally obtained, the nano particle is not required to be added to construct a coarse structure, the low surface energy substance is not required to be additionally used for modification, the solvent is not required to be used, and the preparation process is simple, efficient, energy-saving and environment-friendly.
And the added fluorine-containing acrylic resin contains polymerizable carbon-carbon double bonds and can be subjected to free radical copolymerization with the acrylate, so that the fluorine-containing carbon chain is fixed on the surface of the polyacrylate particles, the super-hydrophobic property of the coating has good heat resistance, and the super-hydrophobic property of the coating is not obviously reduced after the coating is soaked in boiling water for 4 hours.
Drawings
FIG. 1 is a scanning electron micrograph of the surface of the coating layer in example 1.
Detailed Description
The present invention will be described in detail with reference to the accompanying drawings.
Example 1:
mixing 1ml 1, 12-dodecanediol dimethacrylate, 0.02ml 1H,1H,2H, 2H-perfluorooctanol acrylate and 0.05ml 1-hydroxy-cyclohexyl-phenyl ketone, spraying on polycarbonate substrate, irradiating under 254nm ultraviolet lamp for 30min with power of 30mw/cm2And obtaining the polyacrylate super-hydrophobic coating, wherein a scanning electron microscope image of the surface of the polyacrylate super-hydrophobic coating is shown in figure 1, and the water contact angle test result of the polyacrylate super-hydrophobic coating is shown in table 1.
Example 2:
mixing 1ml 1, 10-decanediol dimethacrylate, 0.05ml 2-perfluorodecyl ethyl acrylate and 0.04ml (2,4, 6-trimethylbenzoyl) diphenyl phosphine oxide, spraying on polycarbonate substrate, irradiating under 365nm ultraviolet lamp with power of 10mw/cm for 20min2The polyacrylate super-hydrophobic coating is obtained, and the result is shown in table 1.
Example 3:
mixing 1ml 1, 6-hexanediol dimethacrylate, 0.04ml 2- (perfluorohexyl) ethyl methacrylate and 0.02ml 2-hydroxy-2-methylphenyl acetone, spraying on polycarbonate substrate, irradiating under 254nm ultraviolet lamp for 30min with power of 20mw/cm2The polyacrylate super-hydrophobic coating is obtained, and the result is shown in table 1.
Comparative example: 1ml of 1, 12-dodecanediol dimethacrylate, 0.02ml of 1H,1H,2H, 2H-perfluorooctanol acrylate and 0.04g of azobisisobutyronitrile were mixed by stirring, sprayed on a polycarbonate substrate and left in an oven at 80 ℃ for 1 hour to give a polyacrylate coating, the results of which are shown in Table 1.
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 polyacrylate Superhydrophobic coating Water contact Angle test results
Figure 11913DEST_PATH_IMAGE002
As can be seen from table 1, the superhydrophobic coating can be obtained regardless of the carbon chain length in the acrylate monomer by photo-initiated polymerization, whereas the superhydrophobic performance cannot be obtained even with the longest carbon chain coating by conventional thermal-initiated polymerization.
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 (8)

1. The preparation method of the polyacrylate super-hydrophobic coating is characterized by comprising the following steps of: 0.01-0.05: and 0.02-0.05 of a fluorine-free acrylate monomer, a fluorine-containing acrylate monomer and a free radical photoinitiator, uniformly stirring, spraying on the surface of a substrate, and placing under an ultraviolet lamp for irradiating for a preset time to obtain the polyacrylate super-hydrophobic coating.
2. The method for preparing the polyacrylate superhydrophobic coating according to claim 1, wherein the fluorine-free acrylate monomer is any one of:
1, 12-dodecanediol dimethacrylate, 1, 10-decandiol dimethacrylate, 1, 6-hexanediol dimethacrylate.
3. The preparation method of the polyacrylate superhydrophobic coating according to claim 1, wherein the fluorine-containing acrylate monomer is any one of:
1H,1H,2H, 2H-perfluorooctanol acrylate, 1H,2H, 2H-perfluorodecyl acrylate, 2-perfluorodecyl ethyl acrylate, 2- (perfluorooctyl) ethyl methacrylate, 2- (perfluorohexyl) ethyl methacrylate, 2- (perfluorobutyl) ethyl methacrylate.
4. The method for preparing polyacrylate superhydrophobic coating according to claim 1, wherein the radical photoinitiator is any one of the following:
2-hydroxy-2-methylphenylacetone, methyl benzoylformate, benzoin bis methyl ether, (2,4, 6-trimethylbenzoyl) diphenylphosphine oxide, 1-hydroxy-cyclohexyl-phenyl-methanone.
5. The method for preparing the polyacrylate superhydrophobic coating according to claim 1, wherein the wavelength of the ultraviolet lamp is 250-400 nm.
6. The preparation method of the polyacrylate superhydrophobic coating according to claim 1, wherein the power of the ultraviolet lamp is 5-40 mW/cm2。
7. The method for preparing the polyacrylate superhydrophobic coating according to claim 1, wherein the preset time is 5-60 min.
8. The method for preparing the polyacrylate superhydrophobic coating according to any one of claims 1 to 7, wherein the substrate is glass, silicon wafer, tinplate, aluminum alloy, polycarbonate, filter paper or woven fabric.
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Cited By (3)

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Publication number Priority date Publication date Assignee Title
CN113980501A (en) * 2021-11-19 2022-01-28 国网江苏省电力有限公司电力科学研究院 Photo-induced front-line polymerized graphene super-hydrophobic anticorrosive coating and preparation method thereof
CN114318886A (en) * 2021-12-30 2022-04-12 广西青龙化学建材有限公司 Non-asphalt-based on-site coiled material and preparation method thereof
CN117860433A (en) * 2024-03-13 2024-04-12 上海新耀湃科医疗科技股份有限公司 Intraocular lens conveying device and preparation method thereof

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US20180134904A1 (en) * 2015-05-21 2018-05-17 Sun Chemical Corporation Superhydrophobic uv curable coating
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CN101985499A (en) * 2010-10-28 2011-03-16 浙江工业大学 Method for preparing super-hydrophobic surface polypropylene
CN102688704A (en) * 2012-06-05 2012-09-26 苏州市新能膜材料科技有限公司 Method for preparing lasting super-hydrophobic modified polypropylene hollow fiber membrane
CN102964545A (en) * 2012-11-05 2013-03-13 中科院广州化学有限公司 Ultraviolet-crosslinking fluorine-containing polymer and application thereof in preparing super-amphiphobic surface
US20180134904A1 (en) * 2015-05-21 2018-05-17 Sun Chemical Corporation Superhydrophobic uv curable coating
CN107226920A (en) * 2017-07-12 2017-10-03 中物院成都科学技术发展中心 A kind of preparation method of light-cured type super-hydrophobic composite film
CN108264815A (en) * 2018-01-05 2018-07-10 宁波大学 A kind of preparation method of super-hydrophobic superoleophobic high molecular nanometer coating

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CN113980501A (en) * 2021-11-19 2022-01-28 国网江苏省电力有限公司电力科学研究院 Photo-induced front-line polymerized graphene super-hydrophobic anticorrosive coating and preparation method thereof
CN114318886A (en) * 2021-12-30 2022-04-12 广西青龙化学建材有限公司 Non-asphalt-based on-site coiled material and preparation method thereof
CN117860433A (en) * 2024-03-13 2024-04-12 上海新耀湃科医疗科技股份有限公司 Intraocular lens conveying device and preparation method thereof
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