阅读说明：本技术 一种超疏水涂料改性添加剂 (Super-hydrophobic coating modifying additive ) 是由 朱晨润 张丽 乔来红 于 2019-11-18 设计创作，主要内容包括：一种超疏水涂料改性添加剂,其特征在于,将丙烯酸酯类单体用含氟硅氧烷改性获得,所述含氟硅氧烷的结构式如式(I)：(R<Sup>1</Sup>O)<Sub>3</Sub>SiCH<Sub>2</Sub>-(CH=CH)-CH<Sub>2</Sub>-CR<Sup>2</Sup><Sub>3</Sub>(I),其中,R<Sup>1</Sup>为C1-C3的烷基；R<Sup>2</Sup>为全氟烷基。丙烯酸酯类单体的改性方法为,将丙烯酸酯类单体、功能单体、式(I)所示的含氟硅氧烷、引发剂、溶剂加入到反应容器中,在保护气氛下加热至70-100°C,反应6-20h而成。改性后的丙烯酸酯类单体获得全氟烷基,可以为涂料提供优良的疏水性。硅氧烷基团是可水解基团,在涂料中原位水解得到纳米二氧化硅,配合其所链接的丙烯酸树脂基团和含氟烷基,形成微纳米复合结构,具有超疏水性。(The super-hydrophobic coating modifying additive is characterized in that an acrylate monomer is modified by fluorine-containing siloxane, wherein the structural formula of the fluorine-containing siloxane is as shown in formula (I): (R) 1 O) 3 SiCH 2 ‑(CH=CH)‑CH 2 ‑CR 2 3 (I) Wherein R is 1 Is C1-C3 alkyl; r 2 Is a perfluoroalkyl group. Acrylic acidThe modification method of the ester monomer comprises the steps of adding the acrylate monomer, the functional monomer, the fluorine-containing siloxane shown in the formula (I), the initiator and the solvent into a reaction container, heating to 70-100 ℃ under a protective atmosphere, and reacting for 6-20 h. The modified acrylate monomer obtains perfluoroalkyl group, and can provide excellent hydrophobicity for paint. The siloxane group is a hydrolyzable group, the nano silicon dioxide is obtained by in-situ hydrolysis in the coating, and the micro nano composite structure is formed by matching the acrylic resin group and the fluorine-containing alkyl group linked with the nano silicon dioxide, and has super hydrophobicity.)

1. The super-hydrophobic coating modifying additive is characterized in that an acrylate monomer is modified by fluorine-containing siloxane, wherein the structural formula of the fluorine-containing siloxane is as shown in formula (I):

(R¹O)₃SiCH₂-(CH=CH)-CH₂-CR² ₃（I），

wherein R is¹Is C1-C3 alkyl; r²Is a perfluoroalkyl group.

2. The super hydrophobic coating modifying additive of claim 1 wherein: the method for modifying the acrylate monomer comprises the steps of adding the acrylate monomer, the functional monomer, the fluorine-containing siloxane shown in the formula (I), the initiator and the solvent into a reaction container, heating to 70-100 ℃ under a protective atmosphere, and reacting for 6-20 hours.

3. The super hydrophobic coating modifying additive of claim 1 wherein: wherein R is¹Three R are one or more of methyl, ethyl, propyl or isopropyl¹May be different, different from each other or partially identical.

4. The super hydrophobic coating modifying additive of claim 1 wherein: wherein R is²Is perfluoroalkyl having 3 to 15 carbon atoms.

5. The super hydrophobic coating modifying additive of claim 2 wherein: the acrylate monomer is selected from one or more of methyl acrylate, methyl methacrylate, butyl acrylate, ethyl methacrylate, ethyl acrylate or isooctyl methacrylate.

6. The super hydrophobic coating modifying additive of claim 2 wherein: the functional monomer is selected from one or more of acrylamide, methacrylic acid, hydroxyethyl acrylate, hydroxypropyl acrylate and hydroxyethyl methacrylate.

7. The super hydrophobic coating modifying additive of claim 2 wherein: the initiator is tert-butyl hydroperoxide.

Technical Field

The invention relates to the field of coatings, and relates to a coating hydrophobic modification additive, in particular to an acrylate compound modified by fluorine-containing siloxane.

Background

Generally, the coating will have some hydrophobicity. However, the coating with ordinary hydrophobicity can not meet the application requirements of the coating in special occasions. For example, coatings on building surfaces often need to have a certain superhydrophobicity so that the building surface obtains a certain self-cleaning effect. For another example, the paint on the surface of the ship body is generally required to have certain super-hydrophobicity and antibacterial property, so that the corrosion resistance of the surface of the ship body is greatly enhanced, and the service life of the ship body is prolonged. In addition, in severe cold areas, the coating with super-hydrophobicity can also enable the surface of a substrate coated with the coating to obtain an anti-frost effect.

However, of the existing coatings, the research on the superhydrophobic coating is relatively less. And the existing super-hydrophobic coating on the market often has the defects of insufficient adhesive force and super-hydrophobic effect. Therefore, the invention aims to provide the super-hydrophobic coating modifying additive with excellent adhesive force.

Disclosure of Invention

In order to solve the technical problems in the existing super-hydrophobic coating, the inventor of the invention finds that an acrylate compound obtained by modifying a conventional acrylate monomer with special fluorine-containing siloxane is used as a super-hydrophobic coating modifying additive through a large number of tests, so that the coating has excellent super-hydrophobicity, and the adhesion of the coating and a substrate is stable and firm.

The super-hydrophobic coating modifying additive is prepared by reacting a conventional acrylate monomer and hydrolyzable fluorine-containing siloxane in the presence of an initiator. The fluorine-containing siloxane group is obtained by modifying acrylic resin, so that perfluoroalkyl is obtained in the super-hydrophobic coating modifying additive, excellent hydrophobicity can be provided for the coating, meanwhile, silane in the coating is hydrolyzed in situ to obtain nano silicon dioxide, and a micro-nano composite structure is formed by matching with the acrylic resin group linked with the nano silicon dioxide, so that the super-hydrophobicity is realized. Meanwhile, because the acrylic resin group is directly linked with silicon, the obtained coating can form a compact coating layer which is tightly combined on the surface of the substrate after being cured by the curing agent, and the bonding force of the whole coating and the substrate is obviously improved.

The super-hydrophobic coating modifying additive is characterized in that an acrylate monomer is modified by fluorine-containing siloxane, wherein the structural formula of the fluorine-containing siloxane is as shown in formula (I):

(R¹O)₃SiCH₂-(CH=CH)-CH₂-CR² ₃（I），

wherein R is¹Is C1-C3 alkyl; r²Is a perfluoroalkyl group.

The method for modifying the acrylate monomer comprises the steps of adding the acrylate monomer, the functional monomer, the fluorine-containing siloxane shown in the formula (I), the initiator and the solvent into a reaction container, heating to 70-100 ℃ under a protective atmosphere, and reacting for 6-20 hours.

Wherein R is¹Three R are one or more of methyl, ethyl, propyl or isopropyl¹May be different, different from each other or partially identical.

Wherein R is²Is perfluoroalkyl having 3 to 15 carbon atoms.

Further, the acrylate monomer is selected from one or more of methyl acrylate, methyl methacrylate, butyl acrylate, ethyl methacrylate, ethyl acrylate or isooctyl methacrylate.

Further, the functional monomer is selected from one or more of acrylamide, methacrylic acid, hydroxyethyl acrylate, hydroxypropyl acrylate and hydroxyethyl methacrylate.

Further, the initiator is tert-butyl hydroperoxide.

Compared with the existing super-hydrophobic coating and the additive thereof, the super-hydrophobic coating modifier disclosed by the invention has the following beneficial effects:

1. the conventional acrylate monomer is modified, the raw materials are simple, and the cost is low.

2. Structure of fluorine-containing siloxane modifierIs of the formula (R)¹O)₃SiCH₂-(CH=CH)-CH₂-CR² ₃. The fluorine-containing siloxane is linked with the acrylate monomer through the initiator, so that the modifier can form a compact coating layer which is tightly combined on the surface of the substrate after the coating is cured by the curing agent, and the bonding force of the whole coating and the substrate is obviously improved. The modified acrylate monomer obtains perfluoroalkyl, and can provide excellent hydrophobicity for the coating. The siloxane group is a hydrolyzable group, the nano silicon dioxide is obtained by in-situ hydrolysis in the coating, and the micro nano composite structure is formed by matching the acrylic resin group and the fluorine-containing alkyl group linked with the nano silicon dioxide, and has super hydrophobicity.

3. Tert-butyl hydroperoxide is used as an initiator, and products are tert-butyl alcohol and acetone, so that the method is safe and corrosion-free.

Detailed Description

The present invention will be described in detail with reference to specific examples. Of course, the described embodiments are merely some of the inventive concepts, rather than all of them. Other examples, which would be obtained by one of ordinary skill in the art without any inventive step based on the embodiments of the present invention, are within the scope of the present invention.