阅读说明：本技术 一种氟碳改性化腐植酸微颗粒及其制备方法和应用 (Fluorocarbon modified humic acid micro-particles and preparation method and application thereof ) 是由 王晨 邱冠钧 牛育华 李刚辉 于 2019-11-26 设计创作，主要内容包括：本发明公开了一种氟碳改性化腐植酸微颗粒及其制备方法和应用,包括以下步骤制备：1)将腐植酸和含氟醇放置于三口烧瓶中,加浓硫酸作催化剂,DMF作溶剂。2)将上述反应后的固液混合物进行离心洗涤,真空干燥,所得黑色固体即为氟碳改性化腐植酸产物。将所得固体产物进行研磨得该氟碳改性化腐植酸微颗粒。本发明充分利用腐植酸和氟碳基团的优良性能发明了一种氟碳改性化腐植酸微颗粒。该微颗粒将氟碳基团直接接于腐植酸上,在保持腐植酸抗蚀、耐磨、减磨所有优点的条件下,增加氟碳基团的疏水、耐蚀的优良性能。(The invention discloses fluorocarbon modified humic acid micro-particles and a preparation method and application thereof, and the fluorocarbon modified humic acid micro-particles comprise the following steps: 1) humic acid and fluorine-containing alcohol are placed in a three-mouth flask, concentrated sulfuric acid is added to be used as a catalyst, and DMF is used as a solvent. 2) And (3) centrifugally washing the solid-liquid mixture after the reaction, and drying in vacuum to obtain black solid, namely the fluorocarbon modified humic acid. Grinding the obtained solid product to obtain the fluorocarbon modified humic acid micro-particles. The invention discloses fluorocarbon modified humic acid micro-particles by fully utilizing the excellent performances of humic acid and fluorocarbon groups. The micro-particles directly connect the fluorocarbon group to the humic acid, and increase the excellent hydrophobic and corrosion-resistant performances of the fluorocarbon group under the condition of keeping all the advantages of corrosion resistance, wear resistance and attrition reduction of the humic acid.)

1. A fluorocarbon modified humic acid micro-particle is characterized in that: has the following structural formula:

wherein Rf is a fluorine-containing long-chain alkyl group.

2. A preparation method of fluorocarbon modified humic acid micro-particles is characterized by comprising the following steps:

1) mixing humic acid and fluoroalcohol, adding concentrated sulfuric acid as catalyst and DMF as solvent, and adding zeolite; heating to 140 ℃ and 150 ℃ and refluxing for 4-5h to obtain a solid-liquid mixture;

2) carrying out centrifugal washing and vacuum drying on the solid-liquid mixture to obtain black solid, namely the fluorocarbon modified humic acid; grinding the obtained solid product to obtain the fluorocarbon modified humic acid micro-particles.

3. The method for preparing fluorocarbon-modified phytic acid microparticles as claimed in claim 2, wherein the fluorine-containing alcohol is perfluorooctyl ethyl alcohol.

4. The method for preparing fluorocarbon-modified humic acid microparticles as claimed in claim 2, wherein the mass of the added fluorine-containing alcohol is 1.5-2 times of that of humic acid.

5. The method for preparing fluorocarbon-modified humic acid microparticles as claimed in claim 2, wherein the concentrated sulfuric acid concentration is 98%.

6. The use of fluorocarbon-modified phytic acid microparticles of claim 1 as a hydrophobic additive for coatings.

7. Use according to claim 6, characterized in that it comprises the following steps:

3) methyl methacrylate, butyl acrylate and acrylic acid are taken as monomers, polyvinyl alcohol is taken as a dispersing agent, and acrylic resin is prepared by reflux at the temperature of 75-80 ℃;

4) dispersing the fluorocarbon modified humic acid microparticles into acrylic resin by 2-40% by mass, blending, performing ultrasonic dispersion to obtain a coating, coating the coating on a wood board, and naturally drying.

8. Use according to claim 7, characterized in that the monomer ratio between methyl methacrylate and butyl acrylate is 1: acrylic acid 1/3 based on total monomer with 25% solids.

9. The application of the paint as claimed in claim 7, wherein the paint forms micro-protrusions similar to the micro-nano mastoid structure on the surface of a lotus leaf on the surface of a wood board.

Technical Field

The invention relates to fluorocarbon modified humic acid microparticles, in particular to fluorocarbon modified humic acid microparticles as well as a preparation method and application thereof.

Background

Generally, a coating material reacts with a metal substrate to passivate the surface thereof or form a protective coating film thereon, thereby performing a protective function. Humic acid is taken as a rigid material of the sheet layer, and the rigid structure of the sheet layer can play a role in passivating the coating metal, so that the corrosion resistance of the coating metal is further improved. Meanwhile, the polymer coating is easily damaged by various factors, and the excellent mechanical property and tribological property of the humic acid can improve the wear-reducing and wear-resisting properties of the material. The fluorocarbon group is introduced into the polymer, so that the surface tension of the polymer is reduced, the polymer has better hydrophobic property, and compared with hydrogen atoms, the electron cloud of the fluorine atoms has stronger shielding effect on the C-C bond, so that the fluoropolymer has better corrosion resistance. Therefore, fluorocarbon groups can be introduced into the humic acid for modification, the excellent performance of the fluorocarbon groups is increased under the condition of keeping all the advantages of the humic acid, and the fluorocarbon groups are prepared into micro-particles which are used as additives of acrylic resin coatings, so that the corrosion resistance and the wear resistance of the acrylic resin coatings are improved, and meanwhile, the hydrophobic performance of the acrylic resin coatings is improved.

Disclosure of Invention

The invention aims to provide fluorocarbon modified humic acid microparticles and a preparation method and application thereof. Fluorine atoms are introduced into the microparticles, and C-F bonds reduce intermolecular force and surface tension of the microparticles and improve the hydrophobic property of the microparticles.

The technical scheme adopted by the invention is as follows:

the fluorocarbon modified humic acid micro-particles have the following structural formula:

wherein Rf is a fluorine-containing long-chain alkyl group.

A preparation method of fluorocarbon modified humic acid micro-particles comprises the following steps:

1) mixing humic acid and fluoroalcohol, adding concentrated sulfuric acid as catalyst and DMF as solvent, and adding zeolite; heating to 140 ℃ and 150 ℃ and refluxing for 4-5h to obtain a solid-liquid mixture;

2) carrying out centrifugal washing and vacuum drying on the solid-liquid mixture to obtain black solid, namely the fluorocarbon modified humic acid; grinding the obtained solid product to obtain the fluorocarbon modified humic acid micro-particles.

The fluorine-containing alcohol is perfluorooctyl ethyl alcohol.

The adding mass of the fluorine-containing alcohol is 1.5-2 times of that of humic acid.

The concentrated sulfuric acid concentration is 98%.

The fluorocarbon modified humic acid micro-particles are applied as a hydrophobic additive of the coating.

Preferably, the method comprises the following steps:

3) methyl methacrylate, butyl acrylate and acrylic acid are taken as monomers, polyvinyl alcohol is taken as a dispersing agent, and acrylic resin is prepared by reflux at the temperature of 75-80 ℃;

4) dispersing the fluorocarbon modified humic acid microparticles into acrylic resin by 2-40% by mass, blending, performing ultrasonic dispersion to obtain a coating, coating the coating on a wood board, and naturally drying.

The monomer ratio of methyl methacrylate to butyl acrylate is 1: acrylic acid 1/3 based on total monomer with 25% solids.

The coating forms micro-protrusions similar to the lotus leaf surface micro-nano mastoid structure on the surface of the wood board.

Compared with the prior art, the invention has the following advantages:

the invention provides fluorocarbon modified humic acid micro-particles. The micro-particles directly connect the fluorocarbon group to the humic acid, and increase the excellent hydrophobic and corrosion-resistant performances of the fluorocarbon group under the condition of keeping all the advantages of corrosion resistance, wear resistance and attrition reduction of the humic acid. The micro-particles are mixed in acrylic resin paint and coated on the surface of the wood board, and micro-protrusions similar to the lotus leaf surface micro-nano mastoid structure can be formed on the surface of the wood board, so that the hydrophobic property of the wood board is improved in terms of microstructure. Can be used as a hydrophobic additive in paint.

The humic acid and the fluorine-containing alcohol are synthesized by esterification reaction; grinding and drying the modified substance into fine powder to obtain the fluorocarbon modified humic acid micro-particles. The fluorocarbon modified humic acid micro-particle makes full use of the excellent performances of humic acid and fluorocarbon groups, and the fluorocarbon groups are directly connected with the humic acid, so that the excellent performances of hydrophobicity and corrosion resistance of the fluorocarbon groups are improved under the condition that all the advantages of corrosion resistance, wear resistance and abrasion reduction of the humic acid are maintained. The micro-particles are mixed in acrylic resin paint and coated on the surface of the wood board, and micro-protrusions similar to the lotus leaf surface micro-nano mastoid structure can be formed on the surface of the wood board, so that the hydrophobic property of the wood board is improved in terms of microstructure.

The modified substance is synthesized by the esterification reaction of humic acid and fluorine-containing alcohol by using a catalyst; grinding and drying the modified substance into fine powder to obtain the fluorocarbon modified humic acid micro-particles. The micro-particles are mixed in acrylic resin paint and coated on the surface of a wood board, and micro-protrusions similar to a lotus leaf surface micro-nano mastoid structure can be formed on the surface of the wood board.

Drawings

FIG. 1 is an infrared spectrum of fluorocarbon modified humic acid micro-particles;

figure 2 is the contact angle performance test protocol and 90.1 ° contact angle for example 5.

Detailed Description

The invention relates to fluorocarbon modified humic acid micro-particles, which are prepared by the following steps:

the fluorocarbon modified humic acid micro-particle has the following structure:

wherein Rf is a fluorine-containing long-chain alkyl group

The micro-particles are mixed in acrylic resin paint and coated on the surface of a wood board, and micro-protrusions similar to a lotus leaf surface micro-nano mastoid structure can be formed on the surface of the wood board.

The modified substance is synthesized by the esterification reaction of humic acid and fluorine-containing alcohol by using a catalyst; grinding and drying the modified substance into fine powder to obtain the fluorocarbon modified humic acid micro-particles.

The first step is as follows: the reaction equation of the fluorocarbon modified humic acid micro-particles is as follows:

according to the above reaction mechanism, the method comprises the steps of:

(1) placing humic acid and fluoroalcohol (perfluorooctyl ethyl alcohol) in a three-neck flask, adding concentrated sulfuric acid with the mass concentration of 98% as a catalyst, adding DMF as a solvent, and adding zeolite, wherein the mass of the fluoroalcohol is 1.5-2 times that of the humic acid. Heating to 140 ℃ and 150 ℃ and refluxing for 4-5 h.

(2) And (3) centrifugally washing the solid-liquid mixture after the reaction, and drying in vacuum to obtain black solid, namely the fluorocarbon modified humic acid. Grinding the obtained solid product to obtain the fluorocarbon modified humic acid micro-particles.

The second step is that: the application of fluorocarbon modified humic acid microparticles as hydrophobic additive of paint includes the following steps:

methyl Methacrylate (MMA), Butyl Acrylate (BA) and Acrylic Acid (AA) are used as monomers, polyvinyl alcohol is used as a dispersing agent, and the monomer ratio of MMA to BA is 1: 1, AA accounts for 1/3 of the total monomers, the solid content is 25 percent, and the acrylic resin is prepared by refluxing at 75-80 ℃. Blending the prepared fluorocarbon modified humic acid micro-particles with acrylic resin, dispersing the mixture into the acrylic resin according to five different mass ratios of 2%, 5%, 10%, 20% and 40%, performing ultrasonic dispersion for 10min, coating a film on a wood board, naturally airing, and testing.

The present invention will be described in detail with reference to the following specific examples: