WO2022127116A1

WO2022127116A1 - Preparation method for and application of weather-resistant, wear-resistant and hydrophobic aid

Info

Publication number: WO2022127116A1
Application number: PCT/CN2021/108524
Authority: WO
Inventors: 祝京旭; 张辉
Original assignee: 广东西敦千江粉漆科学研究有限公司
Priority date: 2020-12-19
Filing date: 2021-07-27
Publication date: 2022-06-23
Also published as: ZA202213150B; CN112724428A

Abstract

The present disclosure relates to the field of the preparation of polymeric materials, and in particular to a preparation method for a weather-resistant, wear-resistant and hydrophobic aid, comprising: step one: measuring or preparing a certain quantity of fluororesin particles; and step two: placing the fluororesin particles in a plasma device, treating the fluororesin particles for 1 min - 1 h in a specific gas environment and performing surface activation on the fluororesin particles to produce surface-activated fluororesin particles and form the hydrophobic aid; or chemically modifying the fluororesin particles by means of a chemical modifier; or placing the fluororesin particles in a plasma device, treating the fluororesin particles for 1 min - 1 h in a specific gas environment, performing surface activation on the fluororesin particles to produce surface-activated fluororesin particles, and using the chemical modifier. Further disclosed is an application of the weather-resistant, wear-resistant and hydrophobic aid. The fluororesin particles having low surface energy are modified to produce the hydrophobic aid which has long storage time, has significantly improved compatibility with a film-formed molded material, and can be uniformly dispersed in the film-formed molded material.

Description

A kind of preparation method and application of weather-resistant and wear-resistant hydrophobic auxiliary agent

technical field

The invention relates to the field of preparation of polymer materials, in particular to a preparation method and application of a weather-resistant and wear-resistant hydrophobic auxiliary agent.

Background technique

The super-hydrophobic phenomenon is also known as the "lotus leaf effect". The water contact angle of the super-hydrophobic surface is greater than 150° and the rolling angle is less than 10°. It has broad application prospects in real life. For example, water droplets are usually spherical on the surface of superhydrophobic objects, and only a small tilt angle is required, and the liquid will quickly roll off the surface of the superhydrophobic coating, while taking away contaminants such as dust. The surface of the superhydrophobic coating can also reduce the condensation adhesion of water vapor and the penetration of water. This excellent waterproof and moisture-proof performance can keep the coating surface clean and dry for a long time, and it can also inhibit the growth and reproduction of microorganisms and delay the corrosion of the protected substrate. The development of surface materials with hydrophobic or even super-hydrophobic properties will fundamentally change the materials' water-proof, mildew-proof, anti-corrosion and anti-fouling capabilities.

The basic mechanism of superhydrophobicity lies in the combination of micro- and nano-scale rough structures and low surface energy species. The key to the preparation of superhydrophobic surfaces is to simultaneously realize the preparation of rough structures and the modification of low surface energy substances. At present, there are three types of methods for preparing hydrophobic and superhydrophobic surfaces. The first type is to first prepare the structure by etching or etching, and then coat the low surface energy material; The structure is obtained; the third category is to prepare solid or liquid formulations with both low surface energy substances and micro-nano rough structures, and coat them on the desired surface. Most of the first two require special and specialized equipment, or require complex preparation processes, which are not conducive to large-scale development and application. The last method is relatively simple and effective, and the substrate has strong applicability. Among them, if the formulation only contains a hydrophobic auxiliary agent with low surface energy, but cannot form a rough micro-nano structure, it will only exhibit hydrophobicity, and it is difficult to obtain a superhydrophobic surface.

The most commonly used method in the third category above is to add hydrophobic functional additives to the formulation to achieve hydrophobicization of the surface. Commonly used hydrophobic additives are divided into three categories according to the original and final form. One is liquid small molecular substances, which can easily migrate to the surface of the coating to achieve hydrophobic modification, such as silane or fluorine-containing additives (CN103849208A a waterproof coating). Such additives have limited modification effect themselves, and also require a carrier to assist dispersion when applied to a solvent-free system, and the hydrophobic additives are easily depleted due to migration during use, causing the surface to lose hydrophobicity. The second type is the solid macromolecular wax, which will melt and migrate to the interface between the coating and the air when solidified at high temperature, such as polyethylene wax and polypropylene wax (CN202030687U A coated polyethylene wax micropowder; CN101250268A A preparation method of ultrafine powder wax). Such additives can only achieve limited hydrophobic modification and cannot provide micro- and nano-scale rough structures, so superhydrophobic coatings cannot be obtained. The third category is the hydrophobically modified inorganic particles. The hydrophobic modifiers are long-chain aliphatics or fluorosilanes. These hydrophobic particles are mixed with other components of the formulation, resulting in a surface with a certain roughness and low surface energy. Such as stearic acid-modified iron oxide powder (CN 103589200 A A preparation method of superhydrophobic iron oxide powder coating), silane-modified silica AEROXIDE LE3 (WO2007102960A2 Hydrophobic self-cleaning coating compositions) and fluorosilane-modified Diatomaceous earth powder (US Patent US008216674B2 Superhydrophobic diatomaceous earth). Such additives can impart hydrophobicity or superhydrophobicity to the surface by adjusting the addition ratio, but they have poor film-forming properties and are not wear-resistant. When worn, a large number of hydrophilic parts will be exposed, which will greatly reduce the surface hydrophobicity. However, ordinary fluorine-free modifiers such as long-chain aliphatic have poor weather resistance and are not resistant to outdoor aging. The fourth category is fluorine-containing organic particles, including polytetrafluoroethylene, polyvinylidene fluoride, etc. (CN 107652795 A A super-hydrophobic powder coating and its preparation method and application). These additives can control a wide range of hydrophobicity. And because the F-C bond energy is high, the overall weather resistance is better. However, there is no bonding between the fluororesin and the film-forming substance network, and the compatibility is poor, so the film-forming and formability are poor, and the wear resistance is also poor. Surface treatment of fluorine-containing organic particles is an effective solution, but the traditional DBD (Dielectric Barrier Discharge) plasma treatment method has no stirring and only a gas-phase atmosphere, and the powder is easy to aggregate into agglomerates when being treated. Complete treatment of the particle surface cannot be achieved. Such as CN 203562393 U a kind of particle material surface plasma treatment device. On the other hand, at the same time or after the activation of the plasma surface, chemical grafting is performed on the particle surface immediately, which can not only avoid the deactivation of the particle surface, but also improve the compatibility between the particle surface and the application environment (such as resin, cement, etc.). Sexual and chemical bonding.

SUMMARY OF THE INVENTION

The purpose of the present invention is to provide a preparation and application method of a hydrophobic auxiliary agent for hydrophobic and super-hydrophobic surfaces, so as to solve the problem that the surface of the existing liquid hydrophobic auxiliary agent easily loses hydrophobicity due to migration. Solid wax hydrophobic additives can only adjust the hydrophobicity to a limited extent; the weather resistance of fluorine-free silane modification is not ideal, and the hydrophobic surface prepared by fluorosilane-modified inorganic particles has poor abrasion resistance; the hydrophobic organic particles are unevenly dispersed and have poor film-forming properties; conventional DBD A series of problems such as the poor effect of plasma treatment of powder. The prepared auxiliaries can be stored for a long time, and can be uniformly dispersed in film-forming and forming materials when used, the hydrophobicity can be adjusted in a wide range between 90-163°, the rolling angle is as small as 6°, and it has high weather resistance and wear resistance. In order to solve the above-mentioned technical problems, the technical scheme adopted by the present invention is: a preparation method of a weather-resistant and wear-resistant hydrophobic auxiliary agent, comprising the following steps:

The first step: measuring or preparing a certain amount of fluororesin particles; the fluororesin particles include polytetrafluoroethylene (PTFE), polychlorotrifluoroethylene (PCTFE), polyvinylidene fluoride (PVDF), polyvinylidene fluoride - Hexafluoropropylene copolymer (PVDF-HFP), ethylene-tetrafluoroethylene copolymer (ETFE), ethylene-chlorotrifluoroethylene copolymer (ECTFE), polyvinyl fluoride (PVF) and fluorinated ethylene propylene copolymer (FEP) one or more of );

The second step: placing the fluororesin particles in a plasma device, treating them in a specific gas environment for 1min-1h, and performing surface activation treatment to prepare fluororesin particles after surface activation treatment to form hydrophobic additives;

Or use a chemical modifier to chemically modify the fluororesin particles to make chemically modified fluororesin particles, and then filter and dry them to make hydrophobic additives;

Or place the fluororesin particles in a plasma device, treat them in a specific gas environment for 1min-1h, and perform surface activation treatment to make fluororesin particles after surface activation treatment; and use a chemical modifier to activate the surface. The treated fluororesin particles are chemically modified to form chemically modified fluororesin particles, which are then filtered and dried to form a hydrophobic aid.

In the present invention, fluororesin particles are surface-modified with plasma activation and chemical modifier to obtain modified fluororesin particles. Activated and modified fluororesin particles can be added to raw materials or finished products such as coatings, plastics, cement, etc. to create hydrophobic surfaces. It solves the problem that the existing liquid additives are easy to cause the coating to lose hydrophobicity due to migration, the ability of solid wax hydrophobic additives to adjust the hydrophobicity of the coating is limited, and the hydrophobic coating prepared by fluorine-free silane-modified inorganic particles has weather resistance and resistance. A series of problems such as poor abrasion resistance and poor abrasion resistance of the hydrophobic coating prepared by fluorine-containing silane-modified inorganic particles; the hydrophobic surface prepared by this method has high weather resistance and abrasion resistance.

Compared with the prior art, the beneficial effects of the present invention: the present invention utilizes physical and chemical methods to modify the fluororesin particles with low surface energy, the preparation of the hydrophobic auxiliary agent has a long storage time, and the compatibility with the film-forming product is greatly improved. so that it can be uniformly dispersed in the film-forming material. The hydrophobic surface prepared by using the hydrophobic auxiliary agent in the present invention can adjust the hydrophobicity in a wide range, and the prepared hydrophobic surface has good weather resistance and strong abrasion resistance.

Detailed ways

The technical solutions in the embodiments of the present invention will be clearly and completely described below. Obviously, the described embodiments are only a part of the embodiments of the present invention, rather than all the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those of ordinary skill in the art without creative efforts shall fall within the protection scope of the present invention.

Many specific details are set forth in the following description to facilitate a full understanding of the present invention, but the present invention can also be implemented in other ways different from those described herein, and those skilled in the art can do so without departing from the connotation of the present invention. Similar promotion, therefore, the present invention is not limited by the specific embodiments disclosed below.

A preparation method of a weather-resistant and wear-resistant hydrophobic auxiliary agent of the present invention comprises the following steps:

In this step, the plasma device includes atmospheric pressure plasma, low pressure plasma, or a combination device of one or more of low pressure plasma emitters equipped with microwaves; the specific gas environment includes H2, Ar, A combination of one or more of N2, O2, or a mixed gas of one or more of H2, Ar, N2, and O2 mixed with NH3, acrylic acid, or a silane coupling agent.

In the second step of the present invention, the fluororesin particles are subjected to surface activation treatment, or chemical modification treatment, or chemical modification treatment is carried out after the surface activation treatment; as a preferred embodiment of the present invention, in the second step, using After the surface activation treatment of the fluororesin particles, the chemical modification treatment is carried out.

The chemical modifier includes an ethanol solution containing a silane coupling agent, an ethanol solution mixed with a silane coupling agent and boric acid, and an aqueous acrylic acid solution; the silane coupling agent includes aminopropyltriethoxysilane, aminopropyl A combination of one or more of trimethoxysilane and N-(2-aminoethyl)-3-aminopropyltrimethoxysilane; wherein the ethanol solution containing a silane coupling agent is coupled with silane The solvent used in the ethanol solution mixed with boric acid is ethanol, and the solubility is 10-30%; in the ethanol solution mixed with the silane coupling agent and boric acid, the ratio by weight of the silane coupling agent to the boric acid is 10: 1-1:1; the concentration of the acrylic acid aqueous solution is 10%-50%.

Moreover, in the preferred solution of step 2, after the surface activation treatment of the fluororesin particles is carried out, the chemical modification treatment is carried out. In an environment of 0-80 degrees Celsius, chemically modify the fluororesin particles after the surface activation treatment; when chemically modifying the fluororesin particles after the surface activation treatment, use stirring, mechanical vibration, One or more treatment methods of immersion and reflow.

In the present invention, the particle size range of the measured or prepared fluororesin particles is 0.1um-20um.

Hereinafter, according to the preferred scheme of performing the surface activation treatment on the fluororesin particles in step 2 and then carrying out the chemical modification treatment, and according to the difference in the material composition of the selected or prepared fluororesin particles, the following embodiments are given:

Method Embodiment 1:

(1) At room temperature, take 100g of polytetrafluoroethylene particles with a median particle size of 1um;

(2) Put it into the low-pressure plasma raw material processing chamber, evacuate to 0.2 mbar, fill with N2, turn on the switch of the stirring device and the plasma generator, and take it out from the raw material processing chamber after 10 minutes of treatment to obtain surface-activated PTFE particles or/and under stirring at 1000RPM, add the particle or the surface-activated fluororesin particle to the ethanol solution of 200mL aminopropyltriethoxysilane, and the stirring speed is increased to 2500RPM, and the reaction is 2h; filter with filter paper to obtain a solid The pellets were then air-dried in a fume hood. The dried solid is sampled and detected with a solid content analyzer to ensure that the content of ethanol and water does not exceed 0.1%, to obtain surface-modified fluororesin particles.

For the above steps (1) and (2), there are:

Method Embodiment 2

At room temperature, take 100g of vinylidene fluoride-hexafluoropropylene copolymer particles with a median particle size of 10um;

Put it into the low-pressure plasma raw material processing chamber, evacuate it to 0.2 mbar, fill it with NH3, turn on the stirring device and the switch of the plasma generator, and take it out from the raw material processing chamber after 2 minutes of treatment to obtain the activated vinylidene fluoride-hexafluoropropylene copolymer. Particles without subsequent chemical modification;

Method Embodiment 3

At room temperature, take 100g of ethylene-tetrafluoroethylene copolymer particles with a median particle size of 20um;

Put it into a torch-type atmospheric pressure plasma raw material processing chamber, fill it with N2, turn on the stirring device and the switch of the plasma generator, and take it out from the raw material processing chamber after 5 minutes of treatment to obtain activated ethylene-tetrafluoroethylene copolymer particles; no subsequent chemical modified.

Method Embodiment 4

At room temperature, take 100g of polytetrafluoroethylene particles with a median particle size of 3um;

Put it into the low-pressure plasma raw material processing chamber, evacuate it to 1 mbar, fill it with H2, turn on the stirring device, the switch of the plasma generator and the switch of the microwave generator, and take it out from the raw material processing chamber after 10 minutes of treatment to obtain the surface-activated polytetrafluoroethylene. Vinyl fluoride particles; chemically modified fluororesin particles are obtained after subsequent chemical modification, filtration and drying.

Method Embodiment 5

At room temperature, take 100g of polychlorotrifluoroethylene (PCTFE) resin particles with a particle size of 10um;

Placed in the processing chamber of DBD atmospheric pressure plasma equipment, introduced O2 atmosphere, turned on stirring, and started plasma processing for 2 minutes. Surface-activated polychlorotrifluoroethylene (PCTFE) particles are obtained; after subsequent chemical modification, filtration and drying, chemically modified fluororesin particles are obtained.

Method Embodiment 6

At room temperature, take 100g of fluorinated ethylene propylene copolymer (FEP) particles with a median particle size of 20um;

Placed in the processing chamber of the torch-type atmospheric plasma equipment, turned on the stirring device, filled with air and the plasma generator switch, and took out from the raw material processing chamber after 2 minutes of treatment to obtain the surface-activated fluorinated ethylene propylene copolymer ( FEP) particles; chemically modified fluororesin particles are obtained after subsequent chemical modification, filtration and drying.

For the above-mentioned chemical modification process, there are many other embodiments, such as:

Method Embodiment 7

Under stirring at 1000 RPM, the fluororesin particles weighed in step (1) were added to 200 mL of acrylic acid aqueous solution, the stirring speed was increased to 2500 RPM, and the reaction was carried out for 2 h; the solid particles were obtained by filtering with filter paper, and then placed in a fume hood to air dry; Sampling of the solid obtained is detected by a solid content analyzer to ensure that the content of ethanol and water is not more than 0.1%, that is, surface-modified fluororesin particles are obtained.

Method Embodiment 8

Under stirring at 1000 RPM, the fluororesin particles weighed in step (1) were added to 200 mL of an ethanol solution of aminopropyltriethoxysilane and boric acid, the stirring speed was increased to 2500 RPM, and the reaction was carried out for 2 h; filtered with filter paper to obtain solid particles, Then put it in a fume hood to air dry; take samples of the dried solids and use a solid content analyzer to detect them to ensure that the ethanol and water content does not exceed 0.1%, to obtain surface-modified fluororesin particles.

In the present invention, the hydrophobic auxiliary agent is used in the fields of powder coatings, solvent-based coatings, water-based coatings, plastics, asphalt and cement. In specific use, the hydrophobic auxiliary agent is added to the powder coatings, or solvent-based coatings, Or water-based coatings, or plastics, or asphalt, or cement, fully stir to make a mixture, and then process it into a finished product. As a solution, hydrophobic additives and powder coatings, or solvent-based coatings, or water-based coatings, or plastics , or in the mixture of asphalt or cement, by weight, the proportion of the hydrophobic aid is 0.5%-50%.

Application Example 1

The hydrophobic auxiliary agent prepared in Embodiment 1 of the above-mentioned method is added to the polyester TGIC (Triglycidyl isocyanurate) powder coating raw material in an amount of 5% by weight within one hour; the raw material includes polyester resin, TGIC, Pigments, fillers, degassing agents, leveling agents, etc.;

Fully agitate with a high-speed mixer, then fully knead with a twin-screw extruder at a temperature of 100°C, press and cool it into flakes, and use an air classification mill to pulverize and sieve to a median particle size of 35um;

Sprayed on cast iron plate for powder coating at 35KV, baked at 200°C for 15 minutes to obtain a hydrophobic coating with a water contact angle of 123°, tested for 500h according to the UV aging test standard of coatings ISO 11507-2007, and the contact angle was 121° , rubbed 100 times with P220 sandpaper under a pressure of 9.8KPa, and the contact angle was 118°.

Application Example 2

The hydrophobic auxiliary agent prepared according to the above-mentioned method Embodiment 2 is added to the raw material of polyester TGIC powder coating in an amount of 7.5% by mass within one hour, and the raw material includes polyester resin, TGIC, pigment, filler, degassing agent, fluid equalizer, etc.;

Sprayed on cast iron plate for powder coating at 35KV, baked at 200°C for 15 minutes to obtain a hydrophobic coating with a water contact angle of 132°, tested for 500h according to the UV aging test standard for coatings, ISO 11507-2007, and the contact angle was 131° . Rubbing with P220 sandpaper under the pressure of 9.8KPa for 100 times, the contact angle is 126°.

Application Example 3

The hydrophobic auxiliary agent prepared according to the above-mentioned method embodiment 3 is added to the polyester TGIC powder coating raw material in an amount of 20% by mass within one hour;

Sprayed on cast iron plate for powder coating at 35KV, baked at 200°C for 15 minutes to obtain a hydrophobic coating with a water contact angle of 155° and a rolling angle of 7°, and tested for 500h according to the UV aging test standard for coatings ISO 11507-2007 , the contact angle is still 155°, and the contact angle is 153° by rubbing with P220 sandpaper under the pressure of 9.8KPa for 100 times.

Application Example 4

The hydrophobic auxiliary agent prepared according to the above-mentioned method Embodiment 4 is added to the solvent-based epoxy coating in an amount of 20% by mass, and the liquid coating is fully stirred and mixed with a high-speed mixer, and then brushed on the cast iron plate, and then aired naturally. dry to obtain a hydrophobic coating. The water contact angle is 158° and the rolling angle is 7°. According to the coating UV aging test standard ISO 11507-2007 test for 500h, the contact angle is 154°. Rubbing with P220 sandpaper under the pressure of 9.8KPa for 100 times, the contact angle is 153°.

Application Example 5

The hydrophobic auxiliary agent prepared according to the above-mentioned method Embodiment 5 is added to the polyethylene resin particles in an amount of 20% by mass, fully stirred with a high-speed mixer, and then fully kneaded by a twin-screw extruder at a temperature of 200°C And injection extrusion to make composite materials. The resulting material has a strong hydrophobic surface with a water contact angle of 156° and a rolling angle of 7°. Rubbing with P220 sandpaper under the pressure of 9.8KPa for 100 times, the contact angle is 153°.

Application Example 6

The hydrophobic auxiliary agent prepared according to the above-mentioned method Embodiment 7 is added to the cement product in an amount of 20% by mass, fully stirred with a mixer, and then water is added according to the ratio of the original concrete to water, stirred again, and transferred to the mold, After solidification, hydrophobic cement was obtained with a water contact angle of 158° and a rolling angle of 6°. Rubbing with P220 sandpaper under the pressure of 9.8KPa for 100 times, the contact angle is 158°.

In the above application examples, it is the hydrophobic auxiliary agent prepared by the preparation method of the present invention, which has produced a very good effect.

Comparative Application Example 1

The PTFE particles were added to the polyester TGIC powder coating raw material in an addition amount of 10% by mass. The raw materials include polyester resin, TGIC, pigments, fillers, degassing agents, leveling agents, etc., which are fully mixed with a high-speed mixer, and then fully kneaded by a twin-screw extruder at a temperature of 100°C and pressed and cooled into flakes. , and crushed and sieved with an air classification mill to a median particle size of 35um;

It was sprayed on a cast iron plate for powder coating at 35KV, and baked at 200°C for 15 minutes to obtain a hydrophobic coating with a water contact angle of 140°. According to the coating UV aging test standard ISO 11507-2007 test for 500h, the contact angle is 138°. The coating was rubbed 80 times with P220 sandpaper under a pressure of 9.8KPa, and the contact angle was 20°.

Comparative Application Example 2

AEROXIDE LE3 was added to the polyester TGIC powder coating raw material in an amount of 5% by mass. The raw materials include polyester resin, TGIC, pigments, fillers, degassing agents, leveling agents, etc., which are fully mixed with a high-speed mixer, and then fully kneaded by a twin-screw extruder at a temperature of 100°C and pressed and cooled into flakes. , and crushed and sieved with an air classification mill to a median particle size of 35um;

It was sprayed on a cast iron plate for powder coating at 35KV and baked at 200°C for 15 minutes to obtain a hydrophobic coating with a water contact angle of 170° and a rolling angle of 2°. According to the coating UV aging test standard ISO 11507-2007 test for 500h, the coating becomes a hydrophilic surface with a contact angle of 26°. Rubbing with P220 sandpaper under the pressure of 9.8KPa for 10 times, the contact angle of the coating has been reduced to 65°.

Through the above and the above comparison, the present invention overcomes the deficiencies of the prior art, and provides a preparation and application method of a hydrophobic aid for hydrophobic and superhydrophobic surfaces. It solves the problem that the existing liquid hydrophobic assistant is easy to cause the surface to lose hydrophobicity due to migration; the solid wax hydrophobic assistant can only adjust the hydrophobicity to a limited extent; the weather resistance modified by non-fluorine silane is not ideal; A series of problems such as poor surface wear resistance; uneven dispersion of hydrophobic organic particles and poor film formation; poor effect of conventional DBD plasma treatment of powder. The prepared auxiliaries can be stored for a long time, and can be uniformly dispersed in film-forming and forming materials when used, the hydrophobicity can be adjusted in a wide range between 90-163°, the rolling angle is as small as 6°, and it has high weather resistance and wear resistance. sex.

The above descriptions are only preferred embodiments of the present invention, and are not intended to limit the present invention. Although the present invention has been described in detail with reference to the foregoing embodiments, those skilled in the art can still understand the foregoing embodiments. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention shall be included in the protection scope of the present invention, if the technical solution described is modified, or some technical features thereof are equivalently replaced. Inside.

Claims

A preparation method of a weather-resistant and wear-resistant hydrophobic auxiliary agent, characterized in that the preparation method comprises the following steps:

The first step: measuring or preparing a certain amount of fluororesin particles; the fluororesin particles include polytetrafluoroethylene (PTFE), polychlorotrifluoroethylene (PCTFE), polyvinylidene fluoride (PVDF), polyvinylidene fluoride - Hexafluoropropylene copolymer (PVDF-HFP), ethylene-tetrafluoroethylene copolymer (ETFE), ethylene-chlorotrifluoroethylene copolymer (ECTFE), polyvinyl fluoride (PVF) and fluorinated ethylene propylene copolymer (FEP) one or more of );

The second step: placing the fluororesin particles in a plasma device, treating them in a specific gas environment for 1min-1h, and performing surface activation treatment to prepare fluororesin particles after surface activation treatment to form hydrophobic additives;

Or use a chemical modifier to chemically modify the fluororesin particles to make chemically modified fluororesin particles, and then filter and dry them to make hydrophobic additives;

Or place the fluororesin particles in a plasma device, treat them in a specific gas environment for 1min-1h, and perform surface activation treatment to make fluororesin particles after surface activation treatment; and use a chemical modifier to activate the surface. The treated fluororesin particles are chemically modified to form chemically modified fluororesin particles, which are then filtered and dried to form a hydrophobic aid.
The preparation method according to claim 1, wherein the plasma device comprises a combination device of one or more of atmospheric pressure plasma, low pressure plasma, or a low pressure plasma emitter equipped with microwaves.
The preparation method according to claim 1, characterized in that: in the specific gas environment, one or more combinations of H2, Ar, N2, and O2 are included, or one of H2, Ar, N2, and O2 is included. One or more combinations are mixed with NH3, acrylic or silane coupling agent.
The preparation method according to claim 1, wherein: the chemical modifier comprises an ethanol solution containing a silane coupling agent, an ethanol solution mixed with a silane coupling agent and boric acid, and an aqueous acrylic acid solution; the silane coupling agent The agent comprises a combination of one or more of aminopropyltriethoxysilane, aminopropyltrimethoxysilane, N-(2-aminoethyl)-3-aminopropyltrimethoxysilane.
The preparation method according to claim 4, wherein the solvent used in the ethanol solution containing the silane coupling agent and the ethanol solution mixed with the silane coupling agent and boric acid is ethanol, and the solubility is 10-30%;

In the ethanol solution in which the silane coupling agent and the boric acid are mixed, the ratio of the silane coupling agent to the boric acid is 10:1-1:1 by weight;

The concentration of the acrylic acid aqueous solution is 10%-50%.
The preparation method according to claim 1, characterized in that: in the first step, the particle size range of the fluororesin particles measured or prepared is 0.1um-20um.
The preparation method according to claim 1, wherein in the third step, chemical modification treatment is performed on the surface-activated fluororesin particles in an environment of 0-80 degrees Celsius;

In the third step, when chemically modifying the fluororesin particles after the surface activation treatment, one or more treatment methods of stirring, mechanical vibration, soaking, and reflow are adopted.
The application of the weather-resistant and wear-resistant hydrophobic auxiliary agent prepared by the preparation method according to claim 1 is characterized in that: the hydrophobic auxiliary agent is used in the fields of powder coatings, solvent-based coatings, water-based coatings, plastics, asphalt and cement.
The application according to claim 8, characterized in that: after adding the hydrophobic auxiliary agent to the powder coating, or solvent-based coating, or water-based coating, or plastic, or asphalt, or cement, fully stir to prepare Mixed products, and then processed into finished products.
The application according to claim 9 is characterized in that: in the mixture of hydrophobic auxiliary agent and powder coating, or solvent-based coating, or water-based coating, or plastic, or asphalt, or cement, by weight, the hydrophobic auxiliary The proportion of the agent is 0.5%-50%.