CN112724428A - Preparation method and application of weather-resistant wear-resistant hydrophobic auxiliary agent - Google Patents

Preparation method and application of weather-resistant wear-resistant hydrophobic auxiliary agent Download PDF

Info

Publication number
CN112724428A
CN112724428A CN202011513864.5A CN202011513864A CN112724428A CN 112724428 A CN112724428 A CN 112724428A CN 202011513864 A CN202011513864 A CN 202011513864A CN 112724428 A CN112724428 A CN 112724428A
Authority
CN
China
Prior art keywords
fluororesin particles
auxiliary agent
hydrophobic
prepare
surface activation
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
CN202011513864.5A
Other languages
Chinese (zh)
Inventor
祝京旭
张辉
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Tianjin Xidun Powder Paint Technology Co ltd
Original Assignee
Tianjin Xidun Powder Paint Technology Co ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Tianjin Xidun Powder Paint Technology Co ltd filed Critical Tianjin Xidun Powder Paint Technology Co ltd
Priority to CN202011513864.5A priority Critical patent/CN112724428A/en
Publication of CN112724428A publication Critical patent/CN112724428A/en
Priority to PCT/CN2021/108524 priority patent/WO2022127116A1/en
Priority to ZA2022/13150A priority patent/ZA202213150B/en
Pending legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J3/00—Processes of treating or compounding macromolecular substances
    • C08J3/28—Treatment by wave energy or particle radiation
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B24/00—Use of organic materials as active ingredients for mortars, concrete or artificial stone, e.g. plasticisers
    • C04B24/24—Macromolecular compounds
    • C04B24/26—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C04B24/2682—Halogen containing polymers, e.g. PVC
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J3/00—Processes of treating or compounding macromolecular substances
    • C08J3/12—Powdering or granulating
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/04—Homopolymers or copolymers of ethene
    • C08L23/06—Polyethene
    • 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
    • C09D163/00—Coating compositions based on epoxy resins; Coating compositions based on derivatives of epoxy resins
    • 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
    • C09D167/00—Coating compositions based on polyesters obtained by reactions forming a carboxylic ester link in the main chain; Coating compositions based on derivatives of such polymers
    • 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
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/03—Powdery paints
    • C09D5/033—Powdery paints characterised by the additives
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2323/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
    • C08J2323/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
    • C08J2323/04—Homopolymers or copolymers of ethene
    • C08J2323/08—Copolymers of ethene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2323/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
    • C08J2323/26—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers modified by chemical after-treatment
    • C08J2323/28—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers modified by chemical after-treatment by reaction with halogens or halogen-containing compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2327/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers
    • C08J2327/02—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers not modified by chemical after-treatment
    • C08J2327/12—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers not modified by chemical after-treatment containing fluorine atoms
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2327/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers
    • C08J2327/02—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers not modified by chemical after-treatment
    • C08J2327/12—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers not modified by chemical after-treatment containing fluorine atoms
    • C08J2327/16—Homopolymers or copolymers of vinylidene fluoride
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2327/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers
    • C08J2327/02—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers not modified by chemical after-treatment
    • C08J2327/12—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers not modified by chemical after-treatment containing fluorine atoms
    • C08J2327/18—Homopolymers or copolymers of tetrafluoroethylene

Abstract

The invention relates to the field of preparation of high polymer materials, and particularly discloses a preparation method of a weather-resistant wear-resistant hydrophobic auxiliary agent; comprises the first step: measuring or preparing a certain amount of fluororesin particles; the second step is as follows: placing fluororesin particles in a plasma device, treating for 1min-1h in a specific gas environment, and carrying out surface activation treatment to prepare fluororesin particles subjected to surface activation treatment to form a hydrophobic auxiliary agent; or using a chemical modifier to carry out chemical modification treatment on the fluororesin particles; or placing the fluororesin particles in a plasma device, treating for 1min-1h in a specific gas environment, and carrying out surface activation treatment to prepare fluororesin particles subjected to surface activation treatment; and a chemical modifier is used. The invention also discloses an application of the weather-resistant wear-resistant hydrophobic auxiliary agent; the hydrophobic additive prepared by modifying the fluororesin particles with low surface energy has long storage time, and greatly improves the compatibility with the film-forming object so as to ensure that the hydrophobic additive can be uniformly dispersed in the film-forming object.

Description

Preparation method and application of weather-resistant wear-resistant hydrophobic auxiliary agent
Technical Field
The invention relates to the field of preparation of high polymer materials, in particular to a preparation method and application of a weather-resistant wear-resistant hydrophobic auxiliary agent.
Background
The super-hydrophobic phenomenon is also called as a lotus effect, the water contact angle of the super-hydrophobic surface is more than 150 degrees, the rolling angle is less than 10 degrees, the super-hydrophobic surface has excellent surface properties such as self-cleaning, antifouling, easy deicing, corrosion resistance, antibiosis and the like, and has wide application prospect in actual life. If water drops are generally spherical on the surface of the super-hydrophobic object, the liquid can quickly roll off from the surface of the super-hydrophobic coating only by a small inclination angle, and meanwhile, pollutants such as dust and the like are taken away. The surface of the super-hydrophobic coating can also reduce the condensation adhesion of water vapor and the penetration of water. The excellent waterproof and moistureproof performance can keep the surface of the coating clean and dry for a long time, and can also inhibit the growth and propagation of microorganisms and delay the corrosion of the protected substrate. The development of surface materials with hydrophobic property and even super-hydrophobic property can fundamentally change the waterproof, mildewproof, antiseptic and anti-fouling capability of the materials.
The basic mechanism of superhydrophobicity is the combination of micro-nano-scale roughness and low surface energy materials. The key point of preparing the super-hydrophobic surface is to simultaneously realize the preparation of a rough structure and the modification of a low-surface-energy substance. The current methods for preparing hydrophobic and superhydrophobic surfaces are of three types, the first type is to prepare a structure by corrosion or etching method and then coat a low surface energy substance; second, obtaining a low energy surface, and then cutting the surface to obtain a structure; and the third type is to prepare a solid or liquid formula which has both low surface energy substances and a micro-nano coarse structure and coat the solid or liquid formula on a required surface. The former two methods require special and special equipment or complex preparation process, which is not suitable for large-scale development and application. The last method is simple and effective, and the applicability of the base material is strong. Wherein, if the formula only contains hydrophobic auxiliary agent with low surface energy but can not form a rough micro-nano structure, only the hydrophobic property is presented, and the super-hydrophobic surface is difficult to obtain.
The most common method in the third category is to add a hydrophobic functional assistant to the formulation to achieve surface hydrophobization. The conventional hydrophobic additives are classified into three types according to original and final forms, one type is a liquid small molecular substance which can conveniently migrate to the surface of a coating layer to realize hydrophobic modification, such as silane or fluorine-containing additives (CN103849208A a waterproof coating). The modification effect of the auxiliary agent is limited, a carrier is also needed for assisting dispersion when the auxiliary agent is applied to a solvent-free system, and the hydrophobic auxiliary agent is easy to be exhausted due to migration in the using process, so that the surface loses hydrophobicity. The second type is a solid macromolecular wax which melts and migrates 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). The auxiliary agent can only realize limited hydrophobic modification, and can not provide a micro-nano-scale coarse structure, so that a super-hydrophobic coating can not be obtained. The third type is a hydrophobically modified inorganic particle. The hydrophobic modifier is long-chain fat or fluorosilane. These hydrophobic particles mix together with the other components of the formulation to eventually form a surface with some roughness and low surface energy. Such as stearic acid-modified iron oxide powder (CN 103589200A, a method for preparing super-Hydrophobic iron oxide powder coating), silane-modified silica AEROXIDE LE3(WO2007102960A2 Hydrophobic self-cleaning coating compositions) and fluorosilane-modified diatomaceous earth powder (U.S. Pat. No. 3, 008216674B2 Superhydrobic diatomaceous earth). The addition ratio of the auxiliary agent can be adjusted to endow the surface with hydrophobicity or super hydrophobicity, but the film forming property is poor and the abrasion resistance is not good. When abraded, a large number of hydrophilic moieties are exposed, resulting in a large decrease in surface hydrophobicity. Common fluorine-free modifiers such as long-chain aliphatic have poor weather resistance and do not resist outdoor aging. The fourth type is fluorine-containing organic particles, including polytetrafluoroethylene, polyvinylidene fluoride and the like (CN 107652795A is a super-hydrophobic powder coating and a preparation method and application thereof). Such adjuvants enable a wide range of control of hydrophobicity. And since the F-C bond energy is high, the overall weather resistance is good. However, the fluororesin has no bonding effect with the network of the film-forming material, and has poor compatibility, so that the film-forming property and the formability are poor, and the wear resistance is also poor. The 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 has gas phase atmosphere, and powder is easy to agglomerate when being treated, so that the complete treatment of the particle surface cannot be realized. Such as CN 203562393U, a surface plasma treatment device for particle materials. On the other hand, the chemical grafting treatment is carried out on the particle surface immediately while or after the plasma surface is activated, so that the inactivation of the particle surface can be avoided, and the compatibility and the chemical bonding force between the particle surface and the application environment (such as resin, cement and the like) can be improved.
Disclosure of Invention
The invention aims to provide a preparation method and an application method of a hydrophobic auxiliary agent for hydrophobic and super-hydrophobic surfaces, and solves the problem that the surface loses hydrophobicity due to migration easily of the existing liquid hydrophobic auxiliary agent. The solid wax hydrophobic auxiliary agent can only adjust the hydrophobicity in a limited way; the weather resistance of fluorine-free silane modification is not ideal, and the hydrophobic surface prepared by fluorine-containing silane modified inorganic particles has poor wear resistance; the hydrophobic organic particles are dispersed unevenly and have poor film-forming property; the conventional DBD plasma has a series of problems of poor powder treatment effect and the like. The prepared auxiliary agent can be stored for a long time, can be uniformly dispersed in a film-forming and forming substance when in use, can adjust the hydrophobicity within a large range of 90-163 degrees, has a rolling angle as small as 6 degrees, and has higher weather resistance and wear resistance, and the technical scheme adopted by the invention for solving the technical problems is as follows: a preparation method of a weather-resistant wear-resistant hydrophobic auxiliary agent comprises the following steps:
the first step is as follows: measuring or preparing a certain amount of fluororesin particles; the fluororesin particles comprise one or more of 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);
the second step is as follows: placing the fluororesin particles in a plasma device, treating for 1min-1h in a specific gas environment, and carrying out surface activation treatment to prepare fluororesin particles subjected to surface activation treatment to form a hydrophobic auxiliary agent;
or using a chemical modifier to carry out chemical modification treatment on the fluororesin particles to prepare the fluororesin particles after chemical modification, and then filtering and drying the fluororesin particles to prepare the hydrophobic auxiliary agent;
or placing the fluororesin particles in a plasma device, treating for 1min-1h in a specific gas environment, and carrying out surface activation treatment to prepare fluororesin particles subjected to surface activation treatment; and carrying out chemical modification treatment on the fluororesin particles subjected to surface activation treatment by using a chemical modifier to prepare the fluororesin particles subjected to chemical modification, and then filtering and drying the fluororesin particles to prepare the hydrophobic auxiliary agent.
In the present invention, fluororesin pellets are surface-modified with a plasma activating and chemical modifying agent to obtain modified fluororesin pellets. The activated and modified fluororesin particles can be added to raw materials or finished products of coatings, plastics, cement and the like to generate a hydrophobic surface. The problems that the existing liquid auxiliary agent is easy to cause the coating to lose hydrophobicity due to migration, the capability of adjusting the hydrophobicity of the coating by the solid wax hydrophobic auxiliary agent is limited, the weather resistance and the wear resistance of the hydrophobic coating prepared by inorganic particles modified by fluorine-free silane are poor, the wear resistance of the hydrophobic coating prepared by inorganic particles modified by fluorine-containing silane is poor and the like are solved; the hydrophobic surface prepared by the method has higher weather resistance and wear resistance.
Compared with the prior art, the invention has the beneficial effects that: the invention utilizes physical and chemical methods to modify fluororesin particles with low surface energy, the hydrophobic auxiliary agent prepared by the method has long storage time, and the compatibility with the film forming object is greatly improved so that the hydrophobic auxiliary agent can be uniformly dispersed in the film forming object. The hydrophobic surface prepared by using the hydrophobic auxiliary agent can adjust the hydrophobicity in a large range, and the prepared hydrophobic surface has good weather resistance and strong wear resistance.
Detailed Description
The technical solutions in the embodiments of the present invention are clearly and completely described below, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
In the following description, numerous specific details are set forth in order to provide a thorough understanding of the present invention, but the present invention may be practiced in other ways than those specifically described and will be readily apparent to those of ordinary skill in the art without departing from the spirit of the present invention, and therefore the present invention is not limited to the specific embodiments disclosed below.
The invention discloses a preparation method of a weather-resistant wear-resistant hydrophobic auxiliary agent, which comprises the following steps:
the first step is as follows: measuring or preparing a certain amount of fluororesin particles; the fluororesin particles comprise one or more of 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);
the second step is as follows: placing the fluororesin particles in a plasma device, treating for 1min-1h in a specific gas environment, and carrying out surface activation treatment to prepare fluororesin particles subjected to surface activation treatment to form a hydrophobic auxiliary agent;
or using a chemical modifier to carry out chemical modification treatment on the fluororesin particles to prepare the fluororesin particles after chemical modification, and then filtering and drying the fluororesin particles to prepare the hydrophobic auxiliary agent;
or placing the fluororesin particles in a plasma device, treating for 1min-1h in a specific gas environment, and carrying out surface activation treatment to prepare fluororesin particles subjected to surface activation treatment; and carrying out chemical modification treatment on the fluororesin particles subjected to surface activation treatment by using a chemical modifier to prepare the fluororesin particles subjected to chemical modification, and then filtering and drying the fluororesin particles to prepare the hydrophobic auxiliary agent.
In this step, the plasma device comprises one or more of a combination device of normal pressure plasma, low pressure plasma, or a low pressure plasma emitter equipped with microwave; the specific gas environment comprises a mixed gas of one or more of H2, Ar, N2 and O2 or one or more of H2, Ar, N2 and O2 mixed with NH3, acrylic acid or silane coupling agent.
In the second step of the invention, the fluororesin particles are subjected to surface activation treatment, or chemical modification treatment is carried out after the surface activation treatment; in a preferred embodiment of the present invention, in the second step, the fluororesin pellets are subjected to a surface activation treatment and then to a chemical modification treatment.
The chemical modifier comprises an ethanol solution containing a silane coupling agent, an ethanol solution mixed by the silane coupling agent and boric acid and an acrylic acid aqueous solution; the silane coupling agent comprises one or more of aminopropyltriethoxysilane, aminopropyltrimethoxysilane and N- (2-aminoethyl) -3-aminopropyltrimethoxysilane in combination; wherein the ethanol solution containing the silane coupling agent and the ethanol solution mixed by the silane coupling agent and boric acid use ethanol as a solvent, and the solubility is 10-30%; in the ethanol solution mixed by the silane coupling agent and the boric acid, the ratio of the silane coupling agent to the boric acid is (by weight) 10: 1-1: 1; the concentration of the acrylic acid aqueous solution is 10-50%.
In a preferred embodiment of the second step, the fluororesin pellets are subjected to a surface activation treatment and then to a chemical modification treatment. Carrying out chemical modification treatment on the fluororesin particles subjected to surface activation treatment in an environment of 0-80 ℃; when the fluorine resin particles after the surface activation treatment are subjected to chemical modification treatment, one or more treatment modes of stirring, mechanical vibration, soaking and refluxing are adopted.
In the present invention, the fluororesin pellets are measured or prepared in a particle size range of 0.1um to 20 um.
In the following, according to the preferred embodiment of performing the surface activation treatment on the fluororesin pellets and then performing the chemical modification treatment in the second step, and according to the material composition of the selected or prepared fluororesin pellets, the following embodiments are exemplified:
method embodiment 1:
(1) at room temperature, 100g of polytetrafluoroethylene particles with the medium particle size of 1um are taken;
(2) placing into a low-pressure plasma raw material treatment chamber, vacuumizing to 0.2mbar, charging N2, opening a stirring device and a plasma generator switch, treating for 10min, and taking out from the raw material treatment chamber to obtain surface activated polytetrafluoroethylene particles; or/and under the stirring of 1000RPM, adding the weighed particles or the fluororesin particles with activated surfaces into 200mL of ethanol solution of aminopropyl triethoxysilane, increasing the stirring speed to 2500RPM, and reacting for 2 h; the solid particles were filtered through filter paper and then air dried in a fume hood. And (3) sampling the dried solid, detecting by using a solid content analyzer, and ensuring that the content of ethanol and water is not more than 0.1 percent to obtain the surface modified fluororesin particles.
For the above steps (1) and (2), there are:
method embodiment 2
At room temperature, 100g of vinylidene fluoride-hexafluoropropylene copolymer particles with the medium particle size of 10um are taken;
placing into a low-pressure plasma raw material processing chamber, vacuumizing to 0.2mbar, charging NH3, opening a stirring device and a plasma generator switch, processing for 2min, and taking out from the raw material processing chamber to obtain activated vinylidene fluoride-hexafluoropropylene copolymer particles without subsequent chemical modification;
method embodiment 3
At room temperature, 100g of ethylene-tetrafluoroethylene copolymer particles with the medium particle size of 20um are taken;
putting into torch type normal pressure plasma raw material processing chamber, charging N2, turning on the stirring device and the plasma generator switch, processing for 5min, and taking out from the raw material processing chamber to obtain activated ethylene-tetrafluoroethylene copolymer particles; no subsequent chemical modification is required.
Method embodiment 4
At room temperature, 100g of polytetrafluoroethylene particles with the medium particle size of 3um are taken;
placing the raw material into a low-pressure plasma raw material processing chamber, vacuumizing to 1mbar, filling H2, opening a stirring device, a plasma generator switch and a microwave generator switch, processing for 10 minutes, and taking out the raw material from the raw material processing chamber to obtain surface-activated polytetrafluoroethylene particles; and carrying out subsequent chemical modification, filtering and drying to obtain the chemically modified fluororesin particles.
Method embodiment 5
Taking 100g of Polychlorotrifluoroethylene (PCTFE) resin particles with the particle size of 10um at room temperature;
the resulting mixture was placed in a treatment chamber of a DBD atmospheric pressure plasma apparatus, an atmosphere of O2 was introduced, the stirring was turned on, and the plasma treatment was started for 2 minutes. Obtaining surface-activated Polychlorotrifluoroethylene (PCTFE) particles; and carrying out subsequent chemical modification, filtering and drying to obtain the chemically modified fluororesin particles.
Method embodiment 6
At room temperature, 100g of fluorinated ethylene propylene copolymer (FEP) particles with the medium particle size of 20um are taken;
placing in a treatment chamber of torch type normal pressure plasma equipment, opening a stirring device, charging air and a plasma generator, switching on and off, treating for 2 minutes, and taking out from the raw material treatment chamber to obtain fluorinated ethylene propylene copolymer (FEP) particles with activated surfaces; and carrying out subsequent chemical modification, filtering and drying to obtain the chemically modified fluororesin particles.
There are other various embodiments for the above chemical modification process, such as:
method embodiment 7
Adding the fluororesin particles weighed in the step (1) into 200mL of acrylic acid aqueous solution under the stirring of 1000RPM, increasing the stirring speed to 2500RPM, and reacting for 2 h; filtering with filter paper to obtain solid particles, and air drying in a fume hood; and (3) sampling the dried solid, detecting by using a solid content analyzer, and ensuring that the content of ethanol and water is not more than 0.1 percent to obtain the surface modified fluororesin particles.
Method embodiment 8
Under the stirring of 1000RPM, adding the fluororesin particles weighed in the step (1) into 200mL of ethanol solution of aminopropyltriethoxysilane and boric acid, increasing the stirring speed to 2500RPM, and reacting for 2 h; filtering with filter paper to obtain solid particles, and air drying in a fume hood; and (3) sampling the dried solid, detecting by using a solid content analyzer, and ensuring that the content of ethanol and water is not more than 0.1 percent to obtain the surface modified fluororesin particles.
According to the invention, the hydrophobic auxiliary agent is applied to the fields of powder coating, solvent type coating, water-based coating, plastic, asphalt and cement, when in specific use, the hydrophobic auxiliary agent is added into the powder coating, or solvent type coating, or water-based coating, or plastic, or asphalt, or cement, then fully stirred to prepare a mixture, and then the mixture is processed to prepare a finished product, and as a scheme, the proportion of the hydrophobic auxiliary agent in the mixture of the hydrophobic auxiliary agent and the powder coating, or solvent type coating, or water-based coating, or plastic, or asphalt, or cement is 0.5-50% by weight.
Application example 1
The hydrophobic aid prepared in accordance with method embodiment 1 above was added to the polyester tgic (triglycidyl isocyanurate) powder coating raw material in an amount of 5% by weight within one hour; the raw materials comprise polyester resin, TGIC, pigment, filler, degassing agent, leveling agent and the like;
fully stirring by using a high-speed mixer, fully mixing by using a double-screw extruder at the temperature of 100 ℃, pressing and cooling into sheet materials, and crushing and screening by using an air classification mill until the median particle size is 35 mu m;
spraying the coating on a cast iron plate for powder coating under 35KV, baking for 15 minutes at 200 ℃ to obtain a hydrophobic coating, wherein the water contact angle is 123 degrees, the contact angle is 121 degrees, the coating is rubbed 100 times under the pressure of 9.8KPa by P220 sandpaper according to the test of paint UV aging test standard ISO 11507-2007 for 500 hours, and the contact angle is 118 degrees.
Application example 2
The hydrophobic adjuvant prepared according to the above method embodiment 2 was added to polyester TGIC powder coating raw materials including polyester resin, TGIC, pigment, filler, degassing agent, leveling agent, etc. in an amount of 7.5% by mass within one hour;
fully stirring by using a high-speed mixer, fully mixing by using a double-screw extruder at the temperature of 100 ℃, pressing and cooling into sheet materials, and crushing and screening by using an air classification mill until the median particle size is 35 mu m;
spraying the coating on a cast iron plate for powder coating under 35KV, and baking for 15 minutes at 200 ℃ to obtain a hydrophobic coating, wherein the water contact angle is 132 degrees, and the contact angle is 131 degrees when tested for 500 hours according to the coating UV aging test standard ISO 11507-2007. Rubbing 100 times with P220 sandpaper at 9.8KPa and a contact angle of 126 deg.
Application example 3
The hydrophobic adjuvant prepared according to method embodiment 3 above was added to the polyester TGIC powder coating raw material in an amount of 20% by mass over one hour;
fully stirring by using a high-speed mixer, fully mixing by using a double-screw extruder at the temperature of 100 ℃, pressing and cooling into sheet materials, and crushing and screening by using an air classification mill until the median particle size is 35 mu m;
spraying the coating on a cast iron plate for powder coating under 35KV, baking for 15 minutes at 200 ℃ to obtain a hydrophobic coating, wherein the water contact angle is 155 degrees, the rolling angle is 7 degrees, the contact angle is still 155 degrees according to the test of coating UV aging test standard ISO 11507-2007 for 500 hours, the friction is carried out for 100 times under the pressure of 9.8KPa by using P220 sand paper, and the contact angle is 153 degrees.
Application example 4
The hydrophobic additive prepared in the method embodiment 4 is added to the solvent-based epoxy coating in an amount of 20% by mass, and the solvent-based epoxy coating is fully stirred and mixed by using a high-speed mixer, then the mixture is brushed on a cast iron plate, and the mixture is naturally dried to obtain the hydrophobic coating. The water contact angle is 158 degrees, and the rolling angle is 7 degrees. The contact angle is 154 degrees according to the coating UV aging test standard ISO 11507-2007 test for 500 h. Rubbing 100 times with P220 sandpaper at 9.8KPa and a contact angle of 153 deg.
Application example 5
The hydrophobic additive prepared in the above method embodiment 5 is added to polyethylene resin particles in an amount of 20% by mass, sufficiently stirred by a high-speed mixer, sufficiently kneaded by a twin-screw extruder at a temperature of 200 ℃, and injection-extruded to prepare a composite material. The obtained material has a strong hydrophobic surface, the water contact angle is 156 degrees, and the rolling angle is 7 degrees. Rubbing 100 times with P220 sandpaper at 9.8KPa and a contact angle of 153 deg.
Application example 6
The hydrophobic additive prepared according to the method embodiment 7 is added to a cement finished product in an amount of 20% by mass, sufficiently stirred by a stirrer, added with water according to the original ratio of concrete to water, stirred again, transferred to a mold, and solidified to obtain hydrophobic cement, wherein the water contact angle is 158 ° and the rolling angle is 6 °. Rubbing 100 times with P220 sandpaper at 9.8KPa and a contact angle of 158 deg..
In the application examples, the hydrophobic auxiliary agent prepared by the preparation method of the invention has a very good effect, and for embodying the comparison, the following comparative experiments are performed for the conventional prior art:
comparative application example 1
The PTFE particles were added to the polyester TGIC powder coating raw material in an amount of 10% by mass. The raw materials comprise polyester resin, TGIC, pigment, filler, degasifier, flatting agent and the like, and are fully stirred by a high-speed mixer, then fully mixed by a double-screw extruder at the temperature of 100 ℃, pressed and cooled into sheet materials, and ground by air classification grinding and sieved to have the median particle size of 35 um;
spraying the coating on a cast iron plate for powder coating under 35KV, and baking for 15 minutes at 200 ℃ to obtain a hydrophobic coating with a water contact angle of 140 degrees. The contact angle is 138 degrees according to the coating UV aging test standard ISO 11507-2007 test for 500 h. The coating was abraded with P220 sandpaper at a pressure of 9.8KPa 80 times with a contact angle of 20 °.
Comparative application example 2
AEROXIDE LE3 was added to polyester TGIC powder coating raw material in an addition amount of 5% by mass. The raw materials comprise polyester resin, TGIC, pigment, filler, degasifier, flatting agent and the like, and are fully stirred by a high-speed mixer, then fully mixed by a double-screw extruder at the temperature of 100 ℃, pressed and cooled into sheet materials, and ground by air classification grinding and sieved to have the median particle size of 35 um;
spraying the coating on a cast iron plate for powder coating under 35KV, and baking for 15 minutes at 200 ℃ to obtain a hydrophobic coating, wherein the water contact angle is 170 degrees, and the rolling angle is 2 degrees. The coating becomes a hydrophilic surface and the contact angle is 26 degrees according to the coating UV aging test standard ISO 11507-2007 test for 500 h. The coating contact angle had dropped to 65 deg. by rubbing 10 times with P220 sandpaper at a pressure of 9.8 KPa.
Through the above and the above comparison, the present invention overcomes the disadvantages of the prior art and provides a method for preparing and applying a hydrophobic auxiliary for hydrophobic and superhydrophobic surfaces. The problem that the surface of the existing liquid hydrophobic auxiliary agent is easy to lose hydrophobicity due to migration is solved; the solid wax hydrophobic auxiliary agent can only adjust the hydrophobicity in a limited way; the weather resistance of the fluorine-free silane modification is not ideal; the hydrophobic surface prepared by the fluorosilane modified inorganic particles has poor wear resistance; the hydrophobic organic particles are dispersed unevenly and have poor film-forming property; the conventional DBD plasma has a series of problems of poor powder treatment effect and the like. The prepared auxiliary agent can be stored for a long time, can be uniformly dispersed in a film-forming and forming substance when in use, can adjust the hydrophobicity within a large range of 90-163 degrees, has a rolling angle as small as 6 degrees, and has higher weather resistance and wear resistance.
Although the present invention has been described in detail with reference to the foregoing embodiments, it will be apparent to those skilled in the art that modifications may be made to the embodiments or portions thereof without departing from the spirit and scope of the invention.

Claims (10)

1. The preparation method of the weather-resistant wear-resistant hydrophobic auxiliary agent is characterized by comprising the following steps:
the first step is as follows: measuring or preparing a certain amount of fluororesin particles; the fluororesin particles comprise one or more of 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);
the second step is as follows: placing the fluororesin particles in a plasma device, treating for 1min-1h in a specific gas environment, and carrying out surface activation treatment to prepare fluororesin particles subjected to surface activation treatment to form a hydrophobic auxiliary agent;
or using a chemical modifier to carry out chemical modification treatment on the fluororesin particles to prepare the fluororesin particles after chemical modification, and then filtering and drying the fluororesin particles to prepare the hydrophobic auxiliary agent;
or placing the fluororesin particles in a plasma device, treating for 1min-1h in a specific gas environment, and carrying out surface activation treatment to prepare fluororesin particles subjected to surface activation treatment; and carrying out chemical modification treatment on the fluororesin particles subjected to surface activation treatment by using a chemical modifier to prepare the fluororesin particles subjected to chemical modification, and then filtering and drying the fluororesin particles to prepare the hydrophobic auxiliary agent.
2. The method of claim 1, wherein: the plasma device comprises one or more of a combination of atmospheric pressure plasma, low pressure plasma, or a low pressure plasma emitter equipped with microwaves.
3. The method of claim 1, wherein: and in the specific gas environment, mixed gas which is formed by mixing one or more of H2, Ar, N2 and O2 or one or more of H2, Ar, N2 and O2 with NH3, acrylic acid or silane coupling agent is contained.
4. The method of claim 1, wherein: the chemical modifier comprises an ethanol solution containing a silane coupling agent, an ethanol solution mixed by the silane coupling agent and boric acid and an acrylic acid aqueous solution; the silane coupling agent comprises one or more of aminopropyltriethoxysilane, aminopropyltrimethoxysilane and N- (2-aminoethyl) -3-aminopropyltrimethoxysilane in combination.
5. The method of claim 4, wherein: the solvent used by the ethanol solution containing the silane coupling agent and the ethanol solution mixed by the silane coupling agent and boric acid is ethanol, and the solubility is 10-30%;
in the ethanol solution mixed by the silane coupling agent and the boric acid, the ratio of the silane coupling agent to the boric acid is (by weight) 10: 1-1: 1;
the concentration of the acrylic acid aqueous solution is 10-50%.
6. The method of claim 1, wherein: in the first step, the particle size range of the measured or prepared fluororesin particles is 0.1um-20 um.
7. The method of claim 1, wherein: in the third step, the fluorine resin particles after the surface activation treatment are subjected to chemical modification treatment in an environment of 0-80 ℃;
in the third step, when the fluorine resin particles after the surface activation treatment are subjected to chemical modification treatment, one or more treatment modes of stirring, mechanical vibration, soaking and refluxing are adopted.
8. 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 applied to the fields of powder coating, solvent-based coating, water-based coating, plastic, asphalt and cement.
9. Use according to claim 8, characterized in that: adding the hydrophobic auxiliary agent into the powder coating, or solvent type coating, or water-based coating, or plastic, or asphalt, or cement, fully stirring to prepare a mixture, and then processing to prepare a finished product.
10. Use according to claim 9, characterized in that: in the mixture of hydrophobic auxiliary agent and powder coating, solvent-type coating, water-based coating, plastic, asphalt or cement, the proportion of the hydrophobic auxiliary agent is 0.5-50% by weight.
CN202011513864.5A 2020-12-19 2020-12-19 Preparation method and application of weather-resistant wear-resistant hydrophobic auxiliary agent Pending CN112724428A (en)

Priority Applications (3)

Application Number Priority Date Filing Date Title
CN202011513864.5A CN112724428A (en) 2020-12-19 2020-12-19 Preparation method and application of weather-resistant wear-resistant hydrophobic auxiliary agent
PCT/CN2021/108524 WO2022127116A1 (en) 2020-12-19 2021-07-27 Preparation method for and application of weather-resistant, wear-resistant and hydrophobic aid
ZA2022/13150A ZA202213150B (en) 2020-12-19 2022-12-05 Preparation method and application of weather-resistant, wear-resistant and hydrophobic aid

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202011513864.5A CN112724428A (en) 2020-12-19 2020-12-19 Preparation method and application of weather-resistant wear-resistant hydrophobic auxiliary agent

Publications (1)

Publication Number Publication Date
CN112724428A true CN112724428A (en) 2021-04-30

Family

ID=75603542

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202011513864.5A Pending CN112724428A (en) 2020-12-19 2020-12-19 Preparation method and application of weather-resistant wear-resistant hydrophobic auxiliary agent

Country Status (3)

Country Link
CN (1) CN112724428A (en)
WO (1) WO2022127116A1 (en)
ZA (1) ZA202213150B (en)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2022127116A1 (en) * 2020-12-19 2022-06-23 广东西敦千江粉漆科学研究有限公司 Preparation method for and application of weather-resistant, wear-resistant and hydrophobic aid
CN115465868A (en) * 2022-10-14 2022-12-13 航天规划设计集团有限公司 Thermal insulation material and high-permeability hydrophobic modification method thereof
CN115651459A (en) * 2022-11-09 2023-01-31 兰州空间技术物理研究所 Lubricating coating, and preparation method and application thereof

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN116445055B (en) * 2023-04-21 2023-10-20 江苏中金玛泰医药包装有限公司 Water-based corrosion-resistant composite coating of medicinal composite film and preparation method thereof
CN116410623B (en) * 2023-05-05 2024-03-15 水利部交通运输部国家能源局南京水利科学研究院 Preparation method of carbonized modified red mud-based hydrophobic concrete coating

Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH08134243A (en) * 1994-11-11 1996-05-28 Asahi Glass Co Ltd Method for modifying fluororesin surface
US20030199639A1 (en) * 2002-04-23 2003-10-23 Michael Coates Method of treating fluoropolymer particles and the products thereof
JP2004323593A (en) * 2003-04-22 2004-11-18 Toyota Industries Corp Fluororesin powder and modification method therefor
CN102246317A (en) * 2008-12-08 2011-11-16 旭硝子株式会社 Fluorine resin film and use thereof
CN104046217A (en) * 2013-03-12 2014-09-17 无锡市顺业科技有限公司 Preparation method of high strength superhydrophobic coating
CN106752462A (en) * 2017-01-11 2017-05-31 中国民用航空总局第二研究所 A kind of super hydrophobic material and preparation method thereof
CN107987675A (en) * 2017-12-15 2018-05-04 杭州纳微生物化学有限公司 A kind of wear-resisting super hydrophobic coating composition and its preparation method and application

Family Cites Families (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107652795A (en) * 2017-09-27 2018-02-02 东南大学 A kind of super-hydrophobic powdery paints and its preparation method and application
CN110818919A (en) * 2018-08-09 2020-02-21 臻鼎科技股份有限公司 Modified polytetrafluoroethylene particles, method for preparing same and composition
CN113166442A (en) * 2018-12-05 2021-07-23 Ａｇｃ株式会社 Method for producing modified particle, dispersion liquid, composition, and laminate
CN110484024B (en) * 2019-08-15 2020-12-11 安徽壹石通材料科技股份有限公司 Method for preparing PTFE modified inorganic powder composite filler
CN111454629A (en) * 2020-04-29 2020-07-28 湖北中科博策新材料科技有限公司 Super-hydrophobic water paint and production process thereof
CN112724428A (en) * 2020-12-19 2021-04-30 天津西敦粉漆科技有限公司 Preparation method and application of weather-resistant wear-resistant hydrophobic auxiliary agent

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH08134243A (en) * 1994-11-11 1996-05-28 Asahi Glass Co Ltd Method for modifying fluororesin surface
US20030199639A1 (en) * 2002-04-23 2003-10-23 Michael Coates Method of treating fluoropolymer particles and the products thereof
JP2004323593A (en) * 2003-04-22 2004-11-18 Toyota Industries Corp Fluororesin powder and modification method therefor
CN102246317A (en) * 2008-12-08 2011-11-16 旭硝子株式会社 Fluorine resin film and use thereof
CN104046217A (en) * 2013-03-12 2014-09-17 无锡市顺业科技有限公司 Preparation method of high strength superhydrophobic coating
CN106752462A (en) * 2017-01-11 2017-05-31 中国民用航空总局第二研究所 A kind of super hydrophobic material and preparation method thereof
CN107987675A (en) * 2017-12-15 2018-05-04 杭州纳微生物化学有限公司 A kind of wear-resisting super hydrophobic coating composition and its preparation method and application

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
王振欣等: "氟树脂对聚偏氟乙烯膜疏水性的影响", 《化工新型材料》 *

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2022127116A1 (en) * 2020-12-19 2022-06-23 广东西敦千江粉漆科学研究有限公司 Preparation method for and application of weather-resistant, wear-resistant and hydrophobic aid
CN115465868A (en) * 2022-10-14 2022-12-13 航天规划设计集团有限公司 Thermal insulation material and high-permeability hydrophobic modification method thereof
CN115651459A (en) * 2022-11-09 2023-01-31 兰州空间技术物理研究所 Lubricating coating, and preparation method and application thereof

Also Published As

Publication number Publication date
WO2022127116A1 (en) 2022-06-23
ZA202213150B (en) 2023-03-29

Similar Documents

Publication Publication Date Title
CN112724428A (en) Preparation method and application of weather-resistant wear-resistant hydrophobic auxiliary agent
KR100564264B1 (en) Polyalkoxysiloxane compounds, preparation process thereof and coating compositions the same
KR100370984B1 (en) Curable composition and process for producing the same
EP2688964B1 (en) Alkyd-based coating composition
CN101230224A (en) Fluorosilicone rubber nano composite alloy three-proof paint and production method thereof
CN111518456B (en) Permeable waterproof alkali-resistant coating and preparation method thereof
JP3288180B2 (en) A method for producing an aqueous composition based on a fluoroelastomer for a coating having a high film thickness.
CN110878184A (en) Graphene modified epoxy zinc-rich primer and preparation method thereof
CN111434737A (en) Modified waterborne epoxy resin/nano SiO2Composite hydrophobic coating and preparation method thereof
US20230279259A1 (en) Aspartic polyurea coating
WO2020205879A1 (en) Coating compositions for hydrophobic films and articles having hydrophobic surfaces
CN110628253A (en) Environment-friendly super-hydrophobic antifouling paint and preparation method thereof
JP2008031237A (en) Inorganic paint rich in zinc and method of forming multiple layer coated film using the same
JP2792231B2 (en) Composition for metal surface treatment
CN108059891B (en) Waterproof heat-insulating coating with ultrahigh viscosity and high sunlight reflectance and preparation method thereof
CN108034253A (en) A kind of silicone glass resin
CN108559376B (en) High-hardness low-contact-angle emulsion coating and application thereof
KR20190011558A (en) Water-repellent coating agent and method for manufacturing the same
CN114369290A (en) Surface organic modified talcum powder filler and preparation method and application thereof
CN111876037A (en) Water-based acrylic acid white paint and preparation method thereof
CN111218153A (en) Method for producing structure having superhydrophobic surface
Huang et al. Silicone/silica nanocomposites as culture‐stone protective materials
UMK et al. Effects of nanoclay contents on the properties of water-based coating
JP4491312B2 (en) Method for forming moisture-permeable coating film
WO2019009416A1 (en) Aqueous coating material, film-coated substrate, and production method for film-coated substrate

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
RJ01 Rejection of invention patent application after publication
RJ01 Rejection of invention patent application after publication

Application publication date: 20210430