CN111234237A - Perfluoropolyether modified polysiloxane coating auxiliary agent, preparation method thereof and coating - Google Patents
Perfluoropolyether modified polysiloxane coating auxiliary agent, preparation method thereof and coating Download PDFInfo
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- CN111234237A CN111234237A CN202010167830.9A CN202010167830A CN111234237A CN 111234237 A CN111234237 A CN 111234237A CN 202010167830 A CN202010167830 A CN 202010167830A CN 111234237 A CN111234237 A CN 111234237A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/42—Block-or graft-polymers containing polysiloxane sequences
- C08G77/46—Block-or graft-polymers containing polysiloxane sequences containing polyether sequences
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- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
- C03C17/001—General methods for coating; Devices therefor
- C03C17/002—General methods for coating; Devices therefor for flat glass, e.g. float glass
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- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
- C03C17/28—Surface treatment of glass, not in the form of fibres or filaments, by coating with organic material
- C03C17/30—Surface treatment of glass, not in the form of fibres or filaments, by coating with organic material with silicon-containing compounds
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- 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
- C09D183/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Coating compositions based on derivatives of such polymers
- C09D183/10—Block or graft copolymers containing polysiloxane sequences
- C09D183/12—Block or graft copolymers containing polysiloxane sequences containing polyether sequences
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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
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- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/16—Antifouling paints; Underwater paints
- C09D5/1656—Antifouling paints; Underwater paints characterised by the film-forming substance
- C09D5/1662—Synthetic film-forming substance
- C09D5/1675—Polyorganosiloxane-containing compositions
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- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C2217/00—Coatings on glass
- C03C2217/70—Properties of coatings
- C03C2217/76—Hydrophobic and oleophobic coatings
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- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C2218/00—Methods for coating glass
- C03C2218/10—Deposition methods
- C03C2218/11—Deposition methods from solutions or suspensions
- C03C2218/112—Deposition methods from solutions or suspensions by spraying
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Abstract
The invention discloses a perfluoropolyether modified polysiloxane coating auxiliary agent, a preparation method thereof and a coating, wherein the perfluoropolyether acrylic ester is obtained by reacting perfluoropolyether acrylate with carbon-carbon double bond-containing siloxane and hydrogen-containing silicone oil under the action of a catalyst, the feeding molar ratio of the perfluoropolyether acrylate to the carbon-carbon double bond-containing siloxane to the hydrogen-containing silicone oil is 1-9:1-9:1, and the perfluoropolyether acrylate is obtained by reacting perfluoropolyether acyl chloride and a hydroxyl-containing acrylate compound with the feeding molar ratio of 1: 1-1.5. The fluorine-containing silicone coating agent is obtained by the reaction of perfluoropolyether carboxylic acid, a hydroxyl-containing acrylate compound, carbon-carbon double bond-containing siloxane and hydrogen-containing silicone oil, the problems that a fluorine-containing fluorine-silicon coating agent is easy to have shrinkage, uneven spreading, orange peel, cracking, rough and uneven surface and the like in the coating process are solved, the fluorine-silicon coating agent can be uniformly spread on a hard substrate, and the surface of the substrate can be promoted to obtain better hydrophobic, oleophobic and antifouling effects.
Description
Technical Field
The invention relates to the technical field of chemical materials, in particular to a perfluoropolyether modified polysiloxane coating auxiliary agent used as a flatting agent or a lubricating agent and the like for preventing fouling on the surface of a hard substrate, a preparation method thereof and a coating.
Background
With the development of science and technology, touch screen electronic equipment, ceramics, organic glass and polycarbonate made of lens materials are widely popular in application in life, a layer of hardening film is coated on the surface of a hard substrate to protect the hard substrate in the using process, and the research on the coating agent on the surface of the substrate becomes a hotspot. The coating agent of the surface of the hard substrate is often a coating with low surface energy with hydrophobicity and oleophobicity, and the excellent properties of the perfluoropolyether material and the organosilicon material make the coating agent have important and wide application. However, these high fluorine content fluorosilicone coating agents tend to suffer from problems such as cratering, uneven spreading, orange peel, cracking, and surface roughness during the coating process.
In view of the above, it is necessary to research a coating aid to solve a series of problems encountered during the use of high-content fluorine-containing silicone coating agents, and to provide excellent water-proof, oil-proof, stain-proof, and wear-resistant properties.
Disclosure of Invention
The invention aims to provide a perfluoropolyether modified polysiloxane coating auxiliary agent, a preparation method thereof and a coating thereof, aiming at the defects of the prior art, the perfluoropolyether carboxylic acid, the acrylate compound containing hydroxyl, the siloxane containing carbon-carbon double bonds and the silicone oil containing hydrogen are reacted to obtain the perfluoropolyether modified polysiloxane coating auxiliary agent, so that the problems that the fluorosilicone coating agent with high fluorine content is easy to have shrinkage cavities, uneven spreading, orange peel, cracks, rough and uneven surface and the like in the coating process are solved, the fluorosilicone coating agent can be uniformly spread on a hard substrate, and the surface of the substrate can be promoted to obtain better hydrophobic, oleophobic and antifouling effects.
The technical scheme adopted by the invention to achieve the aim is as follows:
a perfluoropolyether modified polysiloxane coating auxiliary agent is prepared by the reaction of perfluoropolyether acrylate, siloxane containing carbon-carbon double bonds and hydrogen-containing silicone oil under the action of a catalyst; the feeding molar ratio of the perfluoropolyether acrylate to the siloxane containing carbon-carbon double bonds to the hydrogen-containing silicone oil is 1-9:1-9: 1.
Preferably, the perfluoropolyether acrylate is obtained by reacting perfluoropolyether acyl chloride and hydroxyl-containing acrylate compound in a feeding molar ratio of 1: 1-1.5.
Preferably, the perfluoropolyether acyl chloride is obtained by reacting thionyl chloride and perfluoropolyether carboxylic acid in a feeding molar ratio of 3-8:1 under the action of a solvent.
Preferably, the catalyst is a metal catalyst such as rhodium, platinum, nickel or a Lewis acid catalyst such as any one or more of aluminum trichloride and ferric trichloride.
Preferably, the solvent is at least one of hydrofluoroether, hexafluoro-m-xylene, trifluorotrichloroethane, toluene, 1, 4-dioxane, dichloromethane, tetrahydrofuran, toluene and 1, 4-dioxane.
Preferably, the hydroxyl-containing acrylate compound is any one of trihydroxy acrylate, pentaerythritol triacrylate, 2-hydroxyethyl acrylate, hydroxyethyl methacrylate and 4-hydroxybutyl acrylate.
Preferably, the carbon-carbon double bond-containing siloxane has a formula of CH2 ═ CR1R2Si (OR3)3, wherein R1 ═ H, CH 3; r2 ═ COO, CH2CH2, or no R2; r3 ═ CH3, CH2CH3, CH (CH3)2, oc (o) CH2CH3, oc (o) CH ═ CH 3.
Preferably, the perfluoropolyether carboxylic acid has the formula CF3CF 2O (CF3) CF2O) n-COOH, wherein n is 17, 34 and the molecular weight Mw is 3000-6000.
A preparation method of a perfluoropolyether modified polysiloxane coating auxiliary agent comprises the following steps:
(1) preparation of perfluoropolyether acrylate:
s1: dropwise adding thionyl chloride into a three-neck flask of perfluoropolyether carboxylic acid, adding a solvent, magnetically stirring to react for a certain time, washing, and removing unreacted monomers under reduced pressure to obtain perfluoropolyether acyl chloride;
s2: adding perfluoropolyether acyl chloride and a hydroxyl-containing acrylate compound into a three-neck flask according to a set molar ratio, reacting for a certain time under the protection of nitrogen, washing, and removing unreacted monomers under reduced pressure to obtain perfluoropolyether acrylate;
(2) preparation of perfluoropolyether modified polysiloxane
S3: adding perfluoropolyether acrylate, carbon-carbon double bond-containing siloxane and hydrogen-containing silicone oil into a three-neck flask, introducing nitrogen, adding a catalyst, stirring for reacting for a certain time, and cooling to room temperature to obtain a product;
s4: and adding a precipitation solvent into the obtained product to precipitate the polymer, washing to remove unreacted monomers, and distilling under reduced pressure to remove the precipitation solvent to obtain the perfluoropolyether modified polysiloxane.
Preferably, the reaction conditions in the step S1 are temperature of 60-80 ℃ and time of 3-7 hours; the reaction condition in S2 is room temperature reaction time 6-12 hours; the reaction condition in S3 is that stirring reaction is carried out for 2-12 hours at 40-120 ℃; the precipitation solvent is methanol.
A coating containing a perfluoropolyether modified polysiloxane coating aid is prepared by diluting perfluoropolyether modified polysiloxane with a solvent to obtain a coating agent, spraying the coating agent on a clean glass plate, standing at room temperature, and performing vacuum drying and high-temperature baking to obtain an antifouling coating.
Preferably, the weight percentage of the perfluoropolyether modified polysiloxane diluted by the solvent is 0.1-0.3 wt%; the clean glass plate is obtained by any one or more treatment modes of ethanol-acetone ultrasonic treatment, sulfuric acid-hydrogen peroxide chemical treatment, UV ozone irradiation treatment or plasma treatment; standing at room temperature for 10-15 min; the high-temperature baking temperature is 120-; the thickness of the antifouling coating is 10-50 nm.
Compared with the prior art, the invention has the following beneficial effects:
1. the perfluoropolyether modified polysiloxane coating auxiliary agent is obtained by reacting perfluoropolyether carboxylic acid, hydroxyl-containing acrylate compound, carbon-carbon double bond-containing siloxane and hydrogen-containing silicone oil, solves the problems that a fluorine-silicon coating agent with high fluorine content is easy to have shrinkage, uneven spreading, orange peel, cracking, rough and uneven surface and the like in the coating process, can be uniformly spread on a hard substrate, and can promote the surface of the substrate to obtain better hydrophobic, oleophobic and antifouling effects.
2. The fluorine-silicon coating agent containing the perfluoropolyether modified polysiloxane has the effects of spreading, leveling, shrinkage cavity elimination and lubrication in the use process, and when the fluorine-silicon coating agent is used alone, the water contact angle can reach 122 degrees, so that the fluorine-silicon coating agent has excellent hydrophobicity and the antifouling effect is guaranteed.
The foregoing is a summary of the technical solutions of the present invention, and the present invention is further described below with reference to specific embodiments.
The specific implementation mode is as follows:
in order to make the objects, technical solutions and advantages of the present invention more apparent, the following embodiments are described in detail. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
Example 1: the perfluoropolyether modified polysiloxane coating auxiliary agent provided by the embodiment is prepared by reacting perfluoropolyether acrylate with siloxane containing carbon-carbon double bonds and hydrogen-containing silicone oil under the action of a catalyst; the feeding molar ratio of the perfluoropolyether acrylate to the siloxane containing carbon-carbon double bonds to the hydrogen-containing silicone oil is 1-9:1-9: 1. Wherein, the perfluoropolyether acrylate is obtained by the reaction of perfluoropolyether acyl chloride and hydroxyl-containing acrylate compound with the feeding molar ratio of 1: 1-1.5; the perfluoropolyether acyl chloride is obtained by reacting thionyl chloride and perfluoropolyether carboxylic acid with the feeding molar ratio of 3-8:1 under the action of a solvent; the catalyst is metal catalyst such as rhodium, platinum, nickel or Lewis acid catalyst such as any one or more of aluminum trichloride and ferric trichloride; the solvent is at least one of hydrofluoroether, hexafluoro-m-xylene, trifluorotrichloroethane, toluene, 1, 4-dioxane, dichloromethane, tetrahydrofuran, toluene and 1, 4-dioxane; the hydroxyl-containing acrylate compound is any one of trihydroxy acrylate, pentaerythritol triacrylate, 2-hydroxyethyl acrylate, hydroxyethyl methacrylate and 4-hydroxybutyl acrylate; the molecular formula of the carbon-carbon double bond-containing siloxane is CH2 ═ CR1R2Si (OR3)3, wherein R1 ═ H, CH 3; r2 ═ COO, CH2CH2, or no R2; r3 ═ CH3, CH2CH3, CH (CH3)2, oc (o) CH2CH3, oc (o) CH ═ CH 3; the perfluoropolyether carboxylic acids have the formula CF3CF 2O (CF3) CF2O) n-COOH, where n is 17, 34 and the molecular weight Mw is 3000-6000.
The embodiment also provides a preparation method of the perfluoropolyether modified polysiloxane coating auxiliary agent, which comprises the following steps:
(1) preparation of perfluoropolyether acrylate:
s1: dropwise adding excessive thionyl chloride into a three-neck flask of perfluoropolyether carboxylic acid, adding a solvent, magnetically stirring, reacting for a certain time, washing, reacting at the temperature of 60-80 ℃ for 3-7 hours, and distilling under reduced pressure to remove the excessive thionyl chloride to obtain perfluoropolyether acyl chloride;
s2: adding perfluoropolyether acyl chloride and a hydroxyl-containing acrylate compound into a three-neck flask according to a set molar ratio, reacting for a certain time under the protection of nitrogen, washing, reacting for 6-12 hours at room temperature, and removing excessive acrylate compound by reduced pressure distillation to obtain perfluoropolyether acrylate; the reaction scheme is as follows:
rf is perfluoropolyether: CF3CF 2O (CF3) CF2O) n, n is 17, 34
ROH is hydroxyl-containing acrylate compound, such as at least one of trihydroxy acrylate, pentaerythritol triacrylate, 2-hydroxyethyl acrylate, hydroxyethyl methacrylate, and 4-hydroxybutyl acrylate. The solvent is at least one of hydrofluoroether, hexafluoro-m-xylene, trifluorotrichloroethane, toluene, 1, 4-dioxane, dichloromethane and tetrahydrofuran.
(2) Preparation of perfluoropolyether modified polysiloxane
S3: adding perfluoropolyether acrylate, carbon-carbon double bond-containing siloxane and hydrogen-containing silicone oil into a three-neck flask, introducing nitrogen, adding a catalyst, stirring for reacting for a certain time, cooling to room temperature, and reacting at the temperature of 40-120 ℃ for 2-12 hours to obtain a product;
s4: and adding a precipitation solvent methanol into the obtained product to precipitate the polymer, washing to remove unreacted monomer siloxane, and distilling under reduced pressure to remove the solvent to obtain the perfluoropolyether modified polysiloxane. The reaction scheme is as follows:
wherein CH2 ═ CR1R2Si (OR3)3, R1 ═ H, CH 3; r2 ═ COO, CH2CH2, or none; r3 ═ CH3, CH2CH3, CH (CH3)2, oc (o) CH2CH3, oc (o) CH ═ CH 3.
The embodiment also provides a coating containing the perfluoropolyether modified polysiloxane coating auxiliary agent, wherein the perfluoropolyether modified polysiloxane is diluted by a solvent to obtain the coating agent, and the weight percentage of the perfluoropolyether modified polysiloxane diluted by the solvent is 0.1-0.3 wt%; spraying the glass powder on a clean glass plate, wherein the clean glass plate is obtained by any one or more treatment modes of ethanol-acetone ultrasonic treatment, sulfuric acid-hydrogen peroxide chemical treatment, UV ozone irradiation treatment or plasma treatment; standing at room temperature for 10-15min, vacuum drying, and baking at 120-200 deg.C for 15-60min to obtain antifouling coating with thickness of 10-50 nm.
Example 2: the perfluoropolyether modified polysiloxane coating assistant, the preparation method thereof, and the coating provided in this example are substantially the same as those in example 1, except that:
Rf-COOCH2CH2OC (O) C (CH3) ═ CH2(PFPE-HEMA) was synthesized with reference to the procedure of example 1: to a 100ml three-necked flask equipped with a magnetic stirring rotor, nitrogen inlet and reflux condenser, perfluoropolyether acid chloride (RfCOCl, Mw 3000, 15g, 0.005mol) and hydroxyethyl methacrylate (HOCH2CH2OCOC (CH3) ═ CH2), Mw 130.14, 0.6767g, 0.0052mol) were added and stirred at 30 ℃ under nitrogen for 12 h; washing unreacted acrylic ester by using ethanol, and removing the ethanol solvent under reduced pressure to obtain the perfluoropolyether acrylic ester.
And (3) testing and analyzing: a peak (-1794 cm) associated with the ester group of Rf-C (O) OCH 2-appeared in the FTIR analysis-1) Peak (-1735 cm) associated with α unsaturated ester group of CH2OCOCH ═ CH2-1). And sealing and storing the product for later use.
The method of reference example 1: under the protection of nitrogen, hydrogen-containing silicone oil (hydrogen content 1.6%, 0.05g) was added to a 100ml three-necked flask equipped with a magnetic stirring rotor, a nitrogen inlet and a reflux condenser, in a molar ratio of carbon to carbon double bonds of 1: 9 of PFPE-HEMA, vinyl trimethoxy silane, 10 mu L of 400ppm chloroplatinic acid catalyst and 2ml of solvent, heating to 100 ℃, stirring for 1h, washing, and distilling under reduced pressure to obtain clear oily liquid, thus obtaining the perfluoropolyether modified polysiloxane.
Example 3: the perfluoropolyether modified polysiloxane coating assistant, the preparation method thereof and the coating provided by the embodiment are basically the same as those of the embodiments 1 and 2, except that:
Rf-COOCH2CH2OC (O) C (CH3) ═ CH2(PFPE-HEMA) was synthesized according to the procedure of example 2, and perfluoropolyether polysiloxanes were prepared using PFPE-HEMA and vinyltrimethoxysilane with a molar ratio of carbon to carbon double bonds of 2: 8.
Example 4: the perfluoropolyether modified polysiloxane coating assistant, the preparation method thereof and the coating provided by the embodiment are basically the same as those of the embodiments 1 and 2, except that:
Rf-COOCH2CH2OC (O) C (CH3) ═ CH2(PFPE-HEMA) was synthesized according to the procedure of example 2, and perfluoropolyether polysiloxanes were prepared using PFPE-HEMA and vinyltrimethoxysilane with a molar ratio of carbon to carbon double bonds of 3: 7.
Example 5: the perfluoropolyether modified polysiloxane coating assistant, the preparation method thereof, and the coating provided in this example are substantially the same as those in example 1, except that:
Rf-COOCH2CH2OC (O) C (CH3) ═ CH2(PFPE-HEMA) was synthesized according to the procedure of example 2,
the method of reference example 1: to a 100ml three-necked flask equipped with a magnetic stirring rotor, a nitrogen inlet and a reflux condenser, hydrogen-containing silicone oil (hydrogen content 1.6%, 0.05g), PFPE-HEMA and gamma-methacryloxypropyl trimethoxysilane in a carbon-carbon double bond molar ratio of 2:8, 10. mu.L of 400ppm chloroplatinic acid catalyst and 2ml of a fluorine solvent were added under the protection of nitrogen. Heating to 100 ℃, stirring for 1h, washing, and distilling under reduced pressure to obtain a white oil-like liquid, thereby obtaining the perfluoropolyether modified polysiloxane.
Example 6: the perfluoropolyether modified polysiloxane coating assistant, the preparation method thereof and the coating provided by the embodiment are basically the same as those of the embodiment 1, the embodiment 2 and the embodiment 5, except that:
perfluoropolyether polysiloxanes were prepared according to the procedure of example 5 using PFPE-HEMA and gamma-methacryloxypropyltrimethoxysilane with a molar ratio of carbon to carbon double bonds of 3: 7.
Example 7: the perfluoropolyether modified polysiloxane coating assistant, the preparation method thereof and the coating provided by the embodiment are basically the same as those of the embodiments 1 and 2, except that:
Rf-COOCH2CH2OC (O) C (CH3) ═ CH2(PFPE-HEMA) was synthesized according to the procedure of example 2,
the method of reference example 1: to a 100ml three-necked flask equipped with a magnetic stirring rotor, a nitrogen inlet and a reflux condenser, hydrogen-containing silicone oil (hydrogen content 1.6%, 0.1g, 0.0016mol), PFPE-HEMA (4.94g, 0.00159mol), 10. mu.L of 400ppm chloroplatinic acid catalyst and 5ml of a fluorine solvent were added under nitrogen protection. Heating to 100 ℃, stirring for 1h, washing, and distilling under reduced pressure to obtain clear oily liquid, thereby obtaining the perfluoropolyether modified polysiloxane.
Variations and modifications to the above-described embodiments may occur to those skilled in the art, which fall within the scope and spirit of the above description. Therefore, the present invention is not limited to the specific embodiments disclosed and described above, and some modifications and variations of the present invention should fall within the scope of the claims of the present invention.
Claims (12)
1. A perfluoropolyether modified polysiloxane coating auxiliary agent is characterized in that the coating auxiliary agent is prepared by reacting perfluoropolyether acrylate with siloxane containing carbon-carbon double bonds and hydrogen-containing silicone oil under the action of a catalyst; the feeding molar ratio of the perfluoropolyether acrylate to the siloxane containing carbon-carbon double bonds to the hydrogen-containing silicone oil is 1-9:1-9: 1.
2. The perfluoropolyether-modified polysiloxane coating aid of claim 1, wherein the perfluoropolyether acrylate is obtained by reacting perfluoropolyether acid chloride and a hydroxyl-containing acrylate compound in a feed molar ratio of 1:1 to 1.5.
3. The perfluoropolyether-modified polysiloxane coating aid of claim 2, wherein the perfluoropolyether acid chloride is obtained by reacting thionyl chloride and perfluoropolyether carboxylic acid in a molar ratio of 3-8:1 in the presence of a solvent.
4. The perfluoropolyether-modified polysiloxane coating adjuvant of claim 1 wherein said catalyst is a metal catalyst such as rhodium, platinum, nickel or a lewis acid catalyst such as any one or more of aluminum trichloride and ferric trichloride.
5. The perfluoropolyether-modified polysiloxane coating adjuvant of claim 3 wherein said solvent is any one or more of hydrofluoroether, hexafluorom-xylene, trifluorotrichloroethane, toluene, 1, 4-dioxane, dichloromethane, tetrahydrofuran, toluene, 1, 4-dioxane.
6. The perfluoropolyether-modified polysiloxane coating assistant of claim 2, wherein the hydroxyl-containing acrylate compound is any one of trihydroxy acrylate, pentaerythritol triacrylate, 2-hydroxyethyl acrylate, hydroxyethyl methacrylate, and 4-hydroxybutyl acrylate.
7. The perfluoropolyether-modified polysiloxane coating adjuvant of claim 1 wherein the carbon-carbon double bond-containing siloxane has the formula CH2 ═ CR1R2Si (OR3)3, wherein R1 ═ H, CH 3; r2 ═ COO, CH2CH2, or no R2; r3 ═ CH3, CH2CH3, CH (CH3)2, oc (o) CH2CH3, oc (o) CH ═ CH 3.
8. The perfluoropolyether-modified polysiloxane coating adjuvant of claim 1, wherein said perfluoropolyether carboxylic acid has the formula CF3CF2CF2O(CF(CF3)CF2O)n-COOH, wherein n is 17, 34, molecular weight Mw is 3000-6000.
9. The preparation method of the perfluoropolyether modified polysiloxane coating auxiliary agent is characterized by comprising the following steps:
(1) preparation of perfluoropolyether acrylate:
s1: dropwise adding thionyl chloride into a three-neck flask of perfluoropolyether carboxylic acid, adding a solvent, magnetically stirring to react for a certain time, washing, and removing unreacted monomers under reduced pressure to obtain perfluoropolyether acyl chloride;
s2: adding perfluoropolyether acyl chloride and a hydroxyl-containing acrylate compound into a three-neck flask according to a set molar ratio, reacting for a certain time under the protection of nitrogen, washing, and removing unreacted monomers under reduced pressure to obtain perfluoropolyether acrylate;
(2) preparation of perfluoropolyether modified polysiloxane
S3: adding perfluoropolyether acrylate, carbon-carbon double bond-containing siloxane and hydrogen-containing silicone oil into a three-neck flask, introducing nitrogen, adding a catalyst, stirring for reacting for a certain time, and cooling to room temperature to obtain a product;
s4: and adding a precipitation solvent into the obtained product to precipitate the polymer, washing to remove unreacted monomers, and distilling under reduced pressure to remove the precipitation solvent to obtain the perfluoropolyether modified polysiloxane.
10. The method for preparing the perfluoropolyether-modified polysiloxane coating assistant according to claim 10, wherein the reaction conditions in step S1 are 60-80 ℃ for 3-7 hours; the reaction condition in S2 is room temperature reaction time 6-12 hours; the reaction condition in S3 is that stirring reaction is carried out for 2-12 hours at 40-120 ℃; the precipitation solvent is methanol.
11. A coating containing a perfluoropolyether modified polysiloxane coating aid is characterized in that a coating agent is obtained by diluting perfluoropolyether modified polysiloxane with a solvent, is sprayed on a clean glass plate, is placed at room temperature, and is subjected to vacuum drying and high-temperature baking to obtain an antifouling coating.
12. The coating of claim 11, wherein the perfluoropolyether-modified polysiloxane is present in an amount of 0.1 to 0.3 wt% after dilution with a solvent; the clean glass plate is obtained by any one or more treatment modes of ethanol-acetone ultrasonic treatment, sulfuric acid-hydrogen peroxide chemical treatment, UV ozone irradiation treatment or plasma treatment; standing at room temperature for 10-15 min; the high-temperature baking temperature is 120-; the thickness of the antifouling coating is 10-50 nm.
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Cited By (9)
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| CN112694807A (en) * | 2021-02-06 | 2021-04-23 | 郝云霞 | Fluorine-silicon-containing coating composition and preparation method thereof |
| CN113527691A (en) * | 2021-06-24 | 2021-10-22 | 无锡龙驰氟硅新材料有限公司 | Fluorosilicone polymer and preparation method thereof |
| CN114213661A (en) * | 2021-12-29 | 2022-03-22 | 惠州瑞德新材料科技股份有限公司 | Photocuring perfluoropolyether/alkenyl silicone resin, preparation method and application |
| CN114702900A (en) * | 2022-04-07 | 2022-07-05 | 东莞泰岳光学镀膜材料有限公司 | Mobile phone glass rear cover coating liquid and preparation method and application thereof |
| CN115216042A (en) * | 2022-07-13 | 2022-10-21 | 天津日津科技股份有限公司 | Preparation method of hydrophobic and oleophobic PTFE composite membrane |
| CN115584029A (en) * | 2022-11-21 | 2023-01-10 | 东莞市喜发光学材料有限公司 | Silane compound containing perfluoropolyether, preparation and application thereof |
| CN116574263A (en) * | 2022-07-19 | 2023-08-11 | 华诺森（武汉）生物医药技术有限公司 | Preparation method of fluorine-containing hydrophilic macromolecular organic silicon monomer for silicon hydrogel contact lens |
| CN116693958A (en) * | 2023-08-07 | 2023-09-05 | 中石油(上海)新材料研究院有限公司 | High-wear-resistance organic fluorine modified solution polymerized styrene-butadiene rubber and preparation method thereof |
| CN117777857A (en) * | 2023-12-08 | 2024-03-29 | 江苏瑞洋安泰新材料科技有限公司 | Manufacturing method of low-viscosity high-performance environment-friendly silane modified polyether waterproof coating |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN112694807A (en) * | 2021-02-06 | 2021-04-23 | 郝云霞 | Fluorine-silicon-containing coating composition and preparation method thereof |
| CN112694807B (en) * | 2021-02-06 | 2021-12-10 | 佛山市思特四通科技有限公司 | Fluorine-silicon-containing coating composition and preparation method thereof |
| CN113527691A (en) * | 2021-06-24 | 2021-10-22 | 无锡龙驰氟硅新材料有限公司 | Fluorosilicone polymer and preparation method thereof |
| CN114213661A (en) * | 2021-12-29 | 2022-03-22 | 惠州瑞德新材料科技股份有限公司 | Photocuring perfluoropolyether/alkenyl silicone resin, preparation method and application |
| CN114702900A (en) * | 2022-04-07 | 2022-07-05 | 东莞泰岳光学镀膜材料有限公司 | Mobile phone glass rear cover coating liquid and preparation method and application thereof |
| CN114702900B (en) * | 2022-04-07 | 2022-09-27 | 东莞泰岳光学镀膜材料有限公司 | Mobile phone glass rear cover coating liquid and preparation method and application thereof |
| CN115216042A (en) * | 2022-07-13 | 2022-10-21 | 天津日津科技股份有限公司 | Preparation method of hydrophobic and oleophobic PTFE composite membrane |
| CN116574263A (en) * | 2022-07-19 | 2023-08-11 | 华诺森（武汉）生物医药技术有限公司 | Preparation method of fluorine-containing hydrophilic macromolecular organic silicon monomer for silicon hydrogel contact lens |
| CN115584029A (en) * | 2022-11-21 | 2023-01-10 | 东莞市喜发光学材料有限公司 | Silane compound containing perfluoropolyether, preparation and application thereof |
| CN116693958A (en) * | 2023-08-07 | 2023-09-05 | 中石油(上海)新材料研究院有限公司 | High-wear-resistance organic fluorine modified solution polymerized styrene-butadiene rubber and preparation method thereof |
| CN116693958B (en) * | 2023-08-07 | 2023-11-03 | 中石油(上海)新材料研究院有限公司 | High-wear-resistance organic fluorine modified solution polymerized styrene-butadiene rubber and preparation method thereof |
| CN117777857A (en) * | 2023-12-08 | 2024-03-29 | 江苏瑞洋安泰新材料科技有限公司 | Manufacturing method of low-viscosity high-performance environment-friendly silane modified polyether waterproof coating |
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