CN116042087A - Long-acting ceramic non-stick paint containing active fluorosilicone multifunctional auxiliary agent and preparation method thereof - Google Patents

Long-acting ceramic non-stick paint containing active fluorosilicone multifunctional auxiliary agent and preparation method thereof Download PDF

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CN116042087A
CN116042087A CN202211743628.1A CN202211743628A CN116042087A CN 116042087 A CN116042087 A CN 116042087A CN 202211743628 A CN202211743628 A CN 202211743628A CN 116042087 A CN116042087 A CN 116042087A
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fluorosilicone
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auxiliary agent
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CN116042087B (en
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刘海龙
钱涛
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Hangzhou Jihua Polymer Materials Co ltd
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    • 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
    • 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
    • C09D183/04—Polysiloxanes
    • 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
    • C08G77/04—Polysiloxanes
    • C08G77/06—Preparatory processes
    • 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
    • C08G77/04—Polysiloxanes
    • C08G77/20—Polysiloxanes containing silicon bound to unsaturated aliphatic groups
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    • 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
    • C08G77/04—Polysiloxanes
    • C08G77/22—Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen and oxygen
    • C08G77/24—Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen and oxygen halogen-containing groups
    • 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
    • C08G77/04—Polysiloxanes
    • C08G77/38—Polysiloxanes modified by chemical after-treatment
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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
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
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    • C09D7/61—Additives non-macromolecular inorganic
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    • 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
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
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    • C09D7/65—Additives macromolecular
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    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K2201/00—Specific properties of additives
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    • C08L2201/00—Properties
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    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P40/00—Technologies relating to the processing of minerals
    • Y02P40/60—Production of ceramic materials or ceramic elements, e.g. substitution of clay or shale by alternative raw materials, e.g. ashes

Abstract

The invention relates to the field of coatings, and discloses a long-acting ceramic non-stick coating containing an active fluorosilicone multifunctional auxiliary agent and a preparation method thereof. The paint comprises 20-40 parts of silane, 2-4 parts of active fluorosilicone multifunctional auxiliary agent, 0.5-1.5 parts of adhesion promoter, 1.5-4 parts of cosolvent, 15-30 parts of nano silica sol, 30-50 parts of high temperature resistant pigment filler, 0.2-0.5 part of dispersing agent, 0.1-0.3 part of acid catalyst and 40-60 parts of water. The active fluorosilicone multifunctional auxiliary agent not only can play a role in wetting and leveling in the construction process of the ceramic coating, but also can participate in sol-gel reaction of the ceramic coating, and is tightly combined with the coating through chemical bonding. The ceramic non-stick paint containing the active fluorosilicone multifunctional auxiliary agent keeps the original performances of high temperature resistance, abrasion resistance and the like, and meanwhile, the fluorosilicone chain segment with low surface energy is enriched on the surface of the coating through a self-layering mechanism, so that the ceramic non-stick paint has longer-acting non-stick property.

Description

Long-acting ceramic non-stick paint containing active fluorosilicone multifunctional auxiliary agent and preparation method thereof
Technical Field
The invention relates to the field of coatings, in particular to a long-acting ceramic non-stick coating containing an active fluorosilicone multifunctional auxiliary agent and a preparation method thereof.
Background
Compared with the Teflon non-stick coating, the ceramic non-stick coating has rich raw material sources and low VOCs content; the curing temperature is low, and the energy is saved; no toxic or harmful substances are generated during the manufacturing and using process, and the method is healthy and environment-friendly; high hardness, scratch resistance, long service life, resource conservation and the like. Therefore, the development of the ceramic non-stick coating is beneficial to reducing carbon emission, and great economic and social benefits can be generated.
However, the Teflon material has excellent non-stick performance, and the non-stick performance of the ceramic non-stick coating depends on the special structure of the lotus leaf-like surface formed by the micro-nano structure of the surface and the non-stick auxiliary agent with low surface energy. The non-stick auxiliary agents such as dimethyl silicone oil, hydroxyl silicone oil and the like used in the current market have poor binding force with the coating, and can be worn along with friction in the use process, so that the ceramic coating is difficult to maintain long-acting non-stick. Therefore, how to form a layer of low-surface-energy non-sticky substance firmly combined by chemical bonds on the surface of the ceramic coating is an effective method for improving the long-acting non-sticky property of the traditional ceramic coating.
In view of this, researchers have used long-chain fluorocarbon silane coupling agents as non-stick aids for ceramic coatings, which utilize the good reactivity of fluorine-containing silane coupling agents with coatings to form firm chemical bond bonds, improving the non-stick durability of ceramic coatings. However, the long-chain fluorocarbon silane coupling agent has very high price and huge production cost, and is not beneficial to the popularization of products.
Disclosure of Invention
In order to solve the technical problems, the invention provides a long-acting ceramic non-stick coating containing an active fluorosilicone multifunctional auxiliary agent and a preparation method thereof. The ceramic non-stick paint contains the active fluorosilicone multifunctional auxiliary agent, the price of the active fluorosilicone multifunctional auxiliary agent is far lower than that of a long-chain fluorocarbon silane coupling agent, and the low-surface-energy fluorosilicone chain segment is enriched on the surface of the coating through a self-layering mechanism while the original performances of high temperature resistance, high hardness and the like of the ceramic non-stick paint are maintained, so that the ceramic non-stick paint has longer-acting non-stick property. In addition, the active fluorosilicone multifunctional auxiliary agent is applied to the ceramic coating, not only can play a role in wetting and leveling in the construction process to enable the coating to be flat, smooth and uniform, but also can participate in sol-gel reaction of the ceramic coating, and is tightly combined with the coating through chemical bonding after the coating is solidified.
The specific technical scheme of the invention is as follows:
in a first aspect, the invention provides a long-acting ceramic non-stick coating containing an active fluorosilicone multifunctional auxiliary agent, which is prepared from the following raw materials in parts by weight: 20-40 parts of silane, 2-4 parts of active fluorosilicone multifunctional auxiliary agent, 0.5-1.5 parts of adhesion promoter, 1.5-4 parts of cosolvent, 15-30 parts of nano silica sol, 30-50 parts of high temperature resistant pigment and filler, 0.2-0.5 part of dispersing agent, 0.1-0.3 part of acid catalyst and 40-60 parts of water.
The ceramic non-stick coating consists of silane, an active fluorosilicone multifunctional auxiliary agent, an adhesion promoter, a cosolvent, nano silica sol, high-temperature-resistant pigment and filler, a dispersing agent, an acid catalyst and water. The active fluorosilicone multifunctional auxiliary agent is a compound which is prepared from fluorine-containing cyclosiloxane, vinyl double-end socket and trialkoxysilane through ring opening polymerization and hydrosilylation reaction and contains organic fluorine and organic silicon structural units, the durable non-tackiness performance of the active fluorosilicone multifunctional auxiliary agent is obviously superior to that of the traditional non-tackiness auxiliary agent dimethyl silicone oil and hydroxyl silicone oil, and the price of the active fluorosilicone multifunctional auxiliary agent is far lower than that of a substituted long-acting non-tackiness auxiliary agent long-chain fluorocarbon silane coupling agent.
In addition, compared with a long-chain fluorocarbon silane coupling agent, the active fluorosilicone multifunctional additive is applied to ceramic paint, not only can play a very obvious role in wetting and leveling in the construction process to make the coating flat, smooth and uniform, but also can participate in sol-gel reaction of the ceramic paint, and is tightly combined with the coating through chemical bonding after the coating is solidified. In addition, the ceramic non-stick paint containing the active fluorosilicone multifunctional additive maintains the original performances of high temperature resistance, high hardness and the like, and meanwhile, the fluorosilicone chain segments with low surface energy are enriched on the surface of the coating through a self-layering mechanism, so that the ceramic non-stick paint has longer-acting non-stick property.
Preferably, the molecular structural formula of the active fluorosilicone multifunctional auxiliary agent is as follows:
Figure BDA0004025712930000021
wherein R is CH 3 Or CH (CH) 2 CH 3 ；n＝3-40，m＝3-28。
From the molecular structural formula of the active fluorosilicone multifunctional auxiliary agent, the end group of the active fluorosilicone multifunctional auxiliary agent is a methoxy or ethoxy end-capped coupling agent structure, and small molecular methanol or ethanol is easy to hydrolyze and remove when the active fluorosilicone multifunctional auxiliary agent participates in sol-gel reaction of ceramic coating, and the formed silanol has good reactivity with silanol formed by silane and undergoes dehydration condensation reaction. n is the number of repeated structural units of the fluorine-containing chain segment, in theory, the greater n is, the better the non-stick performance of the active fluorosilicone multifunctional auxiliary agent is, but the greater n is, the poor compatibility with a ceramic coating system can be caused, and the application of the active fluorosilicone multifunctional auxiliary agent in the ceramic non-stick coating is hindered, so that the structure formed by opening 1 trifluoropropyl methyl cyclotrisiloxane and 10 trifluoropropyl cyclotetrasiloxane is selected as 3-40; m is the number of repeated structural units of polysiloxane chain segment, which can improve the compatibility of the active fluorosilicone multifunctional auxiliary agent and a ceramic coating system and reduce the product cost, but the chain segment is too long and can influence the non-stick performance, so that 3-28 is selected, namely, 1 hexamethylcyclotrisiloxane to 7 octamethyltetrasiloxane are introduced to form a structure through ring opening.
Preferably, the preparation method of the active fluorosilicone multifunctional auxiliary agent comprises the following steps: adding 1-7 mol parts of cyclosiloxane, 1 mol part of vinyl double-end socket and a solid catalyst into a reaction container, heating to 40-60 ℃ under the protection of inert gas, reacting for 0.5-1h, adding 1-10 mol parts of fluorine-containing cyclosiloxane, continuously reacting for 0.5-1.5h, and taking supernatant after the reaction is finished to obtain vinyl-end capped fluorine-containing polysiloxane; then adding 2-3 mol parts of trialkoxysilane, a platinum catalyst and an organic solvent, uniformly stirring, and then reacting for 2-4 hours at 70-90 ℃, and removing the organic solvent and excessive silane from the product to obtain the active fluorosilicone multifunctional auxiliary agent.
The preparation method comprises the steps of taking cyclosiloxane and fluorine-containing cyclosiloxane as raw materials, preparing vinyl end-capped fluorine-containing polysiloxane under the end-capping regulation and control of a vinyl double-end socket through the balance reaction of ring-opening copolymerization under the action of a solid catalyst, and then carrying out hydrosilylation reaction with excessive or equimolar amount of hydrogen-containing trialkoxysilane under the catalysis of a platinum catalyst to prepare the active fluorosilicone multifunctional auxiliary agent with the two ends being coupling agent structures. The synthesis raw material cost of the active fluorosilicone multifunctional auxiliary agent is low, the process is simple and feasible, and the solid catalyst is easy to separate, so that the active fluorosilicone multifunctional auxiliary agent has a wide industrial prospect.
Preferably, the cyclosiloxane is selected from hexamethylcyclotrisiloxane and octamethyltetrasiloxane; the vinyl double end socket is tetramethyl divinyl disiloxane; the solid catalyst is zeolite for adsorbing trifluoromethanesulfonic acid, and the dosage is 2-5wt% of cyclosiloxane; the fluorine-containing cyclosiloxane is selected from trifluoropropyl methyl cyclotrisiloxane and trifluoropropyl cyclotetrasiloxane; the trialkoxysilane is selected from trimethoxysilane and triethoxysilane; the platinum catalyst is selected from a Speier catalyst and a Karstedt catalyst, and the dosage of the platinum catalyst is 20-50ppm of trialkoxysilane; the organic solvent is selected from N, N-dimethylformamide and N-methylpyrrolidone, and the dosage is 200-400wt% of trialkoxysilane.
Preferably, the silane is selected from methyltrimethoxysilane, methyltriethoxysilane, dimethyldimethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, and diphenyldimethoxysilane.
Preferably, the adhesion promoter is selected from the group consisting of gamma-glycidoxypropyl trimethoxysilane and beta- (3, 4 epoxycyclohexyl) -ethyl trimethoxysilane.
In the research process, the invention discovers that the active fluorosilicone multifunctional auxiliary agent can reduce the surface energy of a coating system, and further can influence the adhesive force with a base material to a certain extent. For this purpose, the invention is improved by adding specific amounts of adhesion promoters to the coating system.
Preferably, the cosolvent is selected from isopropanol, propylene glycol butyl ether and propylene glycol methyl ether acetate.
Preferably, the nano silica sol is selected from the group consisting of Levasil CT30 DH, levasil CT20 DH and Levasil CT8 DH of acid silica sol of Noron.
Preferably, the dispersant is selected from the group consisting of UNIQ-690W, BYK-190 and AFCONA-4560.
Preferably, the high temperature resistant pigment and filler is mixed by any ratio of high temperature resistant pigment and high temperature resistant filler, wherein the pigment is common high temperature resistant pigment in the field, and can be inorganic high temperature resistant pigment such as carbon black, high titanium ash and the like, or organic high temperature resistant pigment such as phthalocyanine green and the like. The filler is a high-temperature-resistant filler commonly used in the field, and can be silicon carbide and aluminum oxide.
Preferably, the acid catalyst is selected from formic acid, acetic acid and hydrochloric acid.
In a second aspect, the invention provides a preparation method of the long-acting ceramic non-stick paint containing the active fluorosilicone multifunctional auxiliary agent, which comprises the following steps:
(1) And uniformly mixing the nano silica sol, the high temperature resistant pigment and filler, the dispersing agent and water, and grinding to obtain the silica slurry.
(2) Adding a mixture consisting of silane, active fluorosilicone multifunctional auxiliary agent, adhesion promoter and cosolvent into the silicon dioxide slurry obtained in the step (1), uniformly mixing, adding an acid catalyst, stirring, and filtering to obtain the long-acting ceramic non-stick coating containing the active fluorosilicone multifunctional auxiliary agent.
The ceramic non-stick coating is prepared by sol-gel reaction: under the catalysis of acid, the silane, the active fluorosilicone multifunctional auxiliary agent and the adhesion promoter are subjected to hydrolysis and polycondensation sol-gel reaction, the reaction between silanol and silicon oxygen groups, the reaction between silanol and hydroxyl on the surface of nano silicon dioxide, the reaction between silanol and hydroxyl on the surface of pigment filler and the coordination bond between molecules are combined to form an organic-inorganic interpenetrating network structure, and finally a ceramic hard coating is formed in the curing stage.
Preferably, the grinding is to a fineness of 10 μm or less.
Compared with the prior art, the invention has the beneficial effects that:
(1) The active fluorosilicone multifunctional auxiliary agent combines the advantages of organic fluorine and organic silicon, can improve the long-acting non-tackiness of ceramic paint, has a price far lower than that of a long-chain fluorocarbon silane coupling agent, greatly prolongs the service life and the use feeling of the ceramic non-tackiness paint, and is beneficial to market popularization.
(2) The active fluorosilicone multifunctional auxiliary agent can be used as a non-stick auxiliary agent to participate in sol-gel reaction of the ceramic coating, so that the non-stick auxiliary agent and the coating form firm chemical bond combination, and the ceramic coating is endowed with long-acting non-stick property.
(3) The active fluorosilicone multifunctional auxiliary agent has good low surface energy and self-layering property, can play a role in wetting and leveling in the construction process without adding a leveling agent, enables a coating to be flat, smooth and uniform, and reduces the occurrence rate of defects such as shrinkage cavity, orange peel and the like.
Detailed Description
The invention is further described below with reference to examples.
General examples
A long-acting ceramic non-stick paint containing active fluorosilicone multifunctional auxiliary agent is prepared from the following raw materials in parts by weight: 20-40 parts of silane, 2-4 parts of active fluorosilicone multifunctional auxiliary agent, 0.5-1.5 parts of adhesion promoter, 1.5-4 parts of cosolvent, 15-30 parts of nano silica sol, 30-50 parts of high temperature resistant pigment and filler, 0.2-0.5 part of dispersing agent, 0.1-0.3 part of acid catalyst and 40-60 parts of water.
Preferably, the silane is selected from methyltrimethoxysilane, methyltriethoxysilane, dimethyldimethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, and diphenyldimethoxysilane. The adhesion promoter is selected from gamma-glycidoxypropyl trimethoxysilane and beta- (3, 4 epoxycyclohexyl) -ethyl trimethoxysilane. The cosolvent is selected from isopropanol, propylene glycol butyl ether and propylene glycol methyl ether acetate. The nano silica sol is selected from acidic silica sol Levasil CT30 DH, levasil CT20 DH and Levasil CT8 DH of Noron company. The dispersant is selected from UNIQ-690W, BYK-190 and AFCONA-4560. The high temperature resistant pigment filler is formed by mixing high temperature resistant pigment and high temperature resistant filler in any ratio, wherein the pigment is common high temperature resistant pigment in the field, and can be inorganic high temperature resistant pigment such as carbon black, high titanium ash and the like, or organic high temperature resistant pigment such as phthalocyanine green and the like. The filler is a high-temperature-resistant filler commonly used in the field, and can be silicon carbide and aluminum oxide. The acid catalyst is selected from formic acid, acetic acid and hydrochloric acid.
The molecular structural formula of the active fluorosilicone multifunctional auxiliary agent is as follows:
Figure BDA0004025712930000051
wherein R is CH 3 Or CH (CH) 2 CH 3 ；n＝3-40，m＝3-28。
The preparation method of the active fluorosilicone multifunctional auxiliary agent comprises the following steps: adding 1-7 mol parts of cyclosiloxane, 1 mol part of vinyl double-end socket and a solid catalyst into a reaction container, heating to 40-60 ℃ under the protection of inert gas, reacting for 0.5-1h, adding 1-10 mol parts of fluorine-containing cyclosiloxane, continuously reacting for 0.5-1.5h, and taking supernatant after the reaction is finished to obtain vinyl-end capped fluorine-containing polysiloxane; then adding 2-3 mol parts of trialkoxysilane, a platinum catalyst and an organic solvent, uniformly stirring, and then reacting for 2-4 hours at 70-90 ℃, and removing the organic solvent and excessive silane from the product to obtain the active fluorosilicone multifunctional auxiliary agent. Wherein the cyclosiloxane is selected from hexamethylcyclotrisiloxane and octamethyltetrasiloxane; the vinyl double end socket is tetramethyl divinyl disiloxane; the solid catalyst is zeolite for adsorbing trifluoromethanesulfonic acid, and the dosage is 2-5wt% of cyclosiloxane; the fluorine-containing cyclosiloxane is selected from trifluoropropyl methyl cyclotrisiloxane and trifluoropropyl cyclotetrasiloxane; the trialkoxysilane is selected from trimethoxysilane and triethoxysilane; the platinum catalyst is selected from a Speier catalyst and a Karstedt catalyst, and the dosage of the platinum catalyst is 20-50ppm of trialkoxysilane; the organic solvent is selected from N, N-dimethylformamide and N-methylpyrrolidone, and the dosage is 200-400wt% of trialkoxysilane.
The preparation method of the long-acting ceramic non-stick paint containing the active fluorosilicone multifunctional auxiliary agent comprises the following steps:
(1) Uniformly mixing nano silica sol, high temperature resistant pigment and filler, dispersing agent and water, and grinding until the fineness is less than or equal to 10 mu m to obtain silica slurry.
(2) Adding a mixture consisting of silane, active fluorosilicone multifunctional auxiliary agent, adhesion promoter and cosolvent into the silicon dioxide slurry obtained in the step (1), uniformly mixing, adding an acid catalyst, stirring for 3-6h, and filtering to obtain the long-acting ceramic non-stick coating containing the active fluorosilicone multifunctional auxiliary agent.
Preparation example of active fluorosilicone multifunctional auxiliary agent:
example 1
1 mole part of octamethyl cyclotetrasiloxane, 1 mole part of vinyl double-end socket and a solid catalyst (5 wt% of octamethyl cyclotetrasiloxane) are added into a reaction bottle, under the protection of nitrogen, after the temperature is raised to 60 ℃ for reaction for 0.5h, 3 mole parts of trifluoropropyl methyl cyclotrisiloxane is added, the reaction is carried out for 0.5h again, the supernatant fluid is taken to obtain vinyl-terminated fluorine-containing polysiloxane, then 2.4 mole parts of trimethoxysilane, karstedt catalyst (20 ppm of trimethoxysilane) and N, N-dimethylformamide (200 wt% of trimethoxysilane) are added, after uniform stirring, the reaction is carried out for 2h at 90 ℃, and the product is removed of organic solvent and excessive silane to obtain the active fluorine-silicon multifunctional auxiliary agent.
Example 2
7 mol parts of octamethyl cyclotetrasiloxane, 1 mol part of vinyl double-end socket and a solid catalyst (2 wt% of octamethyl cyclotetrasiloxane) are added into a reaction bottle, under the protection of nitrogen, after the temperature is raised to 50 ℃ for reaction for 1h, 10 mol parts of trifluoropropyl cyclotetrasiloxane is added, the reaction is carried out for 1.5h again, the supernatant fluid is taken to obtain vinyl-terminated fluorine-containing polysiloxane, then 3 mol parts of triethoxysilane, karstedt catalyst (50 ppm of triethoxysilane) and N-methylpyrrolidone (400 wt% of triethoxysilane) are added, after uniform stirring, the reaction is carried out for 4h at 80 ℃, and the product is removed of organic solvent and excessive silane to obtain the active fluorosilicone multifunctional auxiliary agent.
Example 3
1 mole part of hexamethylcyclotrisiloxane, 1 mole part of vinyl double-end socket and a solid catalyst (2 wt% of octamethyl cyclotrisiloxane) are added into a reaction bottle, under the protection of nitrogen, after the temperature is raised to 40 ℃ for reaction for 1h, 1 mole part of trifluoropropyl methyltrisiloxane is added, the reaction is carried out for 1.5h again, the supernatant fluid is taken to obtain vinyl-terminated fluorine-containing polysiloxane, then 2 mole parts of trimethoxysilane, a Speier catalyst (30 ppm of trimethoxysilane) and N-methylpyrrolidone (200 wt% of trimethoxysilane) are added, after uniform stirring, the reaction is carried out for 3h at 70 ℃, and the product is removed of organic solvent and excessive silane to obtain the active fluorosilicone multifunctional auxiliary agent.
Coating preparation example:
example 4
(1) 15 parts by weight of nano silica sol Levasil CT30 DH, 10 parts by weight of carbon black, 20 parts by weight of silicon carbide, 0.2 part by weight of dispersant UNIQ-690W and 40 parts by weight of deionized water are uniformly mixed, and the mixture is ground to the fineness of less than or equal to 10 mu m, so that the silica slurry is obtained.
(2) Adding a mixture consisting of 15 parts by weight of methyltrimethoxysilane, 5 parts by weight of phenyltrimethoxysilane, 2 parts by weight of the active fluorosilicone multifunctional additive prepared in the embodiment 1, 0.5 part by weight of gamma-glycidol ether oxypropyl trimethoxysilane and 1.5 parts by weight of isopropanol into the silica slurry prepared in the step (1), uniformly mixing, adding 0.1 part by weight of formic acid, stirring for 3 hours, and filtering to obtain the active fluorosilicone multifunctional additive-containing long-acting ceramic non-stick coating.
Example 5
(1) Uniformly mixing 30 parts by weight of nano silica sol Levasil CT20 DH, 15 parts by weight of high titanium ash, 35 parts by weight of alumina, 0.5 part by weight of dispersant BYK-190 and 60 parts by weight of deionized water, and grinding until the fineness is less than or equal to 10 mu m to obtain the silica slurry.
(2) Adding a mixture consisting of 20 parts by weight of methyltriethoxysilane, 10 parts by weight of dimethyldimethoxysilane, 10 parts by weight of phenyltriethoxysilane, 4 parts by weight of the active fluorosilicone multifunctional additive prepared in example 3, 1.5 parts by weight of beta- (3, 4-epoxycyclohexyl) -ethyltrimethoxysilane and 4 parts by weight of propylene glycol butyl ether into the silica slurry prepared in the step (1), uniformly mixing, adding 0.3 part by weight of acetic acid, stirring for 6 hours, and filtering to obtain the active fluorosilicone multifunctional additive-containing long-acting ceramic non-stick coating.
Example 6
(1) Uniformly mixing 25 parts by weight of nano silica sol Levasil CT8 DH, 10 parts by weight of phthalocyanine green, 30 parts by weight of alumina, 0.35 part by weight of dispersant AFCONA-4560 and 50 parts by weight of deionized water, and grinding until the fineness is less than or equal to 10 mu m to obtain the silica slurry.
(2) Adding a mixture consisting of 20 parts by weight of methyltrimethoxysilane, 3 parts by weight of phenyltriethoxysilane, 2 parts by weight of diphenyldimethoxysilane, 3 parts by weight of the active fluorosilicone multifunctional additive prepared in example 2, 1 part by weight of gamma-glycidol ether oxypropyl trimethoxysilane and 2.5 parts by weight of propylene glycol methyl ether acetate into the silica slurry prepared in the step (1), uniformly mixing, adding 0.15 part by weight of hydrochloric acid, stirring for 4 hours, and filtering to obtain the long-acting ceramic non-stick coating containing the active fluorosilicone multifunctional additive.
Comparative example 1
The difference from example 4 is only that in step (2) no reactive fluorosilicone multifunctional auxiliary is added, and that the same parts by weight of hydroxy silicone oil (molecular weight 2000) are used instead, and the rest of the steps and materials and compositions are the same as in example 4.
Comparative example 2
The difference from example 4 is that the reactive fluorosilicone multifunctional auxiliary is not added in the step (2), the heptadecafluorodecyl trimethoxysilane is replaced by the same weight part, and the rest steps and materials and compositions are the same as those of example 4.
Comparative example 3
The difference from example 4 is only that the adhesion promoter gamma-glycidoxypropyl trimethoxysilane was not added in step (2), and the remaining steps and materials and compositions were identical to those of example 4.
Performance testing
The long-acting ceramic non-stick paint containing the active fluorosilicone multifunctional auxiliary agent prepared in the examples 4-6 and the paint prepared in the comparative examples 1-3 are respectively coated on an aluminum substrate (the thickness of the paint film is controlled to be 20 mu m), and then the performances of leveling property, hardness, adhesive force, temperature resistance, non-tackiness and the like of the paint film are detected, wherein the leveling property is judged by observing the appearance of the paint film, the paint film is smooth and has no orange peel and very good, the paint film is flat and has no orange peel but has poor gloss, the slight orange peel of the paint film is general, and the conditions of serious orange peel or shrinkage cavity, serious fog and the like of the paint film are poor; hardness test was carried out as specified in GB/T6739, and the results were evaluated: paint film scratch; the adhesive force test is carried out according to the specification of GB/T9286, and the interval is 2mm; heat resistance was measured according to the standard of GB/T1735, test conditions: 200 ℃ for 30min, and evaluating the result: the chromatic aberration is less than or equal to 2 and is qualified; the non-tackiness is tested according to the method for testing omelet in HG/T4563-2013, more than or equal to 15 are excellent, 10-15 are good, 5-10 are qualified, and less than 5 are unqualified; the test results are shown in Table 1.
Table 1 results of product performance tests for examples 4-6 and comparative examples 1-3:
leveling property Hardness of Adhesion force Heat resistance Non-tackiness
Example 4 Very good 6H Level 1 Qualified product Excellent and excellent properties
Example 5 Very good 6H Level 1 Qualified product Excellent and excellent properties
Example 6 Very good 6H Level 1 Qualified product Excellent and excellent properties
Comparative example 1 In general 6H Level 0 Qualified product Failure to pass
Comparative example 2 Good (good) 6H Level 1 Qualified product Excellent and excellent properties
Comparative example 3 Very good 6H 3 grade Qualified product Excellent and excellent properties
From the comparison of the above table data, it can be seen that:
in comparative example 1, the hydroxyl silicone oil with equal weight parts is used for replacing the active fluorosilicone multifunctional auxiliary agent, and as no fluorine-containing substance is added, the adhesive force of the coating is improved, but the leveling effect is not achieved, slight orange peel appears on the surface of a cured paint film, and in the test of fried eggs, obvious pot sticking phenomenon appears in 2-3 layers, which indicates that the non-adhesive performance of the silicone oil is poor.
In the comparative example 2, heptadecafluorodecyl trimethoxysilane is adopted to replace the active fluorosilicone multifunctional auxiliary agent, and the adhesive has excellent non-tackiness, but because fluorine-containing and silicon-containing chain segments in a molecular structure are far smaller than the active fluorosilicone multifunctional auxiliary agent, the leveling effect is limited, and the price of the heptadecafluorodecyl trimethoxysilane is higher, so that the adhesive is not beneficial to industrial use; the adhesion promoter is not added in comparative example 3, and the adhesion is remarkably reduced.
Compared with comparative examples 1-3, the long-acting ceramic non-stick coating containing the active fluorosilicone multifunctional auxiliary agent of examples 4-6 has excellent non-stick performance of the long-chain fluorocarbon silane coupling agent heptadecafluorodecyl trimethoxy silane, and has a very good leveling effect. In addition, compared with comparative example 3, the addition of the active fluorosilicone multifunctional auxiliary agent and the matching of the adhesion promoter ensure that the ceramic coating has long-acting non-tackiness and still maintains the original performances of high temperature resistance, high hardness and the like.
The raw materials and equipment used in the invention are common raw materials and equipment in the field unless specified otherwise; the methods used in the present invention are conventional in the art unless otherwise specified.
The foregoing description is only a preferred embodiment of the present invention, and is not intended to limit the present invention, and any simple modification, variation and equivalent transformation of the above embodiment according to the technical substance of the present invention still fall within the scope of the technical solution of the present invention.

Claims (10)

1. A long-acting ceramic non-stick paint containing active fluorosilicone multifunctional auxiliary agent is characterized in that: the material is prepared from the following raw materials in parts by weight:
20-40 parts of silane and the balance of the catalyst,
2-4 parts of active fluorosilicone multifunctional auxiliary agent,
0.5 to 1.5 portions of adhesion promoter,
1.5-4 parts of cosolvent,
15-30 parts of nano silica sol,
30-50 parts of high temperature resistant pigment and filler,
0.2 to 0.5 part of dispersing agent,
0.1 to 0.3 part of acid catalyst,
40-60 parts of water;
the active fluorosilicone multifunctional auxiliary agent is a compound which is prepared from fluorine-containing cyclosiloxane, vinyl double-end socket and trialkoxysilane through ring opening polymerization and hydrosilylation reaction and simultaneously contains organic fluorine and an organic silicon structural unit.
2. The long-acting ceramic non-stick coating of claim 1, wherein: the molecular structural formula of the active fluorosilicone multifunctional auxiliary agent is as follows:
Figure FDA0004025712920000011
wherein R is CH 3 Or CH (CH) 2 CH 3 ；n＝3-40，m＝3-28。
3. The long-acting ceramic non-stick coating of claim 2, wherein: the preparation method of the active fluorosilicone multifunctional auxiliary agent comprises the following steps: adding 1-7 mol parts of cyclosiloxane, 1 mol part of vinyl double-end socket and a solid catalyst into a reaction container, heating to 40-60 ℃ under the protection of inert gas, reacting for 0.5-1h, adding 1-10 mol parts of fluorine-containing cyclosiloxane, continuously reacting for 0.5-1.5h, and taking supernatant after the reaction is finished to obtain vinyl-end capped fluorine-containing polysiloxane; then adding 2-3 mol parts of trialkoxysilane, a platinum catalyst and an organic solvent, uniformly stirring, and then reacting for 2-4 hours at 70-90 ℃, and removing the organic solvent and excessive silane from the product to obtain the active fluorosilicone multifunctional auxiliary agent.
4. A long-acting ceramic non-stick coating as claimed in claim 3, wherein:
the cyclosiloxanes are selected from hexamethylcyclotrisiloxane and octamethyltetrasiloxane;
the vinyl double end socket is tetramethyl divinyl disiloxane;
the solid catalyst is zeolite for adsorbing trifluoromethanesulfonic acid, and the dosage is 2-5wt% of cyclosiloxane;
the fluorine-containing cyclosiloxane is selected from trifluoropropyl methyl cyclotrisiloxane and trifluoropropyl cyclotetrasiloxane;
the trialkoxysilane is selected from trimethoxysilane and triethoxysilane;
the platinum catalyst is selected from a Speier catalyst and a Karstedt catalyst, and the dosage of the platinum catalyst is 20-50ppm of trialkoxysilane;
the organic solvent is selected from N, N-dimethylformamide and N-methylpyrrolidone, and the dosage is 200-400wt% of trialkoxysilane.
5. The long-acting ceramic non-stick coating of any one of claims 1-4, wherein: the silane is selected from methyltrimethoxysilane, methyltriethoxysilane, dimethyldimethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, and diphenyldimethoxysilane.
6. A long-acting ceramic non-stick coating containing an active fluorosilicone multifunctional additive as claimed in any one of claims 1 to 4, wherein: the adhesion promoter is selected from gamma-glycidoxypropyl trimethoxysilane and beta- (3, 4 epoxycyclohexyl) -ethyl trimethoxysilane.
7. A long-acting ceramic non-stick coating containing an active fluorosilicone multifunctional additive as claimed in any one of claims 1 to 4, wherein: the cosolvent is selected from isopropanol, propylene glycol butyl ether and propylene glycol methyl ether acetate.
8. A long-acting ceramic non-stick coating containing an active fluorosilicone multifunctional additive as claimed in any one of claims 1 to 4, wherein: the acid catalyst is selected from formic acid, acetic acid and hydrochloric acid.
9. A method for preparing a long-acting ceramic non-stick paint containing an active fluorosilicone multifunctional auxiliary agent according to any one of claims 1-8, which is characterized by comprising the following steps:
(1) Uniformly mixing nano silica sol, high temperature resistant pigment and filler, a dispersing agent and water, and grinding to obtain silica slurry;
(2) Adding a mixture consisting of silane, active fluorosilicone multifunctional auxiliary agent, adhesion promoter and cosolvent into the silicon dioxide slurry obtained in the step (1), uniformly mixing, adding an acid catalyst, uniformly stirring, and filtering to obtain the long-acting ceramic non-stick coating containing the active fluorosilicone multifunctional auxiliary agent.
10. The method of preparing as claimed in claim 9, wherein: the grinding is carried out until the fineness is less than or equal to 10 mu m.
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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103205201A (en) * 2013-01-22 2013-07-17 浙江鹏孚隆科技有限公司 Non-stick ceramic paint and coating method thereof
CN106084233A (en) * 2016-07-20 2016-11-09 杭州吉华高分子材料股份有限公司 A kind of fluorinated polysiloxane does not glue auxiliary agent and preparation method and application
CN114761467A (en) * 2019-12-02 2022-07-15 美国陶氏有机硅公司 Composition for preparing release coating

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103205201A (en) * 2013-01-22 2013-07-17 浙江鹏孚隆科技有限公司 Non-stick ceramic paint and coating method thereof
CN106084233A (en) * 2016-07-20 2016-11-09 杭州吉华高分子材料股份有限公司 A kind of fluorinated polysiloxane does not glue auxiliary agent and preparation method and application
CN114761467A (en) * 2019-12-02 2022-07-15 美国陶氏有机硅公司 Composition for preparing release coating

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