CN112961572B - High-adhesion high-temperature-resistant glass coating and preparation method thereof - Google Patents

High-adhesion high-temperature-resistant glass coating and preparation method thereof Download PDF

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CN112961572B
CN112961572B CN202110176035.0A CN202110176035A CN112961572B CN 112961572 B CN112961572 B CN 112961572B CN 202110176035 A CN202110176035 A CN 202110176035A CN 112961572 B CN112961572 B CN 112961572B
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CN112961572A (en
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蒋弘谷
沈亚汝
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Shanghai Xianquan Optical Fiber Technology Co ltd
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    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09DCOATING 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
    • C09D163/00Coating compositions based on epoxy resins; Coating compositions based on derivatives of epoxy resins
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09DCOATING 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
    • C09D5/00Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/18Fireproof paints including high temperature resistant paints
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09DCOATING 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
    • C09D7/00Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
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    • C09D7/60Additives non-macromolecular
    • C09D7/61Additives non-macromolecular inorganic
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    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K2201/00Specific properties of additives
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    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00Polymer mixtures characterised by other features
    • C08L2205/03Polymer mixtures characterised by other features containing three or more polymers in a blend

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Abstract

The invention discloses a high-adhesion high-temperature-resistant glass coating and a preparation method thereof. The glass coating comprises, by weight, 19-21 parts of nanoparticle slurry, 21-27 parts of an epoxy resin compound, 10-15 parts of a waterborne polyurethane resin, 9-12 parts of a soybean protein binder, 10-15 parts of an organic solvent, 7-13 parts of a curing agent, 1-3 parts of a wetting agent and 0.7-1 part of a leveling agent. Wherein the epoxy resin compound is mainly prepared by reacting eugenol, epichlorohydrin and tetramethyldisiloxane; the curing agent is ethylenediamine, the nano particle slurry is a dispersion liquid of nano ceramic particles and graphene oxide powder in N, N-dimethylformamide, and the mass ratio of the nano ceramic particles to the graphene oxide powder is 4: 1; the wetting agent is alkylaryl polyether alcohol; the leveling agent is an acrylic leveling agent. The glass coating prepared by the invention has high adhesion with a glass substrate, is high-temperature resistant, and has high strength of a cured film layer and is not easy to fall off.

Description

High-adhesion high-temperature-resistant glass coating and preparation method thereof
Technical Field
The invention relates to the technical field of glass coatings, in particular to a high-adhesion high-temperature-resistant glass coating and a preparation method thereof.
Background
The coating protection and decoration of glass and glass products has wide requirements and application in industry and daily life, and the coating protection and decoration of the glass and the glass products refers to a process of coating a specific glass coating on the surface of a glass substrate and forming a film layer after curing.
The glass coating is of various types and can be roughly divided into oil glass coating, water glass coating, ultraviolet curing urethane acrylate glass coating, wear-resistant glass coating, self-cleaning glass coating, heat-insulating glass coating and ultraviolet-resistant glass coating.
At present, oil glass paint and water glass paint are widely used. The oily glass paint takes benzene and ester organic matters as solvents, is stably adhered to the surface of glass to beautify and decorate the glass, has good adhesion with a base material, high glossiness, low cost, simple preparation process and low viscosity in construction, does not generate sagging phenomenon, but uses a large amount of organic solvents such as benzene and the like, thus being easy to pollute the environment and influencing the health of people. The water glass paint mainly comprises polyacrylate, polyurethane oil and acrylate modified polyurethane single-component paint, and a large amount of organic solvents such as benzene and the like are omitted, so that the water glass paint has small environmental pollution. However, the glass paint in the current market has the defects of unsatisfactory adhesive force, weak high-temperature resistance and poor water resistance.
Disclosure of Invention
The invention aims to provide a high-adhesion high-temperature-resistant glass coating and a preparation method thereof, so as to solve the problems in the background technology.
In order to solve the technical problems, the invention provides the following technical scheme: the high-adhesion high-temperature-resistant glass coating comprises, by weight, 19-21 parts of nanoparticle slurry, 21-27 parts of an epoxy resin compound, 10-15 parts of a water-based polyurethane resin, 9-12 parts of a soybean protein binder, 10-15 parts of an organic solvent, 7-13 parts of a curing agent, 1-3 parts of a wetting agent and 0.7-1 part of a leveling agent.
Furthermore, the epoxy resin compound is mainly prepared by reacting eugenol, epichlorohydrin and tetramethyldisiloxane.
Further, the curing agent is ethylenediamine.
Further, the nanoparticle slurry is a dispersion liquid of the nano ceramic particles and the graphene oxide powder in N, N-dimethylformamide, and the mass ratio of the nano ceramic particles to the graphene oxide powder is 4: 1.
Further, the organic solvent is any one or more of ethyl acetate, butyl acetate and butanone; the wetting agent is alkylaryl polyether alcohol; the leveling agent is an acrylic leveling agent.
A preparation method of high-adhesion high-temperature-resistant glass paint comprises the following steps,
(1) preparing an epoxy resin compound:
(2) and preparing a finished glass coating product.
Further, the preparation method of the high-adhesion high-temperature-resistant glass coating comprises the following steps,
(1) preparing an epoxy resin compound: dissolving eugenol in tetrahydrofuran solvent, adding palladium chloride, stirring uniformly, protecting with nitrogen, dropwise adding tetramethyldisiloxane for reaction, keeping the temperature and aging, removing tetrahydrofuran by rotary evaporation, extracting, and drying with anhydrous magnesium sulfate to obtain tetramethyldisiloxane-eugenol;
uniformly mixing tetramethyldisiloxane-eugenol and tetrabutylammonium bromide, adding epoxy chloropropane, stirring, carrying out nitrogen protection, heating for reaction, extracting by using a sodium chloride solution, and drying by using anhydrous magnesium sulfate to obtain an epoxy resin compound;
(2) preparing a finished glass coating product:
s1, adding a curing agent and dicyclohexylcarbodiimide into nano particle slurry, heating to 50-55 ℃, magnetically stirring, adding a soybean protein binder, and oscillating and dispersing to obtain a phase A;
and S2, mixing and dispersing the epoxy resin compound prepared in the step (1), the waterborne polyurethane resin, the organic solvent, the wetting agent and the flatting agent, adding the phase A, and passing through a gauze to obtain a finished glass coating product.
Further, the preparation method of the high-adhesion high-temperature-resistant glass coating comprises the following steps,
(1) preparing an epoxy resin compound: dissolving eugenol in tetrahydrofuran solvent, adding palladium chloride, stirring uniformly, under the protection of nitrogen, heating to 65-70 ℃, dropwise adding tetramethyldisiloxane, reacting for 1-2h, preserving heat, aging for 12-14h, removing tetrahydrofuran by rotary evaporation, extracting, and drying with anhydrous magnesium sulfate to obtain tetramethyldisiloxane-eugenol;
uniformly mixing tetramethyldisiloxane-eugenol and tetrabutylammonium bromide, adding epoxy chloropropane, stirring, carrying out nitrogen protection, heating to 75-80 ℃, reacting for 4-6h, extracting with a sodium chloride solution, and drying with anhydrous magnesium sulfate to obtain an epoxy resin compound;
(2) preparing a finished glass coating product:
s1, adding a curing agent and dicyclohexylcarbodiimide into nanoparticle slurry, heating to 50-55 ℃, magnetically stirring for 2-3h, adding a soybean protein adhesive, and performing vibration dispersion for 20-30min under the condition that the rotation speed is 800 plus 1000r/min to obtain a phase A;
s2, under the condition that the rotating speed is 500-600r/min, mixing the epoxy resin compound prepared in the step (1), the waterborne polyurethane resin, the organic solvent, the wetting agent and the flatting agent, dispersing for 20-30min, adding the phase A, increasing the rotating speed to 600-800r/min, dispersing for 10-20min, and passing through a gauze to obtain a finished glass coating product.
Further, the mesh number of the gauze in the step (2) is 1000-1200 meshes.
Compared with the prior art, the invention has the following beneficial effects:
1. the invention utilizes natural products of eugenol and epoxy chloropropane to prepare the bio-based epoxy resin to replace petroleum-based epoxy resin, thereby reducing pollution and relieving the shortage of petroleum resources. In order to solve the problem, in the prior art, a mode of blending resin and silane coupling agent is generally adopted, and silane coupling agent is used as bridging for connecting organic and inorganic phases, so that a certain effect is achieved. In order to improve the problem, the invention utilizes the-C ═ C-active double bond on the surface of the eugenol molecule to carry out hydrosilylation reaction with tetramethyldisiloxane, and the eugenol and the tetramethyldisiloxane form a stable molecular structure through the hydrosilylation reaction; on one hand, along with the increase of molecular chains, the mechanical strength and the thermal stability of the resin compound are improved, on the other hand, the stable molecular structure cannot be hindered by other components, the eugenol-epoxy resin in the coating is stably connected with the glass substrate through silicon-oxygen bonds, the adhesive force between the glass substrate and the glass coating is improved, and further, the glass coating is not easy to fall off and has good surface texture.
2. The nano particle slurry is added to improve the high temperature resistance of the glass coating. The nano particle slurry is a dispersion liquid formed by nano ceramic particles and graphene oxide powder in an N, N-dimethylformamide solvent, wherein the mass ratio of the nano ceramic particles to the graphene oxide powder is 4: 1. The nano ceramic particles and the graphene oxide are excellent high-temperature-resistant and high-strength materials, and can be used as a filler to be added into the glass coating, so that the high-temperature resistance of the glass coating can be effectively improved.
3. In the process of preparing a finished glass coating product, firstly, mixing nano particle slurry with a curing agent, and reacting an epoxy group open loop of graphene oxide with a part of curing agent ethylenediamine in the mixing process to form aminated graphene oxide; the oxidized graphene with aminated surface reacts with a large amount of carboxyl on the surface of the soybean protein adhesive molecule to form a compact cross-linked structure in the system, so that the adhesive effect of the soybean protein adhesive is enhanced, the improvement of the adhesive force is beneficial to increasing the adhesive degree of inorganic particles and other components in the glass coating system and the glass substrate, and the strength of the glass coating after curing is improved along with the improvement. Meanwhile, a large amount of hydrophilic group carboxyl on the surface of the soybean protein is consumed by amino on the surface of the graphene oxide, so that the water resistance of the soybean protein adhesive is improved.
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 of the embodiments. All other embodiments, which can be obtained by a person skilled in the art without making any creative effort based on the embodiments in the present invention, belong to the protection scope of the present invention.
Example 1
The high-adhesion high-temperature-resistant glass coating comprises, by weight, 19 parts of nanoparticle slurry, 21 parts of an epoxy resin compound, 10 parts of a waterborne polyurethane resin, 9 parts of a soybean protein binder, 10 parts of an organic solvent, 7 parts of a curing agent, 1 part of a wetting agent and 0.7 part of a leveling agent.
The curing agent is ethylenediamine; the nano particle slurry is a dispersion liquid of nano ceramic particles and graphene oxide powder in N, N-dimethylformamide, and the mass ratio of the nano ceramic particles to the graphene oxide powder is 4: 1.
The organic solvent is one or more of ethyl acetate, butyl acetate and butanone; the wetting agent is alkylaryl polyether alcohol; the leveling agent is an acrylic leveling agent.
A preparation method of high-adhesion high-temperature-resistant glass paint comprises the following steps,
(1) preparing an epoxy resin compound: dissolving eugenol in tetrahydrofuran solvent, adding palladium chloride, stirring uniformly, heating to 65 ℃ under the protection of nitrogen, dropwise adding tetramethyldisiloxane, reacting for 1h, preserving heat and aging for 12h, removing tetrahydrofuran by rotary evaporation, extracting, and drying with anhydrous magnesium sulfate to obtain tetramethyldisiloxane-eugenol;
uniformly mixing tetramethyldisiloxane-eugenol and tetrabutylammonium bromide, adding epoxy chloropropane, stirring, carrying out nitrogen protection, heating to 75 ℃, reacting for 4 hours, extracting by using a sodium chloride solution, and drying by using anhydrous magnesium sulfate to obtain an epoxy resin compound;
(2) preparing a finished glass coating product: s1, taking nano particle slurry, adding a curing agent and dicyclohexylcarbodiimide into the nano particle slurry, heating to 50 ℃, magnetically stirring for 2 hours, adding a soybean protein binder, and oscillating and dispersing for 20 minutes at a rotation speed of 800r/min to obtain a phase A;
s2, under the condition that the rotating speed is 500r/min, mixing the epoxy resin compound prepared in the step (1), the waterborne polyurethane resin, the organic solvent, the wetting agent and the flatting agent, dispersing for 20min, adding the phase A, dispersing for 10min under the condition that the rotating speed is increased to 600r/min, and passing through a screen with 1000 meshes to obtain a finished glass coating.
Example 2
The high-adhesion high-temperature-resistant glass coating comprises, by weight, 20 parts of nanoparticle slurry, 24 parts of an epoxy resin compound, 11 parts of waterborne polyurethane resin, 10 parts of a soybean protein binder, 12 parts of an organic solvent, 9 parts of a curing agent, 2 parts of a wetting agent and 0.9 part of a leveling agent.
The curing agent is ethylenediamine; the nano particle slurry is a dispersion liquid of nano ceramic particles and graphene oxide powder in N, N-dimethylformamide, and the mass ratio of the nano ceramic particles to the graphene oxide powder is 4: 1.
The organic solvent is one or more of ethyl acetate, butyl acetate and butanone; the wetting agent is alkylaryl polyether alcohol; the leveling agent is an acrylic leveling agent.
A preparation method of high-adhesion high-temperature-resistant glass paint comprises the following steps,
(1) preparing an epoxy resin compound: dissolving eugenol in tetrahydrofuran solvent, adding palladium chloride, stirring uniformly, heating to 68 ℃ under the protection of nitrogen, dropwise adding tetramethyldisiloxane, reacting for 1.5h, preserving heat and aging for 13h, removing tetrahydrofuran by rotary evaporation, extracting, and drying with anhydrous magnesium sulfate to obtain tetramethyldisiloxane-eugenol;
uniformly mixing tetramethyldisiloxane-eugenol and tetrabutylammonium bromide, adding epoxy chloropropane, stirring, carrying out nitrogen protection, heating to 77 ℃, reacting for 5 hours, extracting by using a sodium chloride solution, and drying by using anhydrous magnesium sulfate to obtain an epoxy resin compound;
(2) preparing a finished glass coating product: s1, adding a curing agent and dicyclohexylcarbodiimide into nano particle slurry, heating to 53 ℃, magnetically stirring for 2.5 hours, adding a soybean protein binder, and vibrating and dispersing for 250 minutes at the rotation speed of 870r/min to obtain phase A;
s2, under the condition that the rotating speed is 570r/min, mixing the epoxy resin compound prepared in the step (1), the waterborne polyurethane resin, the organic solvent, the wetting agent and the flatting agent, dispersing for 25min, adding the phase A, dispersing for 15min under the condition that the rotating speed is increased to 700r/min, and passing through a screen with 1000 meshes to obtain a finished glass coating.
Example 3
The high-adhesion high-temperature-resistant glass coating comprises, by weight, 21 parts of nanoparticle slurry, 27 parts of an epoxy resin compound, 15 parts of a waterborne polyurethane resin, 12 parts of a soybean protein binder, 15 parts of an organic solvent, 13 parts of a curing agent, 3 parts of a wetting agent and 1 part of a leveling agent.
The curing agent is ethylenediamine; the nano particle slurry is a dispersion liquid of nano ceramic particles and graphene oxide powder in N, N-dimethylformamide, and the mass ratio of the nano ceramic particles to the graphene oxide powder is 4: 1.
The organic solvent is one or more of ethyl acetate, butyl acetate and butanone; the wetting agent is alkylaryl polyether alcohol; the leveling agent is an acrylic leveling agent.
A preparation method of high-adhesion high-temperature-resistant glass paint comprises the following steps,
(1) preparing an epoxy resin compound: dissolving eugenol in tetrahydrofuran solvent, adding palladium chloride, stirring uniformly, heating to 70 ℃ under the protection of nitrogen, dropwise adding tetramethyldisiloxane, reacting for 2 hours, preserving heat and aging for 14 hours, removing tetrahydrofuran by rotary evaporation, extracting, and drying with anhydrous magnesium sulfate to obtain tetramethyldisiloxane-eugenol;
uniformly mixing tetramethyldisiloxane-eugenol and tetrabutylammonium bromide, adding epoxy chloropropane, stirring, carrying out nitrogen protection, heating to 80 ℃, reacting for 6 hours, extracting with a sodium chloride solution, and drying with anhydrous magnesium sulfate to obtain an epoxy resin compound;
(2) preparing a finished glass coating product: s1, adding a curing agent and dicyclohexylcarbodiimide into nano particle slurry, heating to 55 ℃, magnetically stirring for 3 hours, adding a soybean protein binder, and vibrating and dispersing for 20-30 minutes at the rotation speed of 1000r/min to obtain a phase A;
s2, under the condition that the rotating speed is 600r/min, mixing the epoxy resin compound prepared in the step (1), the waterborne polyurethane resin, the organic solvent, the wetting agent and the flatting agent, dispersing for 20-30min, adding the phase A, increasing the rotating speed to 800r/min, dispersing for 20min, and passing through a 1000-mesh 1200-mesh gauze to obtain a glass coating finished product.
Comparative example 1
The high-adhesion high-temperature-resistant glass coating comprises, by weight, 20 parts of nanoparticle slurry, 24 parts of an epoxy resin compound, 11 parts of waterborne polyurethane resin, 10 parts of a soybean protein binder, 12 parts of an organic solvent, 9 parts of a curing agent, 2 parts of a wetting agent and 0.9 part of a leveling agent.
The curing agent is ethylenediamine; the nano particle slurry is a dispersion liquid of nano ceramic particles and graphene oxide powder in N, N-dimethylformamide, and the mass ratio of the nano ceramic particles to the graphene oxide powder is 4: 1.
The organic solvent is one or more of ethyl acetate, butyl acetate and butanone; the wetting agent is alkylaryl polyether alcohol; the leveling agent is an acrylic leveling agent.
A preparation method of high-adhesion high-temperature-resistant glass paint comprises the following steps,
(1) preparing an epoxy resin compound: dissolving eugenol in tetrahydrofuran solvent, adding tetrabutylammonium bromide, mixing uniformly, adding epoxy chloropropane, stirring, protecting with nitrogen, heating to 77 ℃, reacting for 5 hours, extracting with sodium chloride solution, drying with anhydrous magnesium sulfate, adding silane coupling agent, and mixing to obtain epoxy resin compound;
(2) preparing a finished glass coating product: s1, adding a curing agent and dicyclohexylcarbodiimide into nano particle slurry, heating to 53 ℃, magnetically stirring for 2.5 hours, adding a soybean protein binder, and vibrating and dispersing for 250 minutes at the rotation speed of 870r/min to obtain phase A;
s2, under the condition that the rotating speed is 570r/min, mixing the epoxy resin compound prepared in the step (1), the waterborne polyurethane resin, the organic solvent, the wetting agent and the flatting agent, dispersing for 25min, adding the phase A, dispersing for 15min under the condition that the rotating speed is increased to 700r/min, and passing through a 1000-mesh gauze to obtain a glass coating finished product.
In the preparation of the epoxy resin mixture, tetramethyldisiloxane was not added, and the rest was the same as in example 2.
Comparative example 2
The high-adhesion high-temperature-resistant glass coating comprises, by weight, 20 parts of nanoparticle slurry, 24 parts of an epoxy resin compound, 11 parts of a waterborne polyurethane resin, 10 parts of a soybean protein binder, 12 parts of an organic solvent, 9 parts of a curing agent, 2 parts of a wetting agent and 0.9 part of a leveling agent.
The curing agent is ethylenediamine; the nano particle slurry is a dispersion liquid of nano ceramic particles and graphene oxide powder in N, N-dimethylformamide, and the mass ratio of the nano ceramic particles to the graphene oxide powder is 4: 1.
The organic solvent is one or more of ethyl acetate, butyl acetate and butanone; the wetting agent is alkylaryl polyether alcohol; the leveling agent is an acrylic leveling agent.
A preparation method of high-adhesion high-temperature-resistant glass paint comprises the following steps,
(1) preparing an epoxy resin compound: dissolving eugenol in tetrahydrofuran solvent, adding palladium chloride, stirring uniformly, heating to 68 ℃ under the protection of nitrogen, dropwise adding tetramethyldisiloxane, reacting for 1.5h, preserving heat and aging for 13h, removing tetrahydrofuran by rotary evaporation, extracting, and drying with anhydrous magnesium sulfate to obtain tetramethyldisiloxane-eugenol;
uniformly mixing tetramethyldisiloxane-eugenol and tetrabutylammonium bromide, adding epoxy chloropropane, stirring, carrying out nitrogen protection, heating to 77 ℃, reacting for 5 hours, extracting by using a sodium chloride solution, and drying by using anhydrous magnesium sulfate to obtain an epoxy resin compound;
(2) preparing a finished glass coating product:
and (2) mixing the epoxy resin compound prepared in the step (1), the nanoparticle slurry, the waterborne polyurethane resin, the soybean protein binder, the organic solvent, the wetting agent and the flatting agent at the rotating speed of 570r/min, dispersing for 25min, adding the phase A, adding the curing agent at the rotating speed of 700r/min, dispersing for 15min, and screening by a screen of 1000 meshes to obtain a finished glass coating.
When the glass coating is prepared, the soy protein binder is directly mixed with the epoxy resin compound, the nanoparticle slurry, the aqueous polyurethane resin, the organic solvent, the wetting agent and the leveling agent, and the rest is the same as that in the example 2.
Examples of effects
Taking 5 pieces of common plate glass with the same size and material, sequentially washing the common plate glass with ethanol, acetone and deionized water, and drying; the glass coatings prepared in examples 1-3 and comparative examples 1-2 were coated on the surfaces of 5 pieces of ordinary flat glass respectively at a coating amount of 20g/m2, and the glass surfaces were cured at 60 ℃ for 12-14h after the coating. Performing performance test on the coating formed by curing, measuring the adhesive force according to the regulation of GB/T1720-1988 paint film adhesive force measuring method, and testing by using a cross-cut method; according to GB/T6739-2006 color paints and varnishes: the pencil method is used for measuring the specified detection strength of paint film hardness; the test results are shown in table 1;
appearance of the coating Grade of adhesion Hardness of pencil 250 ℃/24h, film change Water resistance 30D
Example 1 Smooth, non-sagging and bright 1 2H Without change Without change
Example 2 Smooth, non-sagging and bright 0 3H Without change Without change
Example 3 Smooth, non-sagging and bright 0 3H Without change Without change
Comparative example 1 Smooth, non-sagging and bright 2 1H Cracks and bubbles appear Without change
Comparative example 2 Smooth, non-sagging and bright 2 1H Occurrence of cracks Bubbling occurs
TABLE 1
As can be seen from the data in Table 1, the glass coatings prepared in examples 1-3 have adhesion to glass substrates of 0 grade and 1 grade, and have strong adhesion to the substrates. In comparative example 1, the bio-based epoxy resin is not reacted with siloxane, but modified in a blending way, and compared with example 2, the adhesion of the final glass coating to the glass substrate is reduced to a certain extent. In comparative example 2, the soybean protein binder alone did not have a large amount of amino groups and carboxyl groups combined in the system, and the water resistance and adhesion were reduced and the water resistance was also deteriorated as compared with example 2.
Finally, it should be noted that: 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 changes may be made in the embodiments and/or equivalents thereof without departing from the spirit and scope of the invention. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.

Claims (4)

1. The high-adhesion high-temperature-resistant glass coating is characterized by comprising a base; the glass coating comprises the following raw materials, by weight, 19-21 parts of nanoparticle slurry, 21-27 parts of an epoxy resin compound, 10-15 parts of a waterborne polyurethane resin, 9-12 parts of a soybean protein binder, 10-15 parts of an organic solvent, 7-13 parts of a curing agent, 1-3 parts of a wetting agent and 0.7-1 part of a leveling agent;
the nano particle slurry is a dispersion liquid of nano ceramic particles and graphene oxide powder in N, N-dimethylformamide, and the mass ratio of the nano ceramic particles to the graphene oxide powder is 4: 1;
the preparation method comprises the following steps:
(1) preparing an epoxy resin compound: dissolving eugenol in tetrahydrofuran solvent, adding palladium chloride, stirring uniformly, protecting with nitrogen, dropwise adding tetramethyldisiloxane for reaction, keeping the temperature and aging, removing tetrahydrofuran by rotary evaporation, extracting, and drying with anhydrous magnesium sulfate to obtain tetramethyldisiloxane-eugenol;
uniformly mixing tetramethyldisiloxane-eugenol and tetrabutylammonium bromide, adding epoxy chloropropane, stirring, carrying out nitrogen protection, heating for reaction, extracting by using a sodium chloride solution, and drying by using anhydrous magnesium sulfate to obtain an epoxy resin compound;
(2) preparing a finished glass coating product:
s1, adding a curing agent and dicyclohexylcarbodiimide into nano particle slurry, heating to 50-55 ℃, magnetically stirring, adding a soybean protein binder, and oscillating and dispersing to obtain a phase A;
s2, mixing and dispersing the epoxy resin compound prepared in the step (1), the waterborne polyurethane resin, the organic solvent, the wetting agent and the flatting agent, adding the phase A, and passing through a gauze to obtain a finished glass coating;
the curing agent is ethylenediamine.
2. The high-adhesion high-temperature-resistant glass coating as claimed in claim 1, wherein: the organic solvent is any one or more of ethyl acetate, butyl acetate and butanone; the wetting agent is alkylaryl polyether alcohol; the leveling agent is an acrylic leveling agent.
3. The high-adhesion high-temperature-resistant glass coating as claimed in claim 1, wherein: comprises the following steps of (a) carrying out,
(1) preparing an epoxy resin compound: dissolving eugenol in tetrahydrofuran solvent, adding palladium chloride, stirring uniformly, heating to 65-70 ℃ under the protection of nitrogen, dropwise adding tetramethyldisiloxane, reacting for 1-2h, keeping the temperature and aging for 12-14h, removing tetrahydrofuran by rotary evaporation, extracting, and drying with anhydrous magnesium sulfate to obtain tetramethyldisiloxane-eugenol;
uniformly mixing tetramethyldisiloxane-eugenol and tetrabutylammonium bromide, adding epoxy chloropropane, stirring, reacting for 4-6h under the protection of nitrogen, heating to 75-80 ℃, extracting by using a sodium chloride solution, and drying by using anhydrous magnesium sulfate to obtain an epoxy resin compound;
(2) preparing a finished glass coating product:
s1, adding a curing agent and dicyclohexylcarbodiimide into nano particle slurry, heating to 50-55 ℃, magnetically stirring for 2-3h, adding a soybean protein adhesive, and performing vibration dispersion for 20-30min at the rotation speed of 800-;
s2, under the condition that the rotating speed is 500-600r/min, mixing the epoxy resin compound prepared in the step (1), the waterborne polyurethane resin, the organic solvent, the wetting agent and the flatting agent, dispersing for 20-30min, adding the phase A, increasing the rotating speed to 600-800r/min, dispersing for 10-20min, and passing through a gauze to obtain a finished glass coating.
4. The high-adhesion high-temperature-resistant glass coating as claimed in claim 1, wherein: the mesh number of the gauze in the step (2) is 1000-1200 meshes.
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