CN112011249B - High-strength flame-retardant water-based epoxy resin coating and preparation method thereof - Google Patents
High-strength flame-retardant water-based epoxy resin coating and preparation method thereof Download PDFInfo
- Publication number
- CN112011249B CN112011249B CN202010825274.XA CN202010825274A CN112011249B CN 112011249 B CN112011249 B CN 112011249B CN 202010825274 A CN202010825274 A CN 202010825274A CN 112011249 B CN112011249 B CN 112011249B
- Authority
- CN
- China
- Prior art keywords
- epoxy resin
- solvent
- solution
- hybrid material
- polyvinyl alcohol
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D163/00—Coating compositions based on epoxy resins; Coating compositions based on derivatives of epoxy resins
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/18—Fireproof paints including high temperature resistant paints
-
- 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
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/60—Additives non-macromolecular
- C09D7/61—Additives non-macromolecular inorganic
- C09D7/62—Additives non-macromolecular inorganic modified by treatment with other compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2289—Oxides; Hydroxides of metals of cobalt
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2293—Oxides; Hydroxides of metals of nickel
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/011—Nanostructured additives
Landscapes
- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Carbon And Carbon Compounds (AREA)
Abstract
The invention relates to the technical field of epoxy resin materials, and discloses a high-strength flame-retardant water-based epoxy resin coating which comprises the following formula raw materials: Co-Ni-based carbon hybrid material, silane coupling agent, polyvinyl alcohol-glycine block copolymer, bisphenol A epoxy resin and curing agent. According to the high-strength flame-retardant water-based epoxy resin coating, the carbon microspheres grow on the surfaces of the carbon nanotubes in situ, and the carbon microspheres adsorb Co2+And Ni2+The Co-Ni-based carbon hybrid material with urea generates nickel-cobalt basic carbonate to form a Co-Ni-based carbon hybrid material with high thermal conductivity and thermal conductivity coefficient, so that the thermal conductivity of the epoxy resin is improved, the nickel-cobalt basic carbonate forms CoO and NiO at high temperature during combustion, the carbonization and dehydrogenation reaction of the epoxy resin can be promoted at high temperature to form a compact coke layer, the conduction of combustion heat and the permeation of oxygen are hindered, the cross-linking degree of the epoxy resin is improved by the polyvinyl alcohol-glycine block copolymer, and the tensile strength and the breaking strength of the epoxy resin are enhanced.
Description
Technical Field
The invention relates to the technical field of epoxy resin materials, in particular to a high-strength flame-retardant water-based epoxy resin coating and a preparation method thereof.
Background
The epoxy resin is a high molecular polymer, the molecule of the epoxy resin contains more than two epoxy groups, the epoxy resin is a thermosetting resin, the epoxy groups have good chemical activity, and a compound containing active hydrogen can perform a ring-opening reaction with the epoxy resin to generate a network structure through curing and crosslinking, wherein the bisphenol A epoxy resin has the largest yield and the most complete variety, new modified varieties are continuously increased, and the finished product of the epoxy resin has good physical and mechanical properties, electrical insulation properties and chemical resistance, and has wide application in the fields of coatings, adhesives, electronic casting, encapsulation and the like.
However, the heat conductivity coefficient of the existing epoxy resin is low, the heat resistance of the material is poor, so that the mechanical properties such as toughness, strength and the like of the epoxy resin product at high temperature are seriously affected, the flame retardance of the epoxy resin is poor, and the practicability and the application range of the epoxy resin are greatly reduced.
Technical problem to be solved
Aiming at the defects of the prior art, the invention provides a high-strength flame-retardant water-based epoxy resin coating and a preparation method thereof, and solves the problem that the epoxy resin has poor heat resistance and flame retardance.
(II) technical scheme
In order to achieve the purpose, the invention provides the following technical scheme: the high-strength flame-retardant waterborne epoxy resin coating comprises the following formula raw materials in parts by weight: 4.5-9 parts of Co-Ni-based carbon hybrid material, 0.5-1 part of silane coupling agent, 18-27 parts of polyvinyl alcohol-glycine block copolymer, 60-76 parts of bisphenol A epoxy resin and 1-3 parts of curing agent.
Preferably, the silane coupling agent is 3- (2, 3-glycidoxy) propyltriethoxysilane.
Preferably, the preparation method of the Co-Ni-based carbon hybrid material comprises the following steps:
(1) adding distilled water solvent, glucose and hydroxylated carbon nano tubes into a reaction bottle, uniformly stirring, placing the reaction bottle into an ultrasonic dispersion instrument, carrying out ultrasonic dispersion treatment for 1-2h at 50-70 ℃, transferring the solution into a hydrothermal synthesis reaction kettle, placing the reaction kettle in a reaction kettle heating box, heating to 200-220 ℃, reacting for 2-3h, placing the reaction bottle in a vacuum drying box to remove the solvent, washing the solid product with distilled water, and preparing the carbon microsphere loaded carbon nano tube.
(2) Adding carbon nano tubes loaded by carbon microspheres into distilled water, adding phosphoric acid, stirring at a constant speed at 50-60 ℃ for pre-activation for 20-25h, removing the solvent from the solution through vacuum drying, placing the solid mixture into an atmosphere resistance furnace, introducing N2, heating at a rate of 3-5 ℃/min, carrying out heat preservation and calcination for 2-3h at the temperature of 550-580 ℃, washing the calcination product with distilled water, and fully drying to prepare the activated carbon microspheres.
(3) Adding distilled water solvent, activated carbon microspheres and CoCl into a reaction bottle2、NiCl2Placing a reaction bottle in an ultrasonic dispersion instrument, performing ultrasonic dispersion treatment at 40-50 ℃ for 30-50min, transferring the solution to a ball mill for ball milling for 5-8h until the material passes through a 800-mesh sieve with 1000 meshes, adding urea into the reaction bottle, placing the reaction bottle in an oil bath pot, heating to 100-mesh sieve, stirring at constant speed for reflux reaction for 6-8h, removing the solvent from the solution through vacuum drying, washing the solid product with distilled water, and preparing the Co-Ni-based carbon hybrid materialAnd (5) feeding.
Preferably, the mass ratio of the glucose to the hydroxylated carbon nanotube is 4-7: 1.
Preferably, the mass ratio of the carbon microsphere-loaded carbon nanotube to the phosphoric acid is 1: 1.2-1.5.
Preferably, the activated carbon microspheres, CoCl2、NiCl2And urea, wherein the mass ratio of the urea to the urea is 1:1.3-1.5:2.7-3.2: 6.5-8.7.
Preferably, the oil bath pot includes the base, and the front of base is provided with the control cabinet, and the bath has been seted up at the top of base, and the apron has been placed at the top of bath, and the back fixedly connected with chassis of base, the top activity of chassis are pegged graft and are had the montant, and the horizontal cover has been cup jointed, two in the outside of montant swing joint has the pin between the horizontal cover, and vertical cover has been cup jointed in the outside of pin, and the front of vertical cover is pegged graft and is had the extension rod, the front fixedly connected with lantern ring of extension rod, the inside fixedly connected with spring of the lantern ring, the spring keep away from the lantern ring one end fixedly connected with clamp splice that carries on the back mutually.
Preferably, the preparation method of the polyvinyl alcohol-glycine block copolymer comprises the following steps:
(1) adding an N, N-dimethylformamide solvent, polyvinyl alcohol and glycine into a reaction bottle, stirring at a constant speed until the N, N-dimethylformamide solvent, the polyvinyl alcohol and the glycine are dissolved, adding sulfuric acid to adjust the pH value of the solution to 2-3, placing the reaction bottle in an oil bath pot, heating to 135 ℃ plus materials, stirring at a constant speed for reaction for 20-25 hours, cooling the solution in an ice water bath, adding an acetone solvent until a large amount of precipitate is generated, adding the acetone solvent into the precipitate, placing the precipitate in a dialysis bag to remove impurities, and purifying and drying to obtain a solid product, namely the polyvinyl alcohol-glycine block copolymer.
Preferably, the mass ratio of the polyvinyl alcohol to the glycine is 1: 2.8-3.3.
Preferably, the preparation method of the high-strength flame-retardant water-based epoxy resin coating comprises the following steps:
(1) adding ethanol solvent, 4.5-9 parts of Co-Ni-based carbon hybrid material and 0.5-1 part of silane coupling agent 3- (2, 3-epoxypropoxy) propyltriethoxysilane into a reaction bottle, placing the reaction bottle into an ultrasonic dispersion instrument, carrying out ultrasonic dispersion treatment for 1-2h at 40-50 ℃, placing the reaction bottle into a constant-temperature water bath kettle, heating to 70-80 ℃, carrying out uniform stirring reflux reaction for 10-15h, carrying out reduced pressure concentration on the solution to remove the solvent, washing the solid product with distilled water, and fully drying to prepare the 3- (2, 3-epoxypropoxy) propyltriethoxysilane grafted modified Co-Ni-based carbon hybrid material.
(2) Adding distilled water solvent, 18-27 parts of polyvinyl alcohol-glycine block copolymer and modified Co-Ni-based carbon hybrid material into a reaction bottle, uniformly stirring, transferring the solution into a hydrothermal synthesis reaction kettle, placing the kettle in a reaction kettle heating box, heating to 100 ℃ and 120 ℃, reacting for 8-12h, cooling the solution to room temperature, and removing the solvent through reduced pressure distillation to prepare the Co-Ni-based carbon hybrid material coated by the polyvinyl alcohol-glycine block copolymer.
(3) Adding 1, 4-dioxane solvent, 60-76 parts of bisphenol A epoxy resin and a Co-Ni-based carbon hybrid material coated by a polyvinyl alcohol-glycine block copolymer into a reaction bottle, placing the reaction bottle into an oil bath pot, heating to 120 ℃ and 130 ℃, stirring at a constant speed for reaction for 4-6h, decompressing and concentrating the solution to remove the solvent, adding distilled water solvent and 1-3 parts of curing agent into the concentrated product, controlling the solid-to-liquid ratio to be 70-85%, and stirring at a constant speed to obtain the high-strength flame-retardant waterborne epoxy resin coating.
(III) advantageous technical effects
Compared with the prior art, the invention has the following beneficial technical effects:
according to the high-strength flame-retardant water-based epoxy resin coating, the carbon nano tube has excellent heat conduction performance and large specific surface area, the carbon microspheres prepared by using a hot solvent method grow on the surface and the inner wall of the carbon nano tube in situ, so that the carbon microspheres are uniformly dispersed, the agglomeration and caking phenomena are reduced, and the formed uniformly-dispersed carbon microspheres well adsorb Co2+And Ni2+The carbon microsphere and urea generate nickel-cobalt basic carbonate on the surface of the carbon microsphere to form a Co-Ni-based carbon hybrid material, so that the Co-Ni-based carbon hybrid material has high thermal conductivity and coefficient of thermal conductivity, the conduction rate of heat in epoxy resin is increased, and local heat aggregation is reduced, thereby improving the thermal conductivity of the epoxy resin and avoiding the epoxy resin materialThe toughness and strength are affected at high temperature.
According to the high-strength flame-retardant water-based epoxy resin coating, the nickel-cobalt basic carbonate in the Co-Ni-based carbon hybrid material can absorb heat at high temperature during combustion to dehydrate water and carbon dioxide to form metal oxides CoO and NiO, the NiO and CoO can promote dehydrogenation reaction of epoxy resin at high temperature to enable the epoxy resin to form a compact coke layer, the carbon residue rate during combustion of the epoxy resin is improved, conduction of combustion heat and permeation of oxygen are hindered, continuous and dense expanded carbon is formed during combustion of the carbon-based material in the Co-Ni-based carbon hybrid material, a closed protective layer carbide is generated in the epoxy resin in an aggregation mode, a good smoke suppression effect is achieved, and the epoxy resin coating achieves a good flame-retardant effect.
In the high-strength flame-retardant water-based epoxy resin coating, hydroxyl in a carbon nano tube is bonded by silane coupling agent 3- (2, 3-epoxypropoxy) propyltriethoxysilane, so that a polyvinyl alcohol-glycine block copolymer well coats a Co-Ni-based carbon hybrid material, the polyvinyl alcohol-glycine block copolymer and epoxy resin are physically blended and crosslinked to form a copolymer, the dispersity and compatibility of the Co-Ni-based carbon hybrid material in the epoxy resin are improved, the flame retardant property of the Co-Ni-based carbon hybrid material is enhanced, meanwhile, the crosslinking degree of the epoxy resin is improved by the polyvinyl alcohol-glycine block copolymer, the mechanical properties such as tensile strength, breaking strength and the like of the epoxy resin are enhanced, and meanwhile, a large amount of hydrophilic hydroxyl and amino in the polyvinyl alcohol-glycine block copolymer endow the epoxy resin with hydrophilic property, thereby preparing the water-based epoxy resin coating.
Drawings
FIG. 1 is a front view of the connection structure of the present invention;
FIG. 2 is a partial enlarged view of the connection structure of the present invention;
FIG. 3 is a top view of the connection structure of the present invention;
FIG. 4 is an enlarged view of the collar of the connection structure of the present invention;
fig. 5 is a top exploded view of the connection structure of the present invention.
In the figure: 1-base, 2-console, 3-bath, 4-cover plate, 5-base frame, 6-vertical rod, 7-horizontal sleeve, 8-horizontal rod, 9-vertical sleeve, 10-extension rod, 11-lantern ring, 12-spring, 13-clamp block.
Detailed Description
To achieve the above object, the present invention provides the following embodiments and examples: the high-strength flame-retardant waterborne epoxy resin coating comprises the following formula raw materials in parts by weight: 4.5-9 parts of Co-Ni-based carbon hybrid material, 0.5-1 part of silane coupling agent, 18-27 parts of polyvinyl alcohol-glycine block copolymer, 60-76 parts of bisphenol A epoxy resin and 1-3 parts of curing agent, wherein the silane coupling agent is 3- (2, 3-epoxypropoxy) propyltriethoxysilane.
The preparation method of the Co-Ni-based carbon hybrid material comprises the following steps:
(1) adding distilled water solvent, glucose and hydroxylated carbon nano tubes into a reaction bottle in a mass ratio of 4-7:1, uniformly stirring, placing the reaction bottle into an ultrasonic dispersion instrument, carrying out ultrasonic dispersion treatment at 50-70 ℃ for 1-2h, transferring the solution into a hydrothermal synthesis reaction kettle, placing the reaction kettle in a reaction kettle heating box, heating to 200-220 ℃, reacting for 2-3h, placing the reaction bottle in a vacuum drying box to remove the solvent, and washing the solid product with distilled water to prepare the carbon microsphere loaded carbon nano tube.
(2) Adding carbon microsphere loaded carbon nano tubes into distilled water, adding phosphoric acid, stirring at a constant speed at 50-60 ℃ for pre-activation for 20-25h, removing the solvent from the solution by vacuum drying, placing the solid mixture into an atmosphere resistance furnace, introducing N2, heating at a rate of 3-5 ℃/min, carrying out heat preservation and calcination at 550-580 ℃ for 2-3h, washing the calcination product with distilled water, and fully drying to prepare the activated carbon microspheres.
(3) Adding distilled water solvent, activated carbon microspheres and CoCl into a reaction bottle2、NiCl2Placing a reaction bottle in an ultrasonic dispersion instrument, carrying out ultrasonic dispersion treatment at 40-50 ℃ for 30-50min, transferring the solution to a star ball mill for ball milling for 5-8h until the material passes through a 800-plus-1000-mesh sieve, and adding urea into the reaction bottle, wherein activated carbon microspheres and CoCl2、NiCl2And urea, IVThe mass ratio of 1:1.3-1.5:2.7-3.2:6.5-8.7, and the oil bath pot comprises a base, a control console is arranged on the front side of the base, a bath groove is formed in the top of the base, a cover plate is arranged on the top of the bath groove, an underframe is fixedly connected to the back of the base, a vertical rod is movably inserted into the top of the underframe, a horizontal sleeve is sleeved on the outer side of the vertical rod, a flat rod is movably connected between the two horizontal sleeves, a vertical sleeve is sleeved on the outer side of the flat rod, an extension rod is inserted into the front of the vertical sleeve, a lantern ring is fixedly connected to the front of the extension rod, a spring is fixedly connected to the inner part of the lantern ring, a clamping block is fixedly connected to one end, far away from the opposite side of the lantern ring, of the spring, the spring is heated to 110 ℃, stirring reflux reaction is carried out for 6-8 hours, the solution is subjected to vacuum drying to remove a solvent, a solid product is washed by distilled water, and the Co-Ni-based carbon hybrid material is prepared.
The preparation method of the polyvinyl alcohol-glycine block copolymer comprises the following steps:
(1) adding an N, N-dimethylformamide solvent, polyvinyl alcohol and glycine into a reaction bottle in a mass ratio of 1:2.8-3.3, stirring at a constant speed until the N, N-dimethylformamide solvent, the polyvinyl alcohol and the glycine are dissolved, adding sulfuric acid to adjust the pH value of the solution to 2-3, placing the reaction bottle into an oil bath pot, heating to 135 ℃ and 145 ℃, stirring at a constant speed for reaction for 20-25 hours, cooling the solution in an ice water bath, adding an acetone solvent until a large amount of precipitate is generated, adding the acetone solvent into the precipitate, placing the precipitate into a dialysis bag to remove impurities, and purifying and drying to obtain a solid product, namely the polyvinyl alcohol-glycine block copolymer.
The preparation method of the high-strength flame-retardant waterborne epoxy resin coating comprises the following steps:
(1) adding ethanol solvent, 4.5-9 parts of Co-Ni-based carbon hybrid material and 0.5-1 part of silane coupling agent 3- (2, 3-epoxypropoxy) propyltriethoxysilane into a reaction bottle, placing the reaction bottle into an ultrasonic dispersion instrument, carrying out ultrasonic dispersion treatment for 1-2h at 40-50 ℃, placing the reaction bottle into a constant-temperature water bath kettle, heating to 70-80 ℃, carrying out uniform stirring reflux reaction for 10-15h, carrying out reduced pressure concentration on the solution to remove the solvent, washing the solid product with distilled water, and fully drying to prepare the 3- (2, 3-epoxypropoxy) propyltriethoxysilane grafted modified Co-Ni-based carbon hybrid material.
(2) Adding distilled water solvent, 18-27 parts of polyvinyl alcohol-glycine block copolymer and modified Co-Ni-based carbon hybrid material into a reaction bottle, uniformly stirring, transferring the solution into a hydrothermal synthesis reaction kettle, placing the kettle in a reaction kettle heating box, heating to 100 ℃ and 120 ℃, reacting for 8-12h, cooling the solution to room temperature, and removing the solvent through reduced pressure distillation to prepare the Co-Ni-based carbon hybrid material coated by the polyvinyl alcohol-glycine block copolymer.
(3) Adding 1, 4-dioxane solvent, 60-76 parts of bisphenol A epoxy resin and a Co-Ni-based carbon hybrid material coated by a polyvinyl alcohol-glycine block copolymer into a reaction bottle, placing the reaction bottle into an oil bath pot, heating to 120 ℃ and 130 ℃, stirring at a constant speed for reaction for 4-6h, decompressing and concentrating the solution to remove the solvent, adding distilled water solvent and 1-3 parts of curing agent into the concentrated product, controlling the solid-to-liquid ratio to be 70-85%, and stirring at a constant speed to obtain the high-strength flame-retardant waterborne epoxy resin coating.
Example 1
(1) Adding distilled water solvent, glucose and hydroxylated carbon nano tubes into a reaction bottle according to the mass ratio of 4:1, uniformly stirring, placing the reaction bottle into an ultrasonic dispersion instrument, carrying out ultrasonic dispersion treatment at 50 ℃ for 1h, transferring the solution into a hydrothermal synthesis reaction kettle, placing the reaction kettle in a reaction kettle heating box, heating to 200 ℃, reacting for 2h, placing the reaction bottle in a vacuum drying box to remove the solvent, washing the solid product with distilled water, and preparing the carbon microsphere loaded carbon nano tube component 1.
(2) Preparation of activated carbon microsphere component 1: adding the carbon microsphere loaded carbon nanotube component 1 into distilled water, adding phosphoric acid, stirring at a constant speed at 50 ℃ for preactivation for 20h, drying the solution in vacuum to remove the solvent, placing the solid mixture into an atmosphere resistance furnace, introducing N2, heating at a rate of 3 ℃/min, carrying out heat preservation and calcination for 2h at 550 ℃, washing the calcined product with distilled water, and fully drying to obtain the activated carbon microsphere component 1, wherein the mass ratio of the carbon microsphere loaded carbon nanotube component 1 to the phosphoric acid is 1: 1.2.
(3) Preparation of Co-Ni-based carbon hybrid Material 1: adding distilled water solvent, activated carbon microsphere component 1 and CoCl into a reaction bottle2、NiCl2Placing the reaction bottle in a super-high positionPerforming ultrasonic dispersion treatment at 40 deg.C for 30min in a sound dispersion instrument, transferring the solution, ball milling in a ball mill for 5 hr until the material passes through 800 mesh sieve, and adding urea into a reaction bottle, wherein the activated carbon microsphere component 1 and CoCl2、NiCl2And urea, the mass ratio of the four components is 1:1.3:2.7:6.5, the mixture is placed in an oil bath pot, the oil bath pot comprises a base, a control console is arranged on the front side of the base, a bath is arranged on the top of the base, a cover plate is placed on the top of the bath, a bottom frame is fixedly connected to the back side of the base, a vertical rod is movably inserted into the top of the bottom frame, a horizontal sleeve is sleeved on the outer side of the vertical rod, a flat rod is movably connected between the two horizontal sleeves, a vertical sleeve is sleeved on the outer side of the flat rod, an extension rod is inserted into the front side of the vertical sleeve, a lantern ring is fixedly connected to the front side of the extension rod, a spring is fixedly connected to the inner part of the lantern ring, a clamp block is fixedly connected to one end, away from the opposite side of the lantern ring, the spring is heated to 100 ℃, stirring and refluxing reaction is carried out at a constant speed for 6 hours, the solution is subjected to vacuum drying to removal of solvent, and the solid product is washed by distilled water, so as to prepare the Co-Ni-based carbon hybrid material 1.
(4) Modified Co-Ni-based carbon hybrid material 1: adding ethanol solvent, 4.5 parts of Co-Ni-based carbon hybrid material 1 and 0.5 part of silane coupling agent 3- (2, 3-epoxypropoxy) propyltriethoxysilane into a reaction bottle, placing the reaction bottle into an ultrasonic dispersion instrument, carrying out ultrasonic dispersion treatment for 1h at 40 ℃, placing the reaction bottle into a constant-temperature water bath kettle, heating to 70 ℃, stirring at a constant speed for reflux reaction for 10h, carrying out reduced pressure concentration on the solution to remove the solvent, washing a solid product with distilled water, and fully drying to prepare the 3- (2, 3-epoxypropoxy) propyltriethoxysilane grafted modified Co-Ni-based carbon hybrid material 1.
(5) Preparation of polyvinyl alcohol-glycine block copolymer component 1: adding an N, N-dimethylformamide solvent, polyvinyl alcohol and glycine into a reaction bottle at a mass ratio of 1:2.8, stirring at a constant speed until the two are dissolved, adding sulfuric acid to adjust the pH value of the solution to 3, placing the reaction bottle in an oil bath pot, heating to 135 ℃, stirring at a constant speed for reaction for 20 hours, cooling the solution in an ice water bath, adding an acetone solvent until a large amount of precipitate is generated, adding the precipitate into an acetone solvent, placing the precipitate in a dialysis bag to remove impurities, purifying and drying to obtain a solid product, namely the polyvinyl alcohol-glycine block copolymer component 1.
(6) Preparing a polyvinyl alcohol-glycine block copolymer coated Co-Ni-based carbon hybrid material 1: adding a distilled water solvent, 18 parts of a polyvinyl alcohol-glycine block copolymer component 1 and the modified Co-Ni-based carbon hybrid material 1 into a reaction bottle, uniformly stirring, transferring the solution into a hydrothermal synthesis reaction kettle, placing the kettle in a reaction kettle heating box, heating to 100 ℃, reacting for 8 hours, cooling the solution to room temperature, and removing the solvent through reduced pressure distillation to prepare the Co-Ni-based carbon hybrid material 1 coated with the polyvinyl alcohol-glycine block copolymer.
(7) Preparation of high-strength flame-retardant waterborne epoxy resin coating 1: adding a 1, 4-dioxane solvent, 76 parts of bisphenol A epoxy resin and a polyvinyl alcohol-glycine block copolymer coated Co-Ni-based carbon hybrid material 1 into a reaction bottle, placing the reaction bottle into an oil bath pot, heating to 120 ℃, stirring at a constant speed for 4 hours to react, concentrating the solution under reduced pressure to remove the solvent, adding a distilled water solvent and 1 part of a curing agent into the concentrated product, controlling the solid-to-liquid ratio to be 70%, and stirring at a constant speed to obtain the high-strength flame-retardant waterborne epoxy resin coating 1.
Example 2
(1) Adding distilled water solvent, glucose and hydroxylated carbon nano tubes into a reaction bottle according to the mass ratio of 4:1, uniformly stirring, placing the reaction bottle into an ultrasonic dispersion instrument, carrying out ultrasonic dispersion treatment at 70 ℃ for 1h, transferring the solution into a hydrothermal synthesis reaction kettle, placing the reaction kettle in a reaction kettle heating box, heating to 200 ℃, reacting for 3h, placing the reaction bottle in a vacuum drying box to remove the solvent, washing the solid product with distilled water, and preparing the carbon microsphere loaded carbon nano tube component 2.
(2) Preparation of activated carbon microsphere component 2: adding the carbon microsphere loaded carbon nanotube component 2 into distilled water, adding phosphoric acid, stirring at a constant speed at 60 ℃ for preactivation for 20h, removing the solvent from the solution by vacuum drying, placing the solid mixture into an atmosphere resistance furnace, introducing N2, heating at a rate of 3 ℃/min, carrying out heat preservation and calcination for 2h at 580 ℃, washing the calcined product with distilled water, and fully drying to obtain the activated carbon microsphere component 2, wherein the mass ratio of the carbon microsphere loaded carbon nanotube component 2 to the phosphoric acid is 1: 1.2.
(3) Preparation of Co-Ni-based carbon hybrid Material 2: adding distilled water solvent, activated carbon microsphere component 2 and CoCl into a reaction bottle2、NiCl2Placing the reaction bottle in an ultrasonic dispersion instrument, performing ultrasonic dispersion treatment at 40 ℃ for 30min, transferring the solution, performing ball milling in a star ball mill for 8h until the material passes through a 800-mesh sieve, and adding urea into the reaction bottle, wherein the activated carbon microsphere component 2 and CoCl are2、NiCl2And urea, the mass ratio of the four components is 1:1.5:2.7:6.5, the mixture is placed in an oil bath pot, the oil bath pot comprises a base, a control console is arranged on the front side of the base, a bath is arranged on the top of the base, a cover plate is placed on the top of the bath, a bottom frame is fixedly connected to the back side of the base, a vertical rod is movably inserted into the top of the bottom frame, a horizontal sleeve is sleeved on the outer side of the vertical rod, a flat rod is movably connected between the two horizontal sleeves, a vertical sleeve is sleeved on the outer side of the flat rod, an extension rod is inserted into the front side of the vertical sleeve, a lantern ring is fixedly connected to the front side of the extension rod, a spring is fixedly connected to the inner part of the lantern ring, a clamp block is fixedly connected to one end, far away from the opposite side of the lantern ring, of the spring, the clamp block is heated to 110 ℃, stirring and refluxing reaction is carried out at a constant speed for 8 hours, the solution is subjected to vacuum drying to remove a solvent, and a solid product is washed by distilled water, so as to prepare the Co-Ni-based carbon hybrid material 2.
(4) Modified Co-Ni-based carbon hybrid material 2: adding ethanol solvent, 5.4 parts of Co-Ni-based carbon hybrid material 2 and 0.6 part of silane coupling agent 3- (2, 3-epoxypropoxy) propyltriethoxysilane into a reaction bottle, placing the reaction bottle into an ultrasonic dispersion instrument, carrying out ultrasonic dispersion treatment for 1h at 50 ℃, placing the reaction bottle into a constant-temperature water bath kettle, heating to 70 ℃, stirring at a constant speed for reflux reaction for 15h, carrying out reduced pressure concentration on the solution to remove the solvent, washing a solid product with distilled water, and fully drying to prepare the 3- (2, 3-epoxypropoxy) propyltriethoxysilane grafted modified Co-Ni-based carbon hybrid material 2.
(5) Preparation of polyvinyl alcohol-glycine block copolymer component 2: adding an N, N-dimethylformamide solvent, polyvinyl alcohol and glycine into a reaction bottle at a mass ratio of 1:2.8, stirring at a constant speed until the two are dissolved, adding sulfuric acid to adjust the pH value of the solution to 2, placing the reaction bottle in an oil bath pot, heating to 145 ℃, stirring at a constant speed for reaction for 25 hours, cooling the solution in an ice water bath, adding an acetone solvent until a large amount of precipitate is generated, adding the precipitate into an acetone solvent, placing the precipitate in a dialysis bag to remove impurities, purifying and drying to obtain a solid product, namely the polyvinyl alcohol-glycine block copolymer component 2.
(6) Preparing a polyvinyl alcohol-glycine block copolymer coated Co-Ni-based carbon hybrid material 2: adding a distilled water solvent, 20 parts of a polyvinyl alcohol-glycine block copolymer component 2 and the modified Co-Ni-based carbon hybrid material 2 into a reaction bottle, uniformly stirring, transferring the solution into a hydrothermal synthesis reaction kettle, placing the kettle in a reaction kettle heating box, heating to 100 ℃, reacting for 8 hours, cooling the solution to room temperature, and removing the solvent through reduced pressure distillation to prepare the Co-Ni-based carbon hybrid material 2 coated with the polyvinyl alcohol-glycine block copolymer.
(7) Preparation of high-strength flame-retardant waterborne epoxy resin coating 2: adding 1, 4-dioxane solvent, 72.5 parts of bisphenol A epoxy resin and a polyvinyl alcohol-glycine block copolymer coated Co-Ni-based carbon hybrid material 2 into a reaction bottle, placing the reaction bottle into an oil bath pot, heating to 130 ℃, stirring at a constant speed for 4 hours to react, decompressing and concentrating the solution to remove the solvent, adding distilled water solvent and 1.5 parts of curing agent into the concentrated product, controlling the solid-to-liquid ratio to be 73%, and stirring at a constant speed to obtain the high-strength flame-retardant waterborne epoxy resin coating 2.
Example 3
(1) Adding distilled water solvent, glucose and hydroxylated carbon nano tubes into a reaction bottle according to the mass ratio of 6:1, uniformly stirring, placing the reaction bottle into an ultrasonic dispersion instrument, carrying out ultrasonic dispersion treatment at 60 ℃ for 1.5h, transferring the solution into a hydrothermal synthesis reaction kettle, placing the reaction kettle into a reaction kettle heating box, heating to 210 ℃, reacting for 2.5h, placing the reaction bottle into a vacuum drying box to remove the solvent, washing the solid product with distilled water, and preparing the carbon microsphere loaded carbon nano tube component 3.
(2) Preparation of activated carbon microsphere component 3: adding the carbon microsphere loaded carbon nanotube component 3 into distilled water, adding phosphoric acid, wherein the mass ratio of the two is 1:1.3, stirring at a constant speed at 55 ℃ for preactivation for 22h, removing the solvent from the solution through vacuum drying, placing the solid mixture into an atmosphere resistance furnace, introducing N2, heating at a rate of 4 ℃/min, carrying out heat preservation calcination at 565 ℃ for 2.5h, washing the calcination product with distilled water, and fully drying to obtain the activated carbon microsphere component 3.
(3) Preparation of Co-Ni-based carbon hybrid material 3: adding distilled water solvent, activated carbon microsphere component 3 and CoCl into a reaction bottle2、NiCl2Placing the reaction bottle in an ultrasonic dispersion instrument, performing ultrasonic dispersion treatment at 45 ℃ for 40min, transferring the solution, performing ball milling in a star ball mill for 6h until the material passes through a 1000-mesh sieve, and adding urea into the reaction bottle, wherein the activated carbon microsphere component 3 and CoCl are2、NiCl2And urea, the mass ratio of the four components is 1:1.4:3:7.6, the three components are placed in an oil bath pot, the oil bath pot comprises a base, a control console is arranged on the front side of the base, a bath is arranged on the top of the base, a cover plate is placed on the top of the bath, a bottom frame is fixedly connected to the back side of the base, a vertical rod is movably inserted into the top of the bottom frame, a horizontal sleeve is sleeved on the outer side of the vertical rod, a flat rod is movably connected between the two horizontal sleeves, a vertical sleeve is sleeved on the outer side of the flat rod, an extension rod is inserted into the front side of the vertical sleeve, a sleeve ring is fixedly connected to the front side of the extension rod, a spring is fixedly connected to the inner part of the sleeve ring, a clamping block is fixedly connected to one end, away from the reverse side of the sleeve ring, the spring is heated to 105 ℃, stirring and refluxing reaction is carried out at a constant speed for 7 hours, the solution is subjected to vacuum drying to remove a solvent, and a solid product is washed by distilled water, so as to prepare the Co-Ni-based carbon hybrid material 3.
(4) Modified Co-Ni-based carbon hybrid material 3: adding ethanol solvent, 6.3 parts of Co-Ni-based carbon hybrid material 3 and 0.7 part of silane coupling agent 3- (2, 3-epoxypropoxy) propyltriethoxysilane into a reaction bottle, placing the reaction bottle into an ultrasonic dispersion instrument, carrying out ultrasonic dispersion treatment for 1.5h at 45 ℃, placing the reaction bottle into a constant-temperature water bath kettle, heating to 75 ℃, stirring at a constant speed for reflux reaction for 12h, carrying out reduced pressure concentration on the solution to remove the solvent, washing a solid product with distilled water, and fully drying to prepare the 3- (2, 3-epoxypropoxy) propyltriethoxysilane grafted modified Co-Ni-based carbon hybrid material 3.
(5) Preparation of polyvinyl alcohol-glycine block copolymer component 3: adding an N, N-dimethylformamide solvent, polyvinyl alcohol and glycine into a reaction bottle in a mass ratio of 1:3, stirring at a constant speed until the two are dissolved, adding sulfuric acid to adjust the pH value of the solution to 3, placing the reaction bottle in an oil bath, heating to 140 ℃, stirring at a constant speed for reaction for 22 hours, cooling the solution in an ice water bath, adding an acetone solvent until a large amount of precipitate is generated, adding the precipitate into the acetone solvent, placing the mixture in a dialysis bag to remove impurities, purifying and drying to obtain a solid product, namely the polyvinyl alcohol-glycine block copolymer component 3.
(6) Preparing a polyvinyl alcohol-glycine block copolymer coated Co-Ni-based carbon hybrid material 3: adding a distilled water solvent, 22 parts of a polyvinyl alcohol-glycine block copolymer component 3 and a modified Co-Ni-based carbon hybrid material 3 into a reaction bottle, uniformly stirring, transferring the solution into a hydrothermal synthesis reaction kettle, placing the kettle in a reaction kettle heating box, heating to 110 ℃, reacting for 10 hours, cooling the solution to room temperature, and removing the solvent through reduced pressure distillation to prepare the Co-Ni-based carbon hybrid material 3 coated with the polyvinyl alcohol-glycine block copolymer.
(7) Preparation of high-strength flame-retardant waterborne epoxy resin coating 3: adding a 1, 4-dioxane solvent, 69 parts of bisphenol A epoxy resin and a polyvinyl alcohol-glycine block copolymer coated Co-Ni-based carbon hybrid material 3 into a reaction bottle, placing the reaction bottle into an oil bath pot, heating to 125 ℃, stirring at a constant speed for 5 hours to react, carrying out reduced pressure concentration on the solution to remove the solvent, adding a distilled water solvent and 2 parts of a curing agent into a concentrated product, controlling the solid-to-liquid ratio to be 77%, and stirring at a constant speed to obtain the high-strength flame-retardant waterborne epoxy resin coating 3.
Example 4
(1) Adding distilled water solvent, glucose and hydroxylated carbon nano tubes into a reaction bottle according to the mass ratio of 7:1, uniformly stirring, placing the reaction bottle into an ultrasonic dispersion instrument, carrying out ultrasonic dispersion treatment at 70 ℃ for 1h, transferring the solution into a hydrothermal synthesis reaction kettle, placing the reaction kettle in a reaction kettle heating box, heating to 220 ℃, reacting for 3h, placing the reaction bottle in a vacuum drying box to remove the solvent, washing the solid product with distilled water, and preparing the carbon microsphere loaded carbon nano tube component 4.
(2) Preparation of activated carbon microsphere component 4: adding the carbon microsphere loaded carbon nanotube component 4 into distilled water, adding phosphoric acid, stirring at a constant speed at 50 ℃ for preactivation for 25h, drying the solution in vacuum to remove the solvent, placing the solid mixture in an atmosphere resistance furnace, introducing N2, heating at a rate of 3 ℃/min, carrying out heat preservation and calcination for 3h at 550 ℃, washing the calcined product with distilled water, and fully drying to obtain the activated carbon microsphere component 4, wherein the mass ratio of the carbon microsphere loaded carbon nanotube component 4 to the phosphoric acid is 1: 1.2.
(3) Preparation of Co-Ni-based carbon hybrid material 4: adding distilled water solvent, activated carbon microsphere component 4 and CoCl into a reaction bottle2、NiCl2Placing the reaction bottle in an ultrasonic disperser, performing ultrasonic dispersion treatment at 40 deg.C for 50min, transferring the solution, ball-milling in a ball mill for 8 hr until the material passes through a 1000 mesh sieve, and adding urea into the reaction bottle, wherein the activated carbon microsphere component 4 and CoCl2、NiCl2And urea, the mass ratio of the four components is 1:1.3:2.7:6.5, the oil bath is placed in an oil bath pot, the oil bath pot comprises a base, a control console is arranged on the front side of the base, a bath is arranged on the top of the base, a cover plate is placed on the top of the bath, a bottom frame is fixedly connected to the back side of the base, a vertical rod is movably inserted into the top of the bottom frame, a horizontal sleeve is sleeved on the outer side of the vertical rod, a flat rod is movably connected between the two horizontal sleeves, a vertical sleeve is sleeved on the outer side of the flat rod, an extension rod is inserted into the front side of the vertical sleeve, a lantern ring is fixedly connected to the front side of the extension rod, a spring is fixedly connected to the inner part of the lantern ring, a clamp block is fixedly connected to one end, far away from the opposite side of the lantern ring, of the spring, the clamp block is heated to 110 ℃, stirring and refluxing reaction is carried out at a constant speed for 8 hours, the solution is subjected to vacuum drying to remove a solvent, and a solid product is washed by distilled water, so as to prepare the Co-Ni-based carbon hybrid material 4.
(4) Modified Co-Ni based carbon hybrid 4: adding ethanol solvent, 8.2 parts of Co-Ni-based carbon hybrid material 4 and 0.8 part of silane coupling agent 3- (2, 3-epoxypropoxy) propyltriethoxysilane into a reaction bottle, placing the reaction bottle into an ultrasonic dispersion instrument, carrying out ultrasonic dispersion treatment for 1h at 50 ℃, placing the reaction bottle into a constant-temperature water bath kettle, heating to 70 ℃, stirring at a constant speed for reflux reaction for 15h, carrying out reduced pressure concentration on the solution to remove the solvent, washing the solid product with distilled water, and fully drying to prepare the 3- (2, 3-epoxypropoxy) propyltriethoxysilane grafted modified Co-Ni-based carbon hybrid material 4.
(5) Preparation of polyvinyl alcohol-glycine block copolymer component 4: adding an N, N-dimethylformamide solvent, polyvinyl alcohol and glycine into a reaction bottle at a mass ratio of 1:3.3, stirring at a constant speed until the two are dissolved, adding sulfuric acid to adjust the pH value of the solution to 2, placing the reaction bottle in an oil bath pot, heating to 145 ℃, stirring at a constant speed for reaction for 25 hours, cooling the solution in an ice water bath, adding an acetone solvent until a large amount of precipitate is generated, adding the precipitate into an acetone solvent, placing the precipitate in a dialysis bag to remove impurities, purifying and drying to obtain a solid product, namely the polyvinyl alcohol-glycine block copolymer component 4.
(6) Preparing a polyvinyl alcohol-glycine block copolymer coated Co-Ni-based carbon hybrid material 4: adding distilled water solvent, 25.5 parts of polyvinyl alcohol-glycine block copolymer component 4 and modified Co-Ni-based carbon hybrid material 4 into a reaction bottle, uniformly stirring, transferring the solution into a hydrothermal synthesis reaction kettle, placing the kettle in a reaction kettle heating box, heating to 120 ℃, reacting for 8 hours, cooling the solution to room temperature, and removing the solvent through reduced pressure distillation to prepare the Co-Ni-based carbon hybrid material 4 coated by the polyvinyl alcohol-glycine block copolymer.
(7) Preparation of high-strength flame-retardant waterborne epoxy resin coating 4: adding a 1, 4-dioxane solvent, 63 parts of bisphenol A epoxy resin and a polyvinyl alcohol-glycine block copolymer coated Co-Ni-based carbon hybrid material 4 into a reaction bottle, placing the reaction bottle into an oil bath pot, heating to 130 ℃, stirring at a constant speed for 5 hours to react, concentrating the solution under reduced pressure to remove the solvent, adding a distilled water solvent and 2.5 parts of a curing agent into the concentrated product, controlling the solid-to-liquid ratio to be 80%, and stirring at a constant speed to obtain the high-strength flame-retardant waterborne epoxy resin coating 4.
Example 5
(1) Adding distilled water solvent, glucose and hydroxylated carbon nano tubes into a reaction bottle according to the mass ratio of 7:1, uniformly stirring, placing the reaction bottle into an ultrasonic dispersion instrument, carrying out ultrasonic dispersion treatment at 70 ℃ for 2h, transferring the solution into a hydrothermal synthesis reaction kettle, placing the reaction kettle in a reaction kettle heating box, heating to 220 ℃, reacting for 3h, placing the reaction bottle in a vacuum drying box to remove the solvent, washing the solid product with distilled water, and preparing the carbon microsphere loaded carbon nano tube component 5.
(2) Preparation of activated carbon microsphere component 5: adding the carbon microsphere loaded carbon nanotube component 5 into distilled water, adding phosphoric acid, stirring at a constant speed at 60 ℃ for preactivation for 25h, drying the solution in vacuum to remove the solvent, placing the solid mixture into an atmosphere resistance furnace, introducing N2, heating at a rate of 5 ℃/min, carrying out heat preservation and calcination for 3h at 580 ℃, washing the calcined product with distilled water, and fully drying to obtain the activated carbon microsphere component 5, wherein the mass ratio of the carbon microsphere loaded carbon nanotube component 5 to the phosphoric acid is 1: 1.5.
(3) Preparation of Co-Ni-based carbon hybrid 5: adding distilled water solvent, activated carbon microsphere component 5 and CoCl into a reaction bottle2、NiCl2Placing the reaction bottle in an ultrasonic disperser, performing ultrasonic dispersion treatment at 50 deg.C for 50min, transferring the solution, ball-milling in a ball mill for 8 hr until the material passes through a 1000 mesh sieve, and adding urea into the reaction bottle, wherein the activated carbon microsphere component 5 and CoCl2、NiCl2And urea, the mass ratio of the four components is 1:1.5:3.2:8.7, the mixture is placed in an oil bath pot, the oil bath pot comprises a base, a control console is arranged on the front side of the base, a bath is arranged on the top of the base, a cover plate is placed on the top of the bath, a bottom frame is fixedly connected to the back side of the base, a vertical rod is movably inserted into the top of the bottom frame, a horizontal sleeve is sleeved on the outer side of the vertical rod, a flat rod is movably connected between the two horizontal sleeves, a vertical sleeve is sleeved on the outer side of the flat rod, an extension rod is inserted into the front side of the vertical sleeve, a lantern ring is fixedly connected to the front side of the extension rod, a spring is fixedly connected to the inner part of the lantern ring, a clamp block is fixedly connected to one end, away from the opposite side of the lantern ring, the spring is heated to 110 ℃, stirring and refluxing reaction is carried out at a constant speed for 8 hours, the solution is subjected to vacuum drying to removal of solvent, and the solid product is washed by distilled water, so as to prepare the Co-Ni-based carbon hybrid material 5.
(4) Modified Co-Ni-based carbon hybrid 5: adding ethanol solvent, 9 parts of Co-Ni-based carbon hybrid material 5 and 1 part of silane coupling agent 3- (2, 3-epoxypropoxy) propyltriethoxysilane into a reaction bottle, placing the reaction bottle into an ultrasonic dispersion instrument, carrying out ultrasonic dispersion treatment at 50 ℃ for 2h, placing the reaction bottle into a constant-temperature water bath kettle, heating to 80 ℃, carrying out uniform stirring reflux reaction for 15h, carrying out reduced pressure concentration on the solution to remove the solvent, washing the solid product with distilled water, and fully drying to prepare the 3- (2, 3-epoxypropoxy) propyltriethoxysilane grafted modified Co-Ni-based carbon hybrid material 5.
(5) Preparation of polyvinyl alcohol-glycine block copolymer component 5: adding an N, N-dimethylformamide solvent, polyvinyl alcohol and glycine into a reaction bottle at a mass ratio of 1:3.3, stirring at a constant speed until the two are dissolved, adding sulfuric acid to adjust the pH value of the solution to 2, placing the reaction bottle in an oil bath pot, heating to 145 ℃, stirring at a constant speed for reaction for 25 hours, cooling the solution in an ice water bath, adding an acetone solvent until a large amount of precipitate is generated, adding the precipitate into an acetone solvent, placing the precipitate in a dialysis bag to remove impurities, purifying and drying to obtain a solid product, namely the polyvinyl alcohol-glycine block copolymer component 5.
(6) Preparing a polyvinyl alcohol-glycine block copolymer coated Co-Ni-based carbon hybrid material 5: adding a distilled water solvent, 27 parts of a polyvinyl alcohol-glycine block copolymer component 5 and the modified Co-Ni-based carbon hybrid material 5 into a reaction bottle, uniformly stirring, transferring the solution into a hydrothermal synthesis reaction kettle, placing the kettle in a reaction kettle heating box, heating to 100 ℃, reacting for 12 hours, cooling the solution to room temperature, and removing the solvent through reduced pressure distillation to prepare the Co-Ni-based carbon hybrid material 5 coated with the polyvinyl alcohol-glycine block copolymer.
(7) Preparation of high-strength flame-retardant waterborne epoxy resin coating 5: adding a 1, 4-dioxane solvent, 60 parts of bisphenol A epoxy resin and a polyvinyl alcohol-glycine block copolymer coated Co-Ni-based carbon hybrid material 5 into a reaction bottle, placing the reaction bottle into an oil bath pot, heating to 130 ℃, stirring at a constant speed for 6 hours to react, concentrating the solution under reduced pressure to remove the solvent, adding a distilled water solvent and 3 parts of a curing agent into the concentrated product, controlling the solid-to-liquid ratio to be 85%, and stirring at a constant speed to obtain the high-strength flame-retardant waterborne epoxy resin coating 5.
The high-strength flame-retardant waterborne epoxy resin coatings in the examples 1-5 are cured into films, and the limit oxygen index and the flame retardant property of the film materials are tested by using a YZS-10A type full-automatic oxygen index tester, wherein the test standards are GB/T8626-2007 and GB/T5464-2010.
In summary, the high-strength flame-retardant water-based epoxy resin coating has the advantages that the carbon nano tube has excellent heat conduction performance and large specific surface area, the carbon microspheres prepared by the hot solvent method grow on the surface and the inner wall of the carbon nano tube in situ, the carbon microspheres are uniformly dispersed, the agglomeration and caking phenomena are reduced, and the formed uniformly-dispersed carbon microspheres well adsorb Co2+And Ni2+The nickel-cobalt basic carbonate is generated on the surface of the carbon microsphere with urea to form a Co-Ni-based carbon hybrid material, so that the Co-Ni-based carbon hybrid material has high thermal conductivity and coefficient of heat conductivity, the conduction rate of heat in the epoxy resin is increased, and the local heat aggregation is reduced, thereby improving the thermal conductivity of the epoxy resin and avoiding the problem that the toughness and the strength of the epoxy resin material are influenced at high temperature.
The nickel-cobalt basic carbonate in the Co-Ni-based carbon hybrid material can absorb heat to dehydrate water and carbon dioxide at high temperature during combustion to form metal oxides CoO and NiO, the NiO and CoO can promote dehydrogenation reaction of epoxy resin at high temperature to enable the epoxy resin to form a compact coke layer, the carbon residue rate during combustion of the epoxy resin is improved, conduction of combustion heat and permeation of oxygen are hindered, continuous and dense expanded carbon is formed during combustion of the carbon-based material in the Co-Ni-based carbon hybrid material, a closed protective layer carbide is generated by aggregation in the epoxy resin, a good smoke suppression effect is achieved, and therefore the epoxy resin coating has a good flame retardant effect.
Hydroxyl in the carbon nano tube is bonded by silane coupling agent 3- (2, 3-epoxypropoxy) propyl triethoxysilane, so that the Co-Ni-based carbon hybrid material is well coated by the polyvinyl alcohol-glycine block copolymer, the copolymer is formed by physically blending and crosslinking the polyvinyl alcohol-glycine block copolymer and the epoxy resin, the dispersity and compatibility of the Co-Ni-based carbon hybrid material in the epoxy resin are improved, the flame retardant property of the Co-Ni-based carbon hybrid material is enhanced, meanwhile, the polyvinyl alcohol-glycine block copolymer improves the crosslinking degree of the epoxy resin, enhances the mechanical properties of the epoxy resin such as tensile strength, breaking strength and the like, meanwhile, a large number of hydrophilic hydroxyl groups and amino groups in the polyvinyl alcohol-glycine block copolymer endow the epoxy resin with hydrophilic performance, so that the water-based epoxy resin coating is prepared.
Claims (8)
1. The high-strength flame-retardant waterborne epoxy resin coating comprises the following formula raw materials in parts by weight, and is characterized in that: 4.5-9 parts of Co-Ni-based carbon hybrid material, 0.5-1 part of silane coupling agent, 18-27 parts of polyvinyl alcohol-glycine block copolymer, 60-76 parts of bisphenol A epoxy resin and 1-3 parts of curing agent;
the preparation method of the Co-Ni-based carbon hybrid material comprises the following steps:
(1) adding glucose and a hydroxylated carbon nano tube into a distilled water solvent, carrying out ultrasonic dispersion treatment on the solution at 50-70 ℃ for 1-2h, transferring the solution into a hydrothermal reaction kettle, heating to 200-220 ℃, reacting for 2-3h, removing the solvent from the solution, washing a solid product, and preparing the carbon microsphere loaded carbon nano tube;
(2) adding carbon microspheres loaded with carbon nano tubes into distilled water, adding phosphoric acid, stirring at a constant speed of 50-60 ℃ for 20-25h, removing the solvent from the solution, placing the solid mixture in an atmosphere resistance furnace, introducing N2, heating at a rate of 3-5 ℃/min, carrying out heat preservation and calcination at the temperature of 550-580 ℃ for 2-3h, washing the calcined product, and fully drying to prepare activated carbon microspheres;
(3) adding activated carbon microspheres, CoCl 2 and NiCl 2 into a distilled water solvent, carrying out ultrasonic dispersion treatment on the solution at 40-50 ℃ for 30-50min, transferring the solution to a star ball mill for ball milling for 5-8h until the material passes through a 800-plus-1000-mesh sieve, adding urea into the solution, placing the solution in an oil bath pot, heating to 100-plus-110 ℃, reacting for 6-8h, removing the solvent from the solution, washing a solid product, and preparing to obtain a Co-Ni-based carbon hybrid material;
the preparation method of the high-strength flame-retardant waterborne epoxy resin coating comprises the following steps:
(1) adding 4.5-9 parts of Co-Ni-based carbon hybrid material and 0.5-1 part of silane coupling agent 3- (2, 3-epoxypropoxy) propyltriethoxysilane into an ethanol solvent, performing ultrasonic dispersion treatment on the solution at 40-50 ℃ for 1-2h, heating the solution to 70-80 ℃, reacting for 10-15h, removing the solvent from the solution, washing a solid product, and drying to prepare the 3- (2, 3-epoxypropoxy) propyltriethoxysilane grafted modified Co-Ni-based carbon hybrid material;
(2) adding 18-27 parts of polyvinyl alcohol-glycine block copolymer and modified Co-Ni-based carbon hybrid material into a distilled water solvent, transferring the solution into a hydrothermal reaction kettle, heating to 100 ℃ and 120 ℃, reacting for 8-12h, removing the solvent from the solution, and preparing the Co-Ni-based carbon hybrid material coated by the polyvinyl alcohol-glycine block copolymer;
(3) adding 60-76 parts of bisphenol A epoxy resin and a Co-Ni-based carbon hybrid material coated by a polyvinyl alcohol-glycine block copolymer into a 1, 4-dioxane solvent, heating the solution to 130 ℃, stirring at a constant speed for reaction for 4-6h, removing the solvent from the solution, adding a distilled water solvent and 1-3 parts of a curing agent into a concentrated product, controlling the solid-to-liquid ratio to be 70-85%, and uniformly stirring at a constant speed to obtain the high-strength flame-retardant waterborne epoxy resin coating.
2. The high-strength flame-retardant water-based epoxy resin coating according to claim 1, wherein: the silane coupling agent is 3- (2, 3-epoxypropoxy) propyl triethoxysilane.
3. The high-strength flame-retardant water-based epoxy resin coating according to claim 1, wherein: the mass ratio of the glucose to the hydroxylated carbon nanotube is 4-7: 1.
4. The high-strength flame-retardant water-based epoxy resin coating according to claim 1, wherein: the mass ratio of the carbon microsphere loaded carbon nano tube to the phosphoric acid is 1: 1.2-1.5.
5. The high-strength flame-retardant water-based epoxy resin coating according to claim 1, wherein: the mass ratio of the activated carbon microspheres to the CoCl 2 to the NiCl 2 to the urea is 1:1.3-1.5:2.7-3.2: 6.5-8.7.
6. The high-strength flame-retardant water-based epoxy resin coating according to claim 1, wherein: the oil bath pan comprises a base (1), a console (2) is arranged on the front surface of the base (1), the top of the base (1) is provided with a bath (3), the top of the bath (3) is provided with a cover plate (4), the back of the base (1) is fixedly connected with an underframe (5), the top of the underframe (5) is movably inserted with a vertical rod (6), the outer side of the vertical rod (6) is sleeved with a horizontal sleeve (7), a flat rod (8) is movably connected between the two horizontal sleeves (7), a vertical sleeve (9) is sleeved on the outer side of the flat rod (8), an extension rod (10) is inserted in the front of the vertical sleeve (9), the front surface of the extension rod (10) is fixedly connected with a lantern ring (11), the interior of the lantern ring (11) is fixedly connected with a spring (12), and one end of the spring (12) far away from the reverse side of the lantern ring (11) is fixedly connected with a clamping block (13).
7. The high-strength flame-retardant water-based epoxy resin coating according to claim 1, wherein: the preparation method of the polyvinyl alcohol-glycine block copolymer comprises the following steps:
(1) adding polyvinyl alcohol and glycine into an N, N-dimethylformamide solvent, stirring for dissolving, adding sulfuric acid to adjust the pH value of the solution to 2-3, heating the solution to 135-145 ℃, reacting for 20-25h, cooling the solution in an ice-water bath, adding an acetone solvent until a large amount of precipitate is generated, adding the precipitate into the acetone solvent, placing the acetone solvent into a dialysis bag to remove impurities, and purifying and drying to obtain a solid product, namely the polyvinyl alcohol-glycine block copolymer.
8. The high-strength flame-retardant water-based epoxy resin coating according to claim 7, wherein: the mass ratio of the polyvinyl alcohol to the glycine is 1: 2.8-3.3.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010825274.XA CN112011249B (en) | 2020-08-17 | 2020-08-17 | High-strength flame-retardant water-based epoxy resin coating and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010825274.XA CN112011249B (en) | 2020-08-17 | 2020-08-17 | High-strength flame-retardant water-based epoxy resin coating and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN112011249A CN112011249A (en) | 2020-12-01 |
| CN112011249B true CN112011249B (en) | 2021-11-30 |
Family
ID=73504742
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202010825274.XA Active CN112011249B (en) | 2020-08-17 | 2020-08-17 | High-strength flame-retardant water-based epoxy resin coating and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN112011249B (en) |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2001225150A (en) * | 2000-02-17 | 2001-08-21 | Mishima Kosan Co Ltd | Casting mold for continuous casting |
| CN102816495A (en) * | 2011-06-10 | 2012-12-12 | 上海建冶科技工程股份有限公司 | Environment-friendly nano-epoxy silicone heavy anti-corrosion coating and preparation method and using method thereof |
| CN106784706A (en) * | 2016-12-27 | 2017-05-31 | 陕西科技大学 | A kind of carbon microspheres are used as transition zone titanium carbide growth in situ CNTs three-dimensional composite materials and preparation method thereof |
| CN110970229A (en) * | 2019-12-27 | 2020-04-07 | 中国地质大学（北京） | NiCo2S4@ mesophase carbon microsphere/carbon nanotube composite material and preparation method and application thereof |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2778972B2 (en) * | 1989-02-08 | 1998-07-23 | 福田金属箔粉工業株式会社 | Graphite dispersed Co-Ni based self-lubricating alloy |
-
2020
- 2020-08-17 CN CN202010825274.XA patent/CN112011249B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2001225150A (en) * | 2000-02-17 | 2001-08-21 | Mishima Kosan Co Ltd | Casting mold for continuous casting |
| CN102816495A (en) * | 2011-06-10 | 2012-12-12 | 上海建冶科技工程股份有限公司 | Environment-friendly nano-epoxy silicone heavy anti-corrosion coating and preparation method and using method thereof |
| CN106784706A (en) * | 2016-12-27 | 2017-05-31 | 陕西科技大学 | A kind of carbon microspheres are used as transition zone titanium carbide growth in situ CNTs three-dimensional composite materials and preparation method thereof |
| CN110970229A (en) * | 2019-12-27 | 2020-04-07 | 中国地质大学（北京） | NiCo2S4@ mesophase carbon microsphere/carbon nanotube composite material and preparation method and application thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN112011249A (en) | 2020-12-01 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN108046789B (en) | Preparation method of electromagnetic shielding composite material | |
| CN108690191B (en) | Polybenzoxazine aerogel heat insulation material and preparation method thereof | |
| CN110257019B (en) | Phase-change composite material with photo-thermal conversion function and preparation method thereof | |
| CN109762436B (en) | Low-temperature-resistant heat-conducting insulating resin paint suitable for superconducting insulating material and preparation method and application thereof | |
| CN111763406A (en) | Preparation process of graphene nanocomposite | |
| CN109265687A (en) | A kind of preparation method of the Polycarbosilane containing heterogeneous element | |
| CN110724320B (en) | Heat-conducting rubber composite material and preparation method thereof | |
| CN111509207A (en) | Porous carbon-coated Co-doped MnO lithium ion battery cathode material and preparation method thereof | |
| CN112011249B (en) | High-strength flame-retardant water-based epoxy resin coating and preparation method thereof | |
| CN108831759A (en) | One kind is based on graphene/chitosan multi-porous carbon composite and its preparation method and application | |
| CN101891936B (en) | Preparation method of composite material based on epoxy resin and phosphazene nanotubes | |
| CN114015110B (en) | Low-shrinkage phenolic aerogel and preparation method thereof | |
| CN109824905B (en) | High-temperature-resistant polycarbosilane precursor and preparation method thereof | |
| CN109384942A (en) | A kind of flexibility high thermal conductivity graphene compound polyimide film and preparation method thereof | |
| CN107010961B (en) | The serialization process for calcining and its device of SiC fiber | |
| CN112608486A (en) | High-conductivity carbon nanotube grafted polyurethane composite material and preparation method thereof | |
| CN111548626A (en) | Conductive carbon nanotube modified polyimide film material and preparation method thereof | |
| CN110922918A (en) | Double-component heat storage encapsulating material and preparation method thereof | |
| CN111334028B (en) | Anti-ultraviolet high-thermal-conductivity modified polyurethane composite film material and preparation method thereof | |
| CN109880372A (en) | It is a kind of to utilize heat-conducting silicon rubber made from coated with silica boron nitride and the preparation method and application thereof | |
| CN106928907B (en) | High-temperature stable nanofluid black liquor and preparation method and application thereof | |
| CN113930087A (en) | Surface modified boron nitride powder for heat-conducting filler and preparation method thereof | |
| CN110739095B (en) | Conductive agent prepared from polyacrylonitrile gel and preparation method thereof | |
| CN112029247A (en) | High-thermal-conductivity modified polylactic acid film and preparation method thereof | |
| CN112573502B (en) | Aromatic cyano/aromatic alkynyl porous carbon material and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| TA01 | Transfer of patent application right |
Effective date of registration: 20211115 Address after: 421200 No. 12, Jinyuan Road, songmu Economic Development Zone, shigu District, Hengyang City, Hunan Province Applicant after: Hunan kaiphosphorus yanfengta coating Co., Ltd Address before: 312500 No. 38, Zhutan village, jingling Town, Xinchang County, Shaoxing City, Zhejiang Province Applicant before: Xinchang Xuhui New Material Technology Co., Ltd |
|
| TA01 | Transfer of patent application right | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |