CN111393944A - TiO 22Nanowire modified epoxy acrylic resin anticorrosive coating and preparation method thereof - Google Patents
TiO 22Nanowire modified epoxy acrylic resin anticorrosive coating and preparation method thereof Download PDFInfo
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Abstract
The invention relates to the technical field of epoxy resin corrosion prevention and discloses TiO2Nanowire modified epoxyThe acrylic resin anticorrosive coating comprises the following formula raw materials and components: modified hydroxylated TiO2The nano-wire is prepared from nano-wires, epoxy resin, methyl methacrylate, hydroxyethyl acrylate, an initiator, maleic anhydride and a catalyst. The TiO is2Nanowire modified epoxy acrylic resin anticorrosive coating, ethylene glycol as mediation and Ti4+Form linear chain complex to prepare hydroxylated TiO2The surface of the nanowire contains a large number of hydroxyl structures, and the vinyltrimethoxysilane modified hydroxylated TiO with high grafting rate is obtained2Nanowires, alkenylated epoxy resins, with methylmethacrylate, hydroxyethylacrylate and modified hydroxylated TiO2Nanowire crosslinking polymerization, and improves TiO through the crosslinking effect of chemical bonds2The dispersibility and compatibility of the nano wire in the epoxy resin endow the epoxy resin coating with excellent antibacterial performance and microbial corrosion resistance.
Description
Technical Field
The invention relates to the technical field of epoxy resin corrosion prevention, in particular to TiO2A nanowire modified epoxy acrylic resin anticorrosive coating and a preparation method thereof.
Background
The corrosion refers to the process of generating loss and destruction of metal or nonmetal under the chemical or electrochemical action of surrounding media such as air, water, acid, alkali, solvent and the combined action of physical, mechanical or biological factors, the metal corrosion can be divided into chemical corrosion and microbial corrosion, the chemical corrosion is the corrosion caused by the chemical action of metal in dry gas and non-electrolyte solution, corrosion products are generated on the surface of metal, no current is generated in the corrosion process, when the corrosion products fall off from the surface of metal material, the material loss and destruction are caused, the microbial corrosion is the microbial action of bacteria, fungi and the like, the material corrosion is caused, the microbial corrosion is electrochemical corrosion, the medium changes the physicochemical property of a contact interface due to the reproduction and metabolism of corrosive microorganisms, and the secretion and the external enzymes of intermediate products and final products of microbial cell metabolism can generate microbial corrosion And microbial corrosion can occur to underground oil pipelines, gas pipelines, cable protective layers, oil storage tanks, gas storage tanks and the like, so that huge economic loss and potential safety hazards are generated.
The epoxy resin is a thermosetting resin, can be subjected to ring-opening reaction by using a compound containing active hydrogen, is cured and crosslinked to generate a network structure, has good mechanical property, electrical property and chemical property, mainly comprises general adhesive, high-temperature-resistant adhesive, sealant, civil construction adhesive and the like, has applications in the fields of civil construction, electronic and electrical products, aerospace and the like, but the epoxy resin coating is not high in corrosion resistance and antibacterial property, and the nano TiO coating is2Is a semiconductor material with wide application, can generate photoproduction electrons and holes under the action of light radiation, further react with oxygen and water molecules to generate strong oxidation superoxide radical and hydroxyl radical, and can be mixed with eggs in the bodies of microorganisms such as bacteria, fungi and the likeThe protease and biological macromolecules are subjected to oxidation-reduction reaction, so that the normal metabolism process of microorganisms such as bacteria and the like is inhibited, the effects of killing the microorganisms and reducing the microbial corrosion are achieved, but the nano TiO has the advantages that2The compatibility with epoxy resin is poor, and the epoxy resin is easy to agglomerate and agglomerate in the epoxy resin, so that the mechanical properties such as toughness, wear resistance and the like of the epoxy resin material are seriously influenced.
Technical problem to be solved
Aiming at the defects of the prior art, the invention provides TiO2The nanowire modified epoxy acrylic resin anticorrosive coating and the preparation method thereof solve the problem that a nickel-cobalt nano alloy is easy to agglomerate and aggregate in an electrode material, and simultaneously solve the problem that the nickel-cobalt nano alloy is easy to react with an electrolyte or is directly dissolved by the electrolyte.
(II) technical scheme
In order to achieve the purpose, the invention provides the following technical scheme: TiO 22The nanowire modified epoxy acrylic resin anticorrosive coating comprises the following formula raw materials in parts by weight: 1-4 parts of modified hydroxylated TiO2The nano-wire, 64-81 parts of epoxy resin, 10-15 parts of methyl methacrylate, 4-8 parts of hydroxyethyl acrylate, 1.5-3 parts of initiator, 2-5 parts of maleic anhydride and 0.5-1 part of catalyst.
Preferably, the initiator is dibenzoyl peroxide.
Preferably, the catalyst is tetrabutylammonium bromide.
Preferably, the modified hydroxylated TiO2The preparation method of the nanowire comprises the following steps:
(1) introducing nitrogen into a full-automatic reaction kettle to discharge air, adding an ethylene glycol solvent and titanium tetrachloride, heating to 190 ℃ for 160 plus materials, stirring at a constant speed for reaction for 2-4h, cooling the solution to room temperature, filtering to remove the solvent, washing the solid product with distilled water and ethanol, placing the solid product into a distilled water solvent, stirring at a constant speed for reaction for 1-4h at 90-110 ℃, filtering the solution to remove the solvent, washing the solid product with distilled water, and fully drying to prepare the hydroxylated porous TiO2A nanowire.
(2) Adding distilled water and ethanol solvent into a reaction bottle, wherein the volume ratio of the distilled water to the ethanol solvent is 15-20:1, and adding hydroxylated porous TiO2Uniformly dispersing nanowires by ultrasonic, adding a silane coupling agent, heating to 40-60 ℃, uniformly stirring for reaction for 5-10h, filtering the solution to remove the solvent, washing the solid product by using distilled water, and fully drying to prepare the modified hydroxylated TiO grafted by the silane coupling agent2A nanowire.
Preferably, the silane coupling agent is vinyltrimethoxysilane, hydroxylated porous TiO2The mass ratio of the nano wire to the vinyl trimethoxy silane is 18-25: 1.
Preferably, full-automatic reation kettle includes the cauldron body, the internal portion of cauldron is provided with the heat preservation inner bag, the left side fixedly connected with intake pipe of the cauldron body, intake pipe and air inlet valve swing joint, intake pipe swing joint has the air pump, the right side fixedly connected with outlet duct of the cauldron body, outlet duct and air outlet valve swing joint, the upper left side fixedly connected with feed port of the cauldron body, the top fixedly connected with agitating unit of the cauldron body, agitating unit and connection ball swing joint, connect ball and puddler fixed connection, the puddler surface is provided with the stirring fan piece, the below fixedly connected with discharge gate of the cauldron body, discharge gate and control valve fixed connection, the outside swing joint of the cauldron body has the base, the below swing joint of base has the gyro wheel.
Preferably, the TiO is2The preparation method of the nanowire modified epoxy acrylic resin anticorrosive coating comprises the following steps:
(1) adding 64-80 parts of epoxy resin into a reaction bottle, heating to 50-70 ℃, adding 2-5 parts of maleic anhydride and 0.5-1 part of tetrabutylammonium bromide serving as a catalyst, stirring at a constant speed for reacting for 4-6h, adding an acetone solvent, stirring for dissolving, adding 4-8 parts of hydroxyethyl acrylate, 10-15 parts of methyl methacrylate and 1-4 parts of modified hydroxylated TiO2Heating the nanowire and 1.5-3 parts of initiator dibenzoyl peroxide to 60-90 ℃, uniformly stirring and reacting for 5-8h, adding triethanolamine to adjust the pH value of the solution to be neutral, adding epoxy resin curing agent, pouring the solution into a film-forming mold to be cured into a film, and preparing the TiO2The nanowire modified epoxy acrylic resin anticorrosive coating.
(III) advantageous technical effects
Compared with the prior art, the invention has the following beneficial technical effects:
the TiO is2Nanowire modified epoxy acrylic resin anticorrosive coating, ethylene glycol as mediation, and Ti4+Forming linear chain complex, and preparing the hydroxylated TiO by a hot solvent method and a hydrolysis method2The nano-wire has a large amount of hydroxyl structures on the surface, and can be reacted with hydroxylated TiO by using a small amount of vinyl trimethoxy silane2The reaction is carried out, thereby obtaining the vinyltrimethoxysilane modified hydroxylated TiO with high grafting rate2Nanowires, hydroxylated TiO2Forms a three-dimensional hydrogen bond network with hydroxyethyl acrylate and the like, is adsorbed by the hydroxyethyl acrylate and the like, and can promote the vinyltrimethoxysilane to modify the hydroxylated TiO2The nanowires undergo a cross-linking polymerization reaction.
The TiO is2The nanowire modified epoxy acrylic resin anticorrosive coating is prepared by the steps of using maleic anhydride to perform self ring opening reaction with epoxy groups of epoxy resin under the action of a catalyst to obtain alkenyl epoxy resin, and performing alkenyl radical polymerization with methyl methacrylate, hydroxyethyl acrylate and modified hydroxylated TiO2The mutual crosslinking polymerization of alkenyl of vinyl trimethoxy silane in the nano-wire greatly improves TiO through the crosslinking effect of chemical bonds rather than the physical blending effect2The dispersibility and compatibility of the nano wire in the epoxy resin can obtain the epoxy acrylic resin coating, thereby avoiding the uneven dispersion of the nano TiO2Can affect the mechanical properties of the epoxy resin such as toughness, wear resistance and the like, and meanwhile, TiO2The nano wires endow the epoxy resin coating with excellent antibacterial performance and microbial corrosion resistance, and the acrylic resin and the epoxy resin are crosslinked and polymerized to form the epoxy acrylic resin, so that good hydrophilicity and water resistance are endowed.
Drawings
FIG. 1 is a schematic front view of a reaction vessel body;
fig. 2 is an enlarged front view of the discharge port.
1. A kettle body; 2. a heat preservation liner; 3. an air inlet pipe; 4. an intake valve; 5. an air pump; 6. an air outlet pipe; 7. an air outlet valve; 8. a feed port; 9. a stirring device; 10. a connecting ball; 11. a stirring rod; 12. stirring fan blades; 13. a discharge port; 14. a control valve; 15. a base; 16. and a roller.
Detailed Description
To achieve the above object, the present invention provides the following embodiments and examples: TiO 22The nanowire modified epoxy acrylic resin anticorrosive coating comprises the following formula raw materials in parts by weight: 1-4 parts of modified hydroxylated TiO2The nano-wire, 64-81 parts of epoxy resin, 10-15 parts of methyl methacrylate, 4-8 parts of hydroxyethyl acrylate, 1.5-3 parts of initiator, 2-5 parts of maleic anhydride and 0.5-1 part of catalyst, wherein the initiator is dibenzoyl peroxide and the catalyst is tetrabutylammonium bromide.
Modified hydroxylated TiO2The preparation method of the nanowire comprises the following steps:
(1) introducing nitrogen into a full-automatic reaction kettle to discharge air, wherein the full-automatic reaction kettle comprises a kettle body, a heat-insulating inner container is arranged inside the kettle body, an air inlet pipe is fixedly connected to the left side of the kettle body, the air inlet pipe is movably connected with an air inlet valve, an air outlet pipe is fixedly connected to the right side of the kettle body, the air outlet pipe is movably connected with an air outlet valve, a feeding hole is fixedly connected to the upper left side of the kettle body, a stirring device is fixedly connected to the upper side of the kettle body, the stirring device is movably connected with a connecting ball, the connecting ball is fixedly connected with a stirring rod, a stirring fan sheet is arranged on the surface of the stirring rod, a discharging hole is fixedly connected to the lower side of the kettle body, the discharging hole is fixedly connected with a control valve, a base is movably connected to the outer part of the kettle body, rollers are movably connected to the lower side, cooling the solution to room temperature, filtering to remove the solvent, washing the solid product with distilled water and ethanol, placing the solid product in a distilled water solvent, stirring at a constant speed for reaction for 1-4h at 90-110 ℃, filtering the solution to remove the solvent, washing the solid product with distilled water, and fully drying to prepare the hydroxylated porous TiO2A nanowire.
(2) Adding distilled water and ethanol solvent into a reaction bottle, wherein the volume ratio of the distilled water to the ethanol solvent is 15-20:1, and adding hydroxylated porous TiO2Nano-wire, adding silane coupling agent vinyl trimethoxy silane after ultrasonic dispersion, and hydroxylating porous TiO2The mass ratio of the nano-wire is 1:18-25, the nano-wire is heated to 40-60 ℃, stirred at a constant speed and reacted for 5-10h, the solution is filtered to remove the solvent, the solid product is washed by distilled water and fully dried to prepare the modified hydroxylated TiO grafted by the silane coupling agent2A nanowire.
TiO2The preparation method of the nanowire modified epoxy acrylic resin anticorrosive coating comprises the following steps:
(1) adding 64-80 parts of epoxy resin into a reaction bottle, heating to 50-70 ℃, adding 2-5 parts of maleic anhydride and 0.5-1 part of tetrabutylammonium bromide serving as a catalyst, stirring at a constant speed for reacting for 4-6h, adding an acetone solvent, stirring for dissolving, adding 4-8 parts of hydroxyethyl acrylate, 10-15 parts of methyl methacrylate and 1-4 parts of modified hydroxylated TiO2Heating the nanowire and 1.5-3 parts of initiator dibenzoyl peroxide to 60-90 ℃, uniformly stirring and reacting for 5-8h, adding triethanolamine to adjust the pH value of the solution to be neutral, adding epoxy resin curing agent, pouring the solution into a film-forming mold to be cured into a film, and preparing the TiO2The nanowire modified epoxy acrylic resin anticorrosive coating.
Example 1
(1) Preparation of hydroxylated porous TiO2Nanowire component 1: the full-automatic reaction kettle comprises a kettle body, a heat-insulating inner container is arranged in the kettle body, an air inlet pipe is fixedly connected to the left side of the kettle body and movably connected with an air inlet valve, the air inlet pipe is movably connected with an air pump, an air outlet pipe is fixedly connected to the right side of the kettle body and movably connected with an air outlet valve, a feeding hole is fixedly connected to the upper left side of the kettle body, a stirring device is fixedly connected to the upper side of the kettle body and movably connected with a connecting ball, the connecting ball is fixedly connected with a stirring rod, stirring fan blades are arranged on the surface of the stirring rod, a discharge port is fixedly connected to the lower side of the kettle body and fixedly connected with a control valve, a base is movably connected to the outer part of the kettle body,the method comprises the following steps of movably connecting a roller below a base, adding an ethylene glycol solvent and titanium tetrachloride, heating to 160 ℃, uniformly stirring for reaction for 2 hours, cooling a solution to room temperature, filtering to remove the solvent, washing a solid product with distilled water and ethanol, placing the solid product into a distilled water solvent, uniformly stirring for reaction for 1 hour at 90 ℃, filtering the solution to remove the solvent, washing the solid product with distilled water, fully drying, and preparing the hydroxylated porous TiO2Nanowire component 1.
(2) Preparation of modified hydroxylated TiO2Nanowire component 1: adding distilled water and an ethanol solvent into a reaction bottle, wherein the volume ratio of the distilled water to the ethanol solvent is 15:1, and adding hydroxylated porous TiO2The nanowire component 1 is added with silane coupling agent vinyl trimethoxy silane after being dispersed uniformly by ultrasonic, and is mixed with hydroxylated porous TiO2The mass ratio of the nano-wire is 1:18, the nano-wire is heated to 40 ℃, the nano-wire is stirred at a constant speed for reaction for 5 hours, the solution is filtered to remove the solvent, the solid product is washed by distilled water and fully dried to prepare the modified hydroxylated TiO grafted by the silane coupling agent2Nanowire component 1.
(3) Preparation of TiO2Nanowire-modified epoxy acrylic resin anticorrosive coating material 1: adding 80 parts of epoxy resin into a reaction bottle, heating to 50 ℃, adding 2 parts of maleic anhydride and 0.5 part of tetrabutylammonium bromide serving as a catalyst, stirring at a constant speed for reaction for 4 hours, adding an acetone solvent, stirring for dissolution, adding 4 parts of hydroxyethyl acrylate, 10 parts of methyl methacrylate and 1 part of modified hydroxylated TiO2The preparation method comprises the following steps of heating the nanowire component 1 and 1.5 parts of initiator dibenzoyl peroxide to 60 ℃, uniformly stirring and reacting for 5 hours, adding triethanolamine to adjust the pH value of the solution to be neutral, adding an epoxy resin curing agent, pouring the solution into a film forming mold to be cured into a film, and preparing TiO2A nanowire modified epoxy acrylic resin anticorrosive coating material 1.
Example 2
(1) Preparation of hydroxylated porous TiO2Nanowire component 2: the full-automatic reaction kettle comprises a kettle body, a heat preservation inner container arranged in the kettle body, an air inlet pipe fixedly connected to the left side of the kettle body, an air inlet pipe movably connected with an air inlet valve, and an air inlet pipe movably connected with the air inlet valveThe device is connected with an air pump, the right side of the kettle body is fixedly connected with an air outlet pipe, the air outlet pipe is movably connected with an air outlet valve, the upper left side of the kettle body is fixedly connected with a feeding hole, the upper side of the kettle body is fixedly connected with a stirring device, the stirring device is movably connected with a connecting ball, the connecting ball is fixedly connected with a stirring rod, the surface of the stirring rod is provided with a stirring fan blade, the lower side of the kettle body is fixedly connected with a discharging hole, the discharging hole is fixedly connected with a control valve, the outer part of the kettle body is movably connected with a base, the lower side of the base is movably connected with a roller, ethylene glycol solvent and titanium tetrachloride are added, the heating is carried out to 160 ℃, the stirring reaction is carried out at a constant speed for 4 hours, the solution is cooled to room temperature, the solvent is removed by filtration, the solid product is, fully drying to prepare the hydroxylated porous TiO2Nanowire component 2.
(2) Preparation of modified hydroxylated TiO2Nanowire component 2: adding distilled water and an ethanol solvent into a reaction bottle, wherein the volume ratio of the distilled water to the ethanol solvent is 20:1, and adding hydroxylated porous TiO2The nano-wire component 2 is added with silane coupling agent vinyl trimethoxy silane after being dispersed evenly by ultrasonic, and is mixed with hydroxylated porous TiO2The mass ratio of the nano-wire is 1:18, the nano-wire is heated to 40 ℃, the nano-wire is stirred at a constant speed for reaction for 10 hours, the solution is filtered to remove the solvent, the solid product is washed by distilled water and fully dried to prepare the modified hydroxylated TiO grafted by the silane coupling agent2Nanowire component 2.
(3) Preparation of TiO2Nanowire modified epoxy acrylic resin anticorrosive coating material 2: adding 75 parts of epoxy resin into a reaction bottle, heating to 50 ℃, adding 2.4 parts of maleic anhydride and 0.6 part of tetrabutylammonium bromide serving as a catalyst, stirring at a constant speed for reaction for 6 hours, adding an acetone solvent, stirring for dissolution, adding 5 parts of hydroxyethyl acrylate, 11 parts of methyl methacrylate and 2 parts of modified hydroxylated TiO2The preparation method comprises the following steps of heating the nanowire component 2 and 2 parts of initiator dibenzoyl peroxide to 90 ℃, uniformly stirring and reacting for 8 hours, adding triethanolamine to adjust the pH value of the solution to be neutral, adding an epoxy resin curing agent, pouring the solution into a film forming mold to be cured into a film, and preparing TiO2And (3) a nanowire modified epoxy acrylic resin anticorrosive coating material 2.
Example 3
(1) Preparation of hydroxylated porous TiO2Nanowire component 3: introducing nitrogen into a full-automatic reaction kettle to discharge air, wherein the full-automatic reaction kettle comprises a kettle body, a heat-insulating inner container is arranged in the kettle body, an air inlet pipe is fixedly connected to the left side of the kettle body and is movably connected with an air inlet valve, an air pump is movably connected with the air inlet pipe, an air outlet pipe is fixedly connected to the right side of the kettle body and is movably connected with an air outlet valve, a feeding hole is fixedly connected to the upper left side of the kettle body, a stirring device is fixedly connected to the upper side of the kettle body and is movably connected with a connecting ball, the connecting ball is fixedly connected with a stirring rod, stirring fan blades are arranged on the surface of the stirring rod, a discharging port is fixedly connected to the lower side of the kettle body and is fixedly connected with a control valve, a base is movably connected to the outer part of the kettle body, rollers are movably connected to the lower side of the base, filtering to remove the solvent, washing the solid product with distilled water and ethanol, placing the solid product in a distilled water solvent, stirring at a constant speed for reaction for 2 hours at 100 ℃, filtering the solution to remove the solvent, washing the solid product with distilled water, and fully drying to prepare the hydroxylated porous TiO2Nanowire component 3.
(2) Preparation of modified hydroxylated TiO2Nanowire component 3: adding distilled water and an ethanol solvent into a reaction bottle, wherein the volume ratio of the distilled water to the ethanol solvent is 18:1, and adding hydroxylated porous TiO2The nano-wire component 3 is added with silane coupling agent vinyl trimethoxy silane after being dispersed evenly by ultrasonic, and is mixed with hydroxylated porous TiO2The mass ratio of the nano-wire is 1:22, the nano-wire is heated to 50 ℃, the nano-wire is stirred at a constant speed for reaction for 8 hours, the solution is filtered to remove the solvent, the solid product is washed by distilled water and fully dried to prepare the modified hydroxylated TiO grafted by the silane coupling agent2Nanowire component 3.
(3) Preparation of TiO2Nanowire-modified epoxy acrylic resin anticorrosive coating material 3: 73 parts of epoxy resin are added to a reaction flask, after heating to 60 ℃ 3.3 parts of maleic anhydride and 0.7 part of catalyst are addedTetrabutylammonium bromide is used as a reagent, stirred at a constant speed for reaction for 5 hours, then acetone solvent is added, and after stirring and dissolution, 6 parts of hydroxyethyl acrylate, 12.5 parts of methyl methacrylate and 2.5 parts of modified hydroxylated TiO are added2The preparation method comprises the following steps of heating the nanowire component 3 and 2 parts of initiator dibenzoyl peroxide to 75 ℃, uniformly stirring and reacting for 7 hours, adding triethanolamine to adjust the pH value of the solution to be neutral, adding an epoxy resin curing agent, pouring the solution into a film forming mold to be cured into a film, and preparing TiO2And 3, a nanowire modified epoxy acrylic resin anticorrosive coating material.
Example 4
(1) Preparation of hydroxylated porous TiO2Nanowire component 4: introducing nitrogen into a full-automatic reaction kettle to discharge air, wherein the full-automatic reaction kettle comprises a kettle body, a heat-insulating inner container is arranged in the kettle body, an air inlet pipe is fixedly connected to the left side of the kettle body and is movably connected with an air inlet valve, an air pump is movably connected with the air inlet pipe, an air outlet pipe is fixedly connected to the right side of the kettle body and is movably connected with an air outlet valve, a feeding hole is fixedly connected to the upper left side of the kettle body, a stirring device is fixedly connected to the upper side of the kettle body and is movably connected with a connecting ball, the connecting ball is fixedly connected with a stirring rod, stirring fan blades are arranged on the surface of the stirring rod, a discharging port is fixedly connected to the lower side of the kettle body and is fixedly connected with a control valve, a base is movably connected to the outer part of the kettle body, rollers are movably connected to the lower side of the base, filtering to remove the solvent, washing the solid product with distilled water and ethanol, placing the solid product in a distilled water solvent, stirring at a constant speed for reaction for 4 hours at 110 ℃, filtering the solution to remove the solvent, washing the solid product with distilled water, and fully drying to prepare the hydroxylated porous TiO2Nanowire component 4.
(2) Preparation of modified hydroxylated TiO2Nanowire component 4: adding distilled water and an ethanol solvent into a reaction bottle, wherein the volume ratio of the distilled water to the ethanol solvent is 15:1, and adding hydroxylated porous TiO 24, adding silane coupling agent vinyl trimethoxy silane and hydroxylated porous TiO after ultrasonic dispersion is uniform2The mass ratio of the nanowires was 1:18,heating to 60 ℃, stirring at a constant speed for reaction for 10 hours, filtering the solution to remove the solvent, washing the solid product with distilled water, and fully drying to prepare the modified hydroxylated TiO grafted by the silane coupling agent2Nanowire component 4.
(3) Preparation of TiO2Nanowire-modified epoxy acrylic resin anticorrosive coating material 4: adding 68 parts of epoxy resin into a reaction bottle, heating to 50 ℃, adding 4.2 parts of maleic anhydride and 0.8 part of tetrabutylammonium bromide serving as a catalyst, stirring at a constant speed for reaction for 4 hours, adding an acetone solvent, stirring for dissolution, adding 7 parts of hydroxyethyl acrylate, 14 parts of methyl methacrylate and 3.5 parts of modified hydroxylated TiO 24 parts of nanowire component and 2.5 parts of initiator dibenzoyl peroxide, heating to 90 ℃, uniformly stirring for reaction for 8 hours, adding triethanolamine to adjust the pH value of the solution to be neutral, adding epoxy resin curing agent, pouring the solution into a film forming mold for curing and film forming, and preparing the TiO2And 4, a nanowire modified epoxy acrylic resin anticorrosive coating material.
Example 5
(1) Preparation of hydroxylated porous TiO2Nanowire component 5: introducing nitrogen into a full-automatic reaction kettle to discharge air, wherein the full-automatic reaction kettle comprises a kettle body, a heat-insulating inner container is arranged in the kettle body, an air inlet pipe is fixedly connected to the left side of the kettle body and is movably connected with an air inlet valve, an air pump is movably connected with the air inlet pipe, an air outlet pipe is fixedly connected to the right side of the kettle body and is movably connected with an air outlet valve, a feeding hole is fixedly connected to the upper left side of the kettle body, a stirring device is fixedly connected to the upper side of the kettle body and is movably connected with a connecting ball, the connecting ball is fixedly connected with a stirring rod, stirring fan blades are arranged on the surface of the stirring rod, a discharging port is fixedly connected to the lower side of the kettle body and is fixedly connected with a control valve, a base is movably connected to the outer part of the kettle body, rollers are movably connected to the lower side of the base, filtering to remove solvent, washing solid product with distilled water and ethanol, placing in distilled water solvent, stirring at uniform speed at 110 deg.C for 4 hr, filtering the solution to remove solvent, washing solid product with distilled water, and drying thoroughlyDrying to prepare the hydroxylated porous TiO2Nanowire component 5.
(2) Preparation of modified hydroxylated TiO2Nanowire component 5: adding distilled water and an ethanol solvent into a reaction bottle, wherein the volume ratio of the distilled water to the ethanol solvent is 20:1, and adding hydroxylated porous TiO2The nanowire component 5 is added with silane coupling agent vinyl trimethoxy silane and hydroxylated porous TiO after being uniformly dispersed by ultrasonic2The mass ratio of the nano-wire is 1:25, the nano-wire is heated to 60 ℃, the nano-wire is stirred at a constant speed for reaction for 0h, the solution is filtered to remove the solvent, the solid product is washed by distilled water and fully dried to prepare the modified hydroxylated TiO grafted by the silane coupling agent2Nanowire component 5.
(3) Preparation of TiO2Nanowire-modified epoxy acrylic resin anticorrosive coating material 5: adding 64 parts of epoxy resin into a reaction bottle, heating to 70 ℃, adding 5 parts of maleic anhydride and 1 part of tetrabutylammonium bromide serving as a catalyst, stirring at a constant speed for reaction for 6 hours, adding an acetone solvent, stirring for dissolution, and adding 8 parts of hydroxyethyl acrylate, 15 parts of methyl methacrylate and 4 parts of modified hydroxylated TiO2The preparation method comprises the following steps of heating the nanowire component 5 and 3 parts of initiator dibenzoyl peroxide to 90 ℃, uniformly stirring and reacting for 8 hours, adding triethanolamine to adjust the pH value of the solution to be neutral, adding an epoxy resin curing agent, pouring the solution into a film forming mold to be cured into a film, and preparing TiO2And (3) a nanowire modified epoxy acrylic resin anticorrosive coating material 5.
Testing of TiO in examples 1-5 Using an SC-500 salt fog Chamber test Chamber2The salt spray resistance of the nanowire modified epoxy acrylic resin anticorrosive coating material is tested according to the standard HG/T4759-2014.
In summary, the TiO2Nanowire modified epoxy acrylic resin anticorrosive coating, ethylene glycol as mediation, and Ti4+Forming linear chain complex, and preparing the hydroxylated TiO by a hot solvent method and a hydrolysis method2Nanowires, having a large number of hydroxyl structures on the surface, using a very small amount of vinyltrisMethoxysilanes, with hydroxylated TiO2The reaction is carried out, thereby obtaining the vinyltrimethoxysilane modified hydroxylated TiO with high grafting rate2Nanowires, hydroxylated TiO2Forms a three-dimensional hydrogen bond network with hydroxyethyl acrylate and the like, is adsorbed by the hydroxyethyl acrylate and the like, and can promote the vinyltrimethoxysilane to modify the hydroxylated TiO2The nanowires undergo a cross-linking polymerization reaction.
Maleic anhydride is used for self-opening and reacts with epoxy groups of epoxy resin under the action of a catalyst to obtain alkenyl epoxy resin, and then the alkenyl epoxy resin is reacted with methyl methacrylate, hydroxyethyl acrylate and modified hydroxylated TiO by an alkenyl free radical polymerization method2The mutual crosslinking polymerization of alkenyl of vinyl trimethoxy silane in the nano-wire greatly improves TiO through the crosslinking effect of chemical bonds rather than the physical blending effect2The dispersibility and compatibility of the nano wire in the epoxy resin can obtain the epoxy acrylic resin coating, thereby avoiding the uneven dispersion of the nano TiO2Can affect the mechanical properties of the epoxy resin such as toughness, wear resistance and the like, and meanwhile, TiO2The nano wires endow the epoxy resin coating with excellent antibacterial performance and microbial corrosion resistance, and the acrylic resin and the epoxy resin are crosslinked and polymerized to form the epoxy acrylic resin, so that good hydrophilicity and water resistance are endowed.
Claims (7)
1. TiO 22The nanowire modified epoxy acrylic resin anticorrosive coating comprises the following formula raw materials and components in parts by weight, and is characterized in that: 1-4 parts of modified hydroxylated TiO2The nano-wire, 64-81 parts of epoxy resin, 10-15 parts of methyl methacrylate, 4-8 parts of hydroxyethyl acrylate, 1.5-3 parts of initiator, 2-5 parts of maleic anhydride and 0.5-1 part of catalyst.
2. A TiO according to claim 12The nanowire modified epoxy acrylic resin anticorrosive coating is characterized in that: the initiator is dibenzoyl peroxide.
3. A Ti according to claim 1O2The nanowire modified epoxy acrylic resin anticorrosive coating is characterized in that: the catalyst is tetrabutylammonium bromide.
4. A TiO according to claim 12The nanowire modified epoxy acrylic resin anticorrosive coating is characterized in that: the modified hydroxylated TiO2The preparation method of the nanowire comprises the following steps:
(1) introducing nitrogen into a full-automatic reaction kettle to discharge air, adding an ethylene glycol solvent and titanium tetrachloride, heating to 190 ℃ for 2-4h, filtering the solution, washing a solid product, placing the solid product into a distilled water solvent, reacting for 1-4h at 90-110 ℃, filtering, washing and drying the solution to prepare the hydroxylated porous TiO2A nanowire;
(2) adding hydroxylated porous TiO into a mixed solvent of distilled water and ethanol with a volume ratio of 15-20:12Uniformly dispersing nanowires by ultrasonic, adding a silane coupling agent, heating to 40-60 ℃, reacting for 5-10h, filtering, washing and drying to obtain the modified hydroxylated TiO grafted by the silane coupling agent2A nanowire.
5. A TiO according to claim 42The nanowire modified epoxy acrylic resin anticorrosive coating is characterized in that: the silane coupling agent is vinyl trimethoxy silane and hydroxylated porous TiO2The mass ratio of the nano wire to the vinyl trimethoxy silane is 18-25: 1.
6. A TiO according to claim 42The nanowire modified epoxy acrylic resin anticorrosive coating is characterized in that: full-automatic reation kettle includes the cauldron body, the internal portion of cauldron is provided with the left side fixedly connected with intake pipe, intake pipe and the valve swing joint that admits air of heat preservation inner bag, the cauldron body, intake pipe swing joint has the air pump, the right side fixedly connected with outlet duct, outlet duct and the valve swing joint that gives vent to anger of the cauldron body, the upper left side fixedly connected with feed port of the cauldron body, the top fixedly connected with agitating unit of the cauldron body, agitating unit and connection ball swing joint, connection ballWith puddler fixed connection, the puddler surface is provided with the stirring fan piece, the below fixedly connected with discharge gate of the cauldron body, discharge gate and control flap fixed connection, the outside swing joint of the cauldron body has the base, the below swing joint of base has the gyro wheel.
7. A TiO according to claim 12The nanowire modified epoxy acrylic resin anticorrosive coating is characterized in that: the TiO is2The preparation method of the nanowire modified epoxy acrylic resin anticorrosive coating comprises the following steps:
(1) adding 64-80 parts of epoxy resin into a reaction bottle, heating to 50-70 ℃, adding 2-5 parts of maleic anhydride and 0.5-1 part of tetrabutylammonium bromide serving as a catalyst, reacting for 4-6h, adding an acetone solvent, stirring to dissolve, adding 4-8 parts of hydroxyethyl acrylate, 10-15 parts of methyl methacrylate and 1-4 parts of modified hydroxylated TiO2Heating the nanowire and 1.5-3 parts of initiator dibenzoyl peroxide to 60-90 ℃, stirring for reaction for 5-8h, adding triethanolamine to adjust the pH value of the solution to be neutral, adding epoxy resin curing agent, pouring the solution into a film-forming mold for curing and film-forming to prepare TiO2The nanowire modified epoxy acrylic resin anticorrosive coating.
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