CN112391101A - Antirust spray paint for protecting iron braided product and preparation method thereof - Google Patents
Antirust spray paint for protecting iron braided product and preparation method thereof Download PDFInfo
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- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D163/00—Coating compositions based on epoxy resins; Coating compositions based on derivatives of epoxy resins
- C09D163/10—Epoxy resins modified by unsaturated compounds
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/08—Processes
- C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
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- C08G18/584—Epoxy resins having nitrogen
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- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
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- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
- C08G18/76—Polyisocyanates or polyisothiocyanates cyclic aromatic
- C08G18/7614—Polyisocyanates or polyisothiocyanates cyclic aromatic containing only one aromatic ring
- C08G18/7621—Polyisocyanates or polyisothiocyanates cyclic aromatic containing only one aromatic ring being toluene diisocyanate including isomer mixtures
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- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/32—Phosphorus-containing compounds
- C08K2003/321—Phosphates
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Abstract
The invention discloses an antirust spray paint for protecting iron braided products and a preparation method thereof, wherein the antirust spray paint comprises the following raw materials in parts by weight: 35-55 parts of modified epoxy resin, 10-20 parts of antirust composite filler, 3-10 parts of iron oxide red powder, 0.1-0.5 part of THIX-278 water-based defoaming agent, 10-20 parts of dimethylbenzene, 0.5-1 part of sodium carboxymethylcellulose and 20-30 parts of deionized water; ball-milling the prepared slurry to 50 mu m, then adding the slurry into modified epoxy resin, dispersing for 30min, adding a THIX-278 aqueous defoaming agent, continuing dispersing for 10min, dropwise adding ammonia water with the mass fraction of 10% to adjust the pH until the pH is 8, and preparing the antirust spray paint for protecting the iron knitted product; when the filler acts on the metal surface, an adsorption layer can be formed and attached to the metal surface, so that the metal is prevented from contacting with water, electrochemical corrosion of the metal is prevented, and the filler has excellent antirust performance.
Description
Technical Field
The invention belongs to the technical field of coatings, and particularly relates to an antirust spray paint for protecting iron braided products and a preparation method thereof.
Background
At present, the most commonly used antirust coatings are polyethylene-based, epoxy resin-based, polyurethane-based and the like, but the existing antirust coatings have the problems of poor heat resistance and weather resistance, poor adhesion, short anticorrosion time and the like. Meanwhile, the existing paint mostly adopts organic solvent which is harmful to the environment. Therefore, the development of the antirust coating which has no pollution to the environment and strong adhesion to the base material is of great significance.
The Chinese patent CN107129748A discloses a nano-material composite unsaturated polyester antirust paint and a preparation method thereof, the antirust paint is prepared from nano-material composite unsaturated polyester resin, deionized water, a stabilizer and amino resin, and the preparation process comprises the following steps: (1) preparing modified montmorillonite with nano montmorillonite, deionized water and intercalation agent; (2) synthesizing nano-material composite unsaturated polyester resin by taking isophthalic acid, polyether glycol, ethylene glycol, methacrylic acid, styrene and modified montmorillonite as raw materials and dibutyltin dilaurate as a catalyst; (3) adding the nano-material composite unsaturated polyester resin into the amino resin, uniformly stirring, adding deionized water and a stabilizer, and uniformly stirring again to obtain the nano-material composite unsaturated polyester antirust paint.
Disclosure of Invention
In order to overcome the technical problems, the invention provides an antirust paint for protecting iron braided products and a preparation method thereof.
The technical problems to be solved by the invention are as follows:
at present, the most commonly used antirust coatings are polyethylene-based, epoxy resin-based, polyurethane-based and the like, but the existing antirust coatings have the problems of poor adhesion, short anticorrosion time and the like.
The purpose of the invention can be realized by the following technical scheme:
the rust-proof spray paint for protecting the iron braided product comprises the following raw materials in parts by weight: 35-55 parts of modified epoxy resin, 10-20 parts of antirust composite filler, 3-10 parts of iron oxide red powder, 0.1-0.5 part of defoaming agent, 10-20 parts of dimethylbenzene, 0.5-1 part of thickening agent and 20-30 parts of deionized water;
the rust-proof spray paint for protecting the iron braided product is prepared by the following method:
firstly, adding iron oxide red powder, an antirust composite filler and xylene into deionized water, stirring at a high speed of 500r/min for 30min at a speed of 450-;
and secondly, ball-milling the prepared slurry to 50-60 mu m, adding the slurry into modified epoxy resin, dispersing for 30-45min, adding a defoaming agent, continuously dispersing for 10min, dropwise adding ammonia water with the mass fraction of 10% to adjust the pH until the pH is 8-9, and thus obtaining the antirust spray paint for protecting the iron knitted product.
Further, the defoaming agent is a THIX-278 water-based defoaming agent, and the thickening agent is one or two of sodium carboxymethylcellulose and propylene glycol sodium alginate which are mixed according to any proportion.
Further, the modified epoxy resin is prepared by the following method:
step S1, adding bisphenol A and epichlorohydrin into a three-neck flask, introducing nitrogen, heating in a water bath at 40-50 ℃, uniformly stirring and dropwise adding 1, 6-hexamethylene diisocyanate at a rotation speed of 120r/min, controlling the dropwise adding time to be 20min, uniformly stirring and reacting for 2h after the dropwise adding is finished, heating to 60-70 ℃, adding a sodium hydroxide solution with a mass fraction of 20%, continuously stirring and reacting for 2h, washing with deionized water for 3 times, standing and layering, collecting an organic phase, and carrying out reduced pressure distillation until no fraction appears to prepare the aqueous epoxy resin, wherein in step S1, the weight ratio of the bisphenol A, the epichlorohydrin, the 1, 6-hexamethylene diisocyanate and the sodium hydroxide solution is controlled to be 1: 5: 0.5: 0.3-0.5;
step S2, adding hydroxyl-terminated polybutadiene into a three-neck flask, heating at 90-100 ℃ for 10min, vacuum degassing, cooling to 40-50 ℃, adding toluene diisocyanate, heating to 90-100 ℃ at a heating rate of 5 ℃/min, reacting at the temperature for 3h, vacuum degassing for 15min, terminating the reaction, and vacuumizing to obtain a prepolymer, wherein the weight ratio of the hydroxyl-terminated polybutadiene to the toluene diisocyanate is controlled to be 1: 1;
and S3, adding the prepolymer prepared in the step S2 into the waterborne epoxy resin prepared in the step S1, heating in a water bath at 90-100 ℃, stirring at the rotating speed of 150-.
Step S1, mixing bisphenol A and 1, 6-hexamethylene diisocyanate in epichlorohydrin, reacting bisphenol A and 1, 6-hexamethylene diisocyanate to generate a reaction product, reacting the reaction product with epichlorohydrin under the action of sodium hydroxide to generate epoxy resin, wherein one part of epichlorohydrin is used as a solvent, and the other part of epichlorohydrin is used as a reactant, step S2, adding hydroxyl-terminated polybutadiene into a three-neck flask, cooling to dehydrate the hydroxyl-terminated polybutadiene after vacuum degassing, preventing side reaction in the system caused by water, preparing a prepolymer, mixing epoxy resin and prepolymer in step S3, reacting isocyanate groups on the prepolymer with hydroxyl groups on the epoxy resin, grafting the prepolymer into an epoxy resin curing network when the hydroxyl groups on the epoxy resin are more than the isocyanate groups, adding the epoxy resin into the three-neck flask during the reaction process, the temperature is increased to 95-100 ℃ for dehydration, so that the generation of side reaction in the system is prevented, the reaction efficiency is improved, the toughness and the bonding property of the epoxy resin can be obviously improved by grafting the prepolymer on the epoxy resin, and the prepared antirust paint has excellent adhesiveness.
Further, the antirust composite filler is prepared by the following method:
step S11, adding calcium oxide into a three-neck flask, adding deionized water, dropwise adding 60 mass percent phosphoric acid aqueous solution after stirring at a constant speed for 30min, controlling the dropwise adding time to be 15min, continuously stirring for 30min after dropwise adding to prepare intermediate emulsion, adding barium sulfate and talcum powder into the intermediate emulsion, stirring for 30min at a rotating speed of 150 plus 200r/min to prepare suspension, then adding nano titanium dioxide and 10 mass percent barium chloride solution into the suspension, heating to 80-100 ℃, stirring at a constant speed for 35min, then carrying out vacuum filtration, placing a filter cake into a drying oven at 100 ℃ for drying for 4h, then transferring into a muffle furnace, roasting for 10h at 300 ℃ to prepare doped filler, controlling the weight ratio of the calcium oxide, the phosphoric acid aqueous solution, the barium sulfate, the talcum powder and the deionized water to be 3: 1: 10-15, the weight ratio of the calcium oxide to the nano titanium dioxide to the barium chloride solution is 1: 2: 0.1-0.5;
step S12, adding fatty acid into a three-neck flask, heating to 110-.
A preparation method of an antirust spray paint for protecting an iron braided product comprises the following steps:
firstly, adding iron oxide red powder, an antirust composite filler and xylene into deionized water, stirring at a high speed of 500r/min for 30min at a speed of 450-;
and secondly, ball-milling the prepared slurry to 50-60 mu m, adding the slurry into modified epoxy resin, dispersing for 30-45min, adding a defoaming agent, continuously dispersing for 10min, dropwise adding ammonia water with the mass fraction of 10% to adjust the pH until the pH is 8-9, and thus obtaining the antirust spray paint for protecting the iron knitted product.
The invention has the beneficial effects that:
(1) the invention relates to an antirust spray paint for protecting iron-braided products, which is prepared by taking modified epoxy resin and antirust composite filler as raw materials, mixing bisphenol A and 1, 6-hexamethylene diisocyanate in epichlorohydrin in a step S1 in the preparation process of the modified epoxy resin, reacting the bisphenol A and the 1, 6-hexamethylene diisocyanate to generate a reaction product, reacting the reaction product with the epichlorohydrin under the action of sodium hydroxide to generate epoxy resin, wherein one part of the epichlorohydrin is used as a solvent, the other part of the epichlorohydrin can be used as a reactant, adding hydroxyl-terminated polybutadiene into a three-neck flask in a step S2, cooling and dehydrating the hydroxyl-terminated polybutadiene after vacuum degassing to prevent side reaction in a system due to the occurrence of water, preparing a prepolymer, mixing the epoxy resin and the prepolymer in the step S3, and reacting isocyanate groups on the prepolymer with hydroxyl groups on the epoxy resin, the prepolymer can be grafted in an epoxy resin curing network when the hydroxyl on the epoxy resin is more than the isocyanate group, the epoxy resin is firstly added into a three-neck flask in the reaction process, the temperature is raised to 95-100 ℃ for dehydration, the side reaction in the system is prevented, the reaction efficiency is improved, the toughness and the bonding property of the prepared antirust paint can be obviously improved when the prepolymer is grafted on the epoxy resin, and the prepared antirust paint has excellent adhesiveness.
(2) The invention prepares an antirust composite filler, the antirust composite filler is prepared by mixing calcium oxide and phosphoric acid solution in the preparation process, reacting to generate an intermediate, the intermediate is calcium hydroxy phosphate, then mixing suspension prepared by the intermediate with nano titanium dioxide to prepare a doped filler, the nano titanium dioxide is a dispersed phase and is coated on the surface of the calcium hydroxy phosphate, so that the doped filler has excellent antirust performance, then a reaction product is prepared by fatty acid and diethanol amine, boric acid is added and then the doped filler is mixed to prepare the antirust composite filler, and an adsorption layer can be formed and attached to the surface of metal when the filler acts on the surface of the metal, so that the metal is prevented from contacting with water, electrochemical corrosion of the metal is prevented, and the antirust composite filler has excellent antirust performance.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1
The rust-proof spray paint for protecting the iron braided product comprises the following raw materials in parts by weight: 35 parts of modified epoxy resin, 10 parts of antirust composite filler, 3 parts of iron oxide red powder, 0.1 part of THIX-278 water-based defoaming agent, 10 parts of dimethylbenzene, 0.5 part of sodium carboxymethylcellulose and 20 parts of deionized water;
the rust-proof spray paint for protecting the iron braided product is prepared by the following method:
firstly, adding iron oxide red powder, an antirust composite filler and xylene into deionized water, stirring at a high speed of 450r/min for 30min, adding sodium carboxymethylcellulose after stirring is finished, and continuing stirring for 30min to prepare slurry;
and secondly, ball-milling the prepared slurry to 50 microns, adding the slurry into modified epoxy resin, dispersing for 30min, adding a THIX-278 aqueous defoaming agent, continuously dispersing for 10min, dropwise adding ammonia water with the mass fraction of 10% to adjust the pH until the pH is 8, and thus obtaining the antirust spray paint for protecting the iron knitted product.
The modified epoxy resin is prepared by the following method:
step S1, adding bisphenol A and epichlorohydrin into a three-neck flask, introducing nitrogen, heating in a water bath at 40 ℃, uniformly stirring at a rotating speed of 100r/min and dropwise adding 1, 6-hexamethylene diisocyanate, controlling the dropwise adding time to be 20min, uniformly stirring and reacting for 2h after the dropwise adding is finished, heating to 60 ℃, adding a sodium hydroxide solution with the mass fraction of 20%, continuously stirring and reacting for 2h, washing with deionized water for 3 times, standing and layering, collecting an organic phase, and distilling under reduced pressure until no fraction appears to prepare the waterborne epoxy resin, wherein in step S1, the weight ratio of the bisphenol A, the epichlorohydrin, the 1, 6-hexamethylene diisocyanate and the sodium hydroxide solution is controlled to be 1: 5: 0.5: 0.3;
step S2, adding hydroxyl-terminated polybutadiene into a three-neck flask, heating at 90 ℃ for 10min, vacuum degassing, cooling to 40 ℃, adding toluene diisocyanate, heating to 90 ℃ at a heating rate of 5 ℃/min, reacting at the temperature for 3h, vacuum degassing for 15min, terminating the reaction, and vacuumizing to obtain a prepolymer, wherein the weight ratio of the hydroxyl-terminated polybutadiene to the toluene diisocyanate is controlled to be 1: 1;
and S3, adding the prepolymer prepared in the step S2 into the waterborne epoxy resin prepared in the step S1, heating in water bath at 90 ℃, stirring at the rotating speed of 150r/min for 30min, cooling to 40 ℃, continuously stirring and reacting for 30min to prepare the modified epoxy resin, wherein the weight ratio of the waterborne epoxy resin to the prepolymer is controlled to be 1: 0.5.
The antirust composite filler is prepared by the following method:
step S11, adding calcium oxide into a three-neck flask, adding deionized water, stirring at constant speed for 30min, then adding 60% phosphoric acid aqueous solution dropwise, controlling the dropwise adding time to be 15min, continuing stirring for 30min after the dropwise adding is finished to prepare intermediate emulsion, adding barium sulfate and talcum powder into the intermediate emulsion, stirring for 30min at the rotating speed of 150r/min to prepare a suspension, then adding nano titanium dioxide and a barium chloride solution with the mass fraction of 10 percent into the suspension, heating to 80 ℃, stirring at constant speed for 35min at the temperature, then performing vacuum filtration, drying the filter cake in a drying oven at 100 ℃ for 4h, then transferring to a muffle furnace, roasting at 300 ℃ for 10h to prepare a doped filler, wherein the weight ratio of calcium oxide, aqueous solution of phosphoric acid, barium sulfate, talcum powder and deionized water is controlled to be 3: 1: 10, and the weight ratio of calcium oxide, nano titanium dioxide and barium chloride solution is controlled to be 1: 2: 0.1;
step S12, adding fatty acid into a three-neck flask, heating to 100 ℃, preserving heat for 30min at the temperature, then adding diethanolamine, uniformly stirring, heating to 140 ℃, reacting at the temperature, detecting the amine value of the system until the amine value is more than 30mgKOH/g, stopping the reaction to obtain a reaction product, transferring the reaction product and boric acid into the beaker for mixing, heating to 120 ℃, preserving heat at the temperature and reacting for 4h, then adding a doped filler, and uniformly stirring for 2h to obtain the antirust composite filler, wherein the weight ratio of the substances of the fatty acid, the diethanolamine and the boric acid is controlled to be 3: 1: 3, and the weight ratio of the reaction product to the doped filler is 1: 3.
Example 2
The rust-proof spray paint for protecting the iron braided product comprises the following raw materials in parts by weight: 40 parts of modified epoxy resin, 14 parts of antirust composite filler, 5 parts of iron oxide red powder, 0.3 part of THIX-278 water-based defoaming agent, 14 parts of dimethylbenzene, 0.6 part of sodium carboxymethylcellulose and 24 parts of deionized water;
the rust-proof spray paint for protecting the iron braided product is prepared by the following method:
firstly, adding iron oxide red powder, an antirust composite filler and xylene into deionized water, stirring at a high speed of 450r/min for 30min, adding sodium carboxymethylcellulose after stirring is finished, and continuing stirring for 30min to prepare slurry;
and secondly, ball-milling the prepared slurry to 50 microns, adding the slurry into modified epoxy resin, dispersing for 30min, adding a THIX-278 aqueous defoaming agent, continuously dispersing for 10min, dropwise adding ammonia water with the mass fraction of 10% to adjust the pH until the pH is 8, and thus obtaining the antirust spray paint for protecting the iron knitted product.
The modified epoxy resin is prepared by the following method:
step S1, adding bisphenol A and epichlorohydrin into a three-neck flask, introducing nitrogen, heating in a water bath at 40 ℃, uniformly stirring at a rotating speed of 100r/min and dropwise adding 1, 6-hexamethylene diisocyanate, controlling the dropwise adding time to be 20min, uniformly stirring and reacting for 2h after the dropwise adding is finished, heating to 60 ℃, adding a sodium hydroxide solution with the mass fraction of 20%, continuously stirring and reacting for 2h, washing with deionized water for 3 times, standing and layering, collecting an organic phase, and distilling under reduced pressure until no fraction appears to prepare the waterborne epoxy resin, wherein in step S1, the weight ratio of the bisphenol A, the epichlorohydrin, the 1, 6-hexamethylene diisocyanate and the sodium hydroxide solution is controlled to be 1: 5: 0.5: 0.3;
step S2, adding hydroxyl-terminated polybutadiene into a three-neck flask, heating at 90 ℃ for 10min, vacuum degassing, cooling to 40 ℃, adding toluene diisocyanate, heating to 90 ℃ at a heating rate of 5 ℃/min, reacting at the temperature for 3h, vacuum degassing for 15min, terminating the reaction, and vacuumizing to obtain a prepolymer, wherein the weight ratio of the hydroxyl-terminated polybutadiene to the toluene diisocyanate is controlled to be 1: 1;
and S3, adding the prepolymer prepared in the step S2 into the waterborne epoxy resin prepared in the step S1, heating in water bath at 90 ℃, stirring at the rotating speed of 150r/min for 30min, cooling to 40 ℃, continuously stirring and reacting for 30min to prepare the modified epoxy resin, wherein the weight ratio of the waterborne epoxy resin to the prepolymer is controlled to be 1: 0.5.
The antirust composite filler is prepared by the following method:
step S11, adding calcium oxide into a three-neck flask, adding deionized water, stirring at constant speed for 30min, then adding 60% phosphoric acid aqueous solution dropwise, controlling the dropwise adding time to be 15min, continuing stirring for 30min after the dropwise adding is finished to prepare intermediate emulsion, adding barium sulfate and talcum powder into the intermediate emulsion, stirring for 30min at the rotating speed of 150r/min to prepare a suspension, then adding nano titanium dioxide and a barium chloride solution with the mass fraction of 10 percent into the suspension, heating to 80 ℃, stirring at constant speed for 35min at the temperature, then performing vacuum filtration, drying the filter cake in a drying oven at 100 ℃ for 4h, then transferring to a muffle furnace, roasting at 300 ℃ for 10h to prepare a doped filler, wherein the weight ratio of calcium oxide, aqueous solution of phosphoric acid, barium sulfate, talcum powder and deionized water is controlled to be 3: 1: 10, and the weight ratio of calcium oxide, nano titanium dioxide and barium chloride solution is controlled to be 1: 2: 0.1;
step S12, adding fatty acid into a three-neck flask, heating to 100 ℃, preserving heat for 30min at the temperature, then adding diethanolamine, uniformly stirring, heating to 140 ℃, reacting at the temperature, detecting the amine value of the system until the amine value is more than 30mgKOH/g, stopping the reaction to obtain a reaction product, transferring the reaction product and boric acid into the beaker for mixing, heating to 120 ℃, preserving heat at the temperature and reacting for 4h, then adding a doped filler, and uniformly stirring for 2h to obtain the antirust composite filler, wherein the weight ratio of the substances of the fatty acid, the diethanolamine and the boric acid is controlled to be 3: 1: 3, and the weight ratio of the reaction product to the doped filler is 1: 3.
Example 3
The rust-proof spray paint for protecting the iron braided product comprises the following raw materials in parts by weight: 45 parts of modified epoxy resin, 16 parts of antirust composite filler, 8 parts of iron oxide red powder, 0.4 part of THIX-278 water-based defoaming agent, 16 parts of dimethylbenzene, 0.8 part of sodium carboxymethylcellulose and 26 parts of deionized water;
the rust-proof spray paint for protecting the iron braided product is prepared by the following method:
firstly, adding iron oxide red powder, an antirust composite filler and xylene into deionized water, stirring at a high speed of 450r/min for 30min, adding sodium carboxymethylcellulose after stirring is finished, and continuing stirring for 30min to prepare slurry;
and secondly, ball-milling the prepared slurry to 50 microns, adding the slurry into modified epoxy resin, dispersing for 30min, adding a THIX-278 aqueous defoaming agent, continuously dispersing for 10min, dropwise adding ammonia water with the mass fraction of 10% to adjust the pH until the pH is 8, and thus obtaining the antirust spray paint for protecting the iron knitted product.
The modified epoxy resin is prepared by the following method:
step S1, adding bisphenol A and epichlorohydrin into a three-neck flask, introducing nitrogen, heating in a water bath at 40 ℃, uniformly stirring at a rotating speed of 100r/min and dropwise adding 1, 6-hexamethylene diisocyanate, controlling the dropwise adding time to be 20min, uniformly stirring and reacting for 2h after the dropwise adding is finished, heating to 60 ℃, adding a sodium hydroxide solution with the mass fraction of 20%, continuously stirring and reacting for 2h, washing with deionized water for 3 times, standing and layering, collecting an organic phase, and distilling under reduced pressure until no fraction appears to prepare the waterborne epoxy resin, wherein in step S1, the weight ratio of the bisphenol A, the epichlorohydrin, the 1, 6-hexamethylene diisocyanate and the sodium hydroxide solution is controlled to be 1: 5: 0.5: 0.3;
step S2, adding hydroxyl-terminated polybutadiene into a three-neck flask, heating at 90 ℃ for 10min, vacuum degassing, cooling to 40 ℃, adding toluene diisocyanate, heating to 90 ℃ at a heating rate of 5 ℃/min, reacting at the temperature for 3h, vacuum degassing for 15min, terminating the reaction, and vacuumizing to obtain a prepolymer, wherein the weight ratio of the hydroxyl-terminated polybutadiene to the toluene diisocyanate is controlled to be 1: 1;
and S3, adding the prepolymer prepared in the step S2 into the waterborne epoxy resin prepared in the step S1, heating in water bath at 90 ℃, stirring at the rotating speed of 150r/min for 30min, cooling to 40 ℃, continuously stirring and reacting for 30min to prepare the modified epoxy resin, wherein the weight ratio of the waterborne epoxy resin to the prepolymer is controlled to be 1: 0.5.
The antirust composite filler is prepared by the following method:
step S11, adding calcium oxide into a three-neck flask, adding deionized water, stirring at constant speed for 30min, then adding 60% phosphoric acid aqueous solution dropwise, controlling the dropwise adding time to be 15min, continuing stirring for 30min after the dropwise adding is finished to prepare intermediate emulsion, adding barium sulfate and talcum powder into the intermediate emulsion, stirring for 30min at the rotating speed of 150r/min to prepare a suspension, then adding nano titanium dioxide and a barium chloride solution with the mass fraction of 10 percent into the suspension, heating to 80 ℃, stirring at constant speed for 35min at the temperature, then performing vacuum filtration, drying the filter cake in a drying oven at 100 ℃ for 4h, then transferring to a muffle furnace, roasting at 300 ℃ for 10h to prepare a doped filler, wherein the weight ratio of calcium oxide, aqueous solution of phosphoric acid, barium sulfate, talcum powder and deionized water is controlled to be 3: 1: 10, and the weight ratio of calcium oxide, nano titanium dioxide and barium chloride solution is controlled to be 1: 2: 0.1;
step S12, adding fatty acid into a three-neck flask, heating to 100 ℃, preserving heat for 30min at the temperature, then adding diethanolamine, uniformly stirring, heating to 140 ℃, reacting at the temperature, detecting the amine value of the system until the amine value is more than 30mgKOH/g, stopping the reaction to obtain a reaction product, transferring the reaction product and boric acid into the beaker for mixing, heating to 120 ℃, preserving heat at the temperature and reacting for 4h, then adding a doped filler, and uniformly stirring for 2h to obtain the antirust composite filler, wherein the weight ratio of the substances of the fatty acid, the diethanolamine and the boric acid is controlled to be 3: 1: 3, and the weight ratio of the reaction product to the doped filler is 1: 3.
Example 4
The rust-proof spray paint for protecting the iron braided product comprises the following raw materials in parts by weight: 55 parts of modified epoxy resin, 20 parts of antirust composite filler, 10 parts of iron oxide red powder, 0.5 part of THIX-278 water-based defoaming agent, 20 parts of dimethylbenzene, 1 part of sodium carboxymethylcellulose and 30 parts of deionized water;
the rust-proof spray paint for protecting the iron braided product is prepared by the following method:
firstly, adding iron oxide red powder, an antirust composite filler and xylene into deionized water, stirring at a high speed of 450r/min for 30min, adding sodium carboxymethylcellulose after stirring is finished, and continuing stirring for 30min to prepare slurry;
and secondly, ball-milling the prepared slurry to 50 microns, adding the slurry into modified epoxy resin, dispersing for 30min, adding a THIX-278 aqueous defoaming agent, continuously dispersing for 10min, dropwise adding ammonia water with the mass fraction of 10% to adjust the pH until the pH is 8, and thus obtaining the antirust spray paint for protecting the iron knitted product.
The modified epoxy resin is prepared by the following method:
step S1, adding bisphenol A and epichlorohydrin into a three-neck flask, introducing nitrogen, heating in a water bath at 40 ℃, uniformly stirring at a rotating speed of 100r/min and dropwise adding 1, 6-hexamethylene diisocyanate, controlling the dropwise adding time to be 20min, uniformly stirring and reacting for 2h after the dropwise adding is finished, heating to 60 ℃, adding a sodium hydroxide solution with the mass fraction of 20%, continuously stirring and reacting for 2h, washing with deionized water for 3 times, standing and layering, collecting an organic phase, and distilling under reduced pressure until no fraction appears to prepare the waterborne epoxy resin, wherein in step S1, the weight ratio of the bisphenol A, the epichlorohydrin, the 1, 6-hexamethylene diisocyanate and the sodium hydroxide solution is controlled to be 1: 5: 0.5: 0.3;
step S2, adding hydroxyl-terminated polybutadiene into a three-neck flask, heating at 90 ℃ for 10min, vacuum degassing, cooling to 40 ℃, adding toluene diisocyanate, heating to 90 ℃ at a heating rate of 5 ℃/min, reacting at the temperature for 3h, vacuum degassing for 15min, terminating the reaction, and vacuumizing to obtain a prepolymer, wherein the weight ratio of the hydroxyl-terminated polybutadiene to the toluene diisocyanate is controlled to be 1: 1;
and S3, adding the prepolymer prepared in the step S2 into the waterborne epoxy resin prepared in the step S1, heating in water bath at 90 ℃, stirring at the rotating speed of 150r/min for 30min, cooling to 40 ℃, continuously stirring and reacting for 30min to prepare the modified epoxy resin, wherein the weight ratio of the waterborne epoxy resin to the prepolymer is controlled to be 1: 0.5.
The antirust composite filler is prepared by the following method:
step S11, adding calcium oxide into a three-neck flask, adding deionized water, stirring at constant speed for 30min, then adding 60% phosphoric acid aqueous solution dropwise, controlling the dropwise adding time to be 15min, continuing stirring for 30min after the dropwise adding is finished to prepare intermediate emulsion, adding barium sulfate and talcum powder into the intermediate emulsion, stirring for 30min at the rotating speed of 150r/min to prepare a suspension, then adding nano titanium dioxide and a barium chloride solution with the mass fraction of 10 percent into the suspension, heating to 80 ℃, stirring at constant speed for 35min at the temperature, then performing vacuum filtration, drying the filter cake in a drying oven at 100 ℃ for 4h, then transferring to a muffle furnace, roasting at 300 ℃ for 10h to prepare a doped filler, wherein the weight ratio of calcium oxide, aqueous solution of phosphoric acid, barium sulfate, talcum powder and deionized water is controlled to be 3: 1: 10, and the weight ratio of calcium oxide, nano titanium dioxide and barium chloride solution is controlled to be 1: 2: 0.1;
step S12, adding fatty acid into a three-neck flask, heating to 100 ℃, preserving heat for 30min at the temperature, then adding diethanolamine, uniformly stirring, heating to 140 ℃, reacting at the temperature, detecting the amine value of the system until the amine value is more than 30mgKOH/g, stopping the reaction to obtain a reaction product, transferring the reaction product and boric acid into the beaker for mixing, heating to 120 ℃, preserving heat at the temperature and reacting for 4h, then adding a doped filler, and uniformly stirring for 2h to obtain the antirust composite filler, wherein the weight ratio of the substances of the fatty acid, the diethanolamine and the boric acid is controlled to be 3: 1: 3, and the weight ratio of the reaction product to the doped filler is 1: 3.
Comparative example 1
This comparative example compares with example 1, replacing the modified epoxy resin with an epoxy resin.
Comparative example 2
Compared with example 1, the comparative example does not add the antirust composite filler.
Comparative example 3
This comparative example is an anti-rust paint in the market.
The adhesion, salt spray resistance and hardness of examples 1 to 4 and comparative examples 1 to 3 were measured, and the results are shown in the following table;
as can be seen from the above table, examples 1 to 4 had an adhesion rating of 1, a hardness of 5H, no blistering and no peeling in the salt spray resistance test; comparative examples 1-3 adhesive force grades 3-2, hardness 3H-4H, appear bubble in the salt spray resistance test, take place to strip, so the hydroxyl on the epoxy resin is more than the isocyanate group can be in epoxy resin solidification network with prepolymer grafting, add epoxy resin into three-necked flask first in the reaction course, heat up to 95-100 duC and dehydrate, prevent the production of side reaction in the system, raise the reaction efficiency, and graft prepolymer on epoxy resin can improve its toughness and adhesive property apparently, give the excellent adhesiveness of antirust paint prepared.
In the description herein, references to the description of "one embodiment," "an example," "a specific example" or the like are intended to mean that a particular feature, structure, material, or characteristic described in connection with the embodiment or example is included in at least one embodiment or example of the invention. In this specification, the schematic representations of the terms used above do not necessarily refer to the same embodiment or example. Furthermore, the particular features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples.
The foregoing is illustrative and explanatory only and is not intended to be exhaustive or to limit the invention to the precise embodiments described, and various modifications, additions, and substitutions may be made by those skilled in the art without departing from the scope of the invention or exceeding the scope of the claims.
Claims (5)
1. The antirust spray paint for protecting the iron braided product is characterized by comprising the following raw materials in parts by weight: 35-55 parts of modified epoxy resin, 10-20 parts of antirust composite filler, 3-10 parts of iron oxide red powder, 0.1-0.5 part of defoaming agent, 10-20 parts of dimethylbenzene, 0.5-1 part of thickening agent and 20-30 parts of deionized water;
the rust-proof spray paint for protecting the iron braided product is prepared by the following method:
firstly, adding iron oxide red powder, an antirust composite filler and xylene into deionized water, stirring at a high speed of 500r/min for 30min at a speed of 450-;
and secondly, ball-milling the prepared slurry to 50-60 mu m, adding the slurry into modified epoxy resin, dispersing for 30-45min, adding a defoaming agent, continuously dispersing for 10min, dropwise adding ammonia water with the mass fraction of 10% to adjust the pH until the pH is 8-9, and thus obtaining the antirust spray paint for protecting the iron knitted product.
2. The antirust spray paint for protecting iron-braided products, according to claim 1, is characterized in that the defoaming agent is a THIX-278 water-based defoaming agent, and the thickening agent is one or two of sodium carboxymethylcellulose and propylene glycol sodium alginate which are mixed according to any proportion.
3. The rust inhibitive paint for protecting iron-braided articles according to claim 1, wherein said modified epoxy resin is prepared by the following method:
step S1, adding bisphenol A and epichlorohydrin into a three-neck flask, introducing nitrogen, heating in a water bath at 40-50 ℃, uniformly stirring and dropwise adding 1, 6-hexamethylene diisocyanate at a rotation speed of 120r/min, controlling the dropwise adding time to be 20min, uniformly stirring and reacting for 2h after the dropwise adding is finished, heating to 60-70 ℃, adding a sodium hydroxide solution with a mass fraction of 20%, continuously stirring and reacting for 2h, washing with deionized water for 3 times, standing and layering, collecting an organic phase, and carrying out reduced pressure distillation until no fraction appears to prepare the aqueous epoxy resin, wherein in step S1, the weight ratio of the bisphenol A, the epichlorohydrin, the 1, 6-hexamethylene diisocyanate and the sodium hydroxide solution is controlled to be 1: 5: 0.5: 0.3-0.5;
step S2, adding hydroxyl-terminated polybutadiene into a three-neck flask, heating at 90-100 ℃ for 10min, vacuum degassing, cooling to 40-50 ℃, adding toluene diisocyanate, heating to 90-100 ℃ at a heating rate of 5 ℃/min, reacting at the temperature for 3h, vacuum degassing for 15min, terminating the reaction, and vacuumizing to obtain a prepolymer, wherein the weight ratio of the hydroxyl-terminated polybutadiene to the toluene diisocyanate is controlled to be 1: 1;
and S3, adding the prepolymer prepared in the step S2 into the waterborne epoxy resin prepared in the step S1, heating in a water bath at 90-100 ℃, stirring at the rotating speed of 150-.
4. The antirust paint for protecting iron-braided products according to claim 1, wherein the antirust composite filler is prepared by the following method:
step S11, adding calcium oxide into a three-neck flask, adding deionized water, dropwise adding 60 mass percent phosphoric acid aqueous solution after stirring at a constant speed for 30min, controlling the dropwise adding time to be 15min, continuously stirring for 30min after dropwise adding to prepare intermediate emulsion, adding barium sulfate and talcum powder into the intermediate emulsion, stirring for 30min at a rotating speed of 150 plus 200r/min to prepare suspension, then adding nano titanium dioxide and 10 mass percent barium chloride solution into the suspension, heating to 80-100 ℃, stirring at a constant speed for 35min, then carrying out vacuum filtration, placing a filter cake into a drying oven at 100 ℃ for drying for 4h, then transferring into a muffle furnace, roasting for 10h at 300 ℃ to prepare doped filler, controlling the weight ratio of the calcium oxide, the phosphoric acid aqueous solution, the barium sulfate, the talcum powder and the deionized water to be 3: 1: 10-15, the weight ratio of the calcium oxide to the nano titanium dioxide to the barium chloride solution is 1: 2: 0.1-0.5;
step S12, adding fatty acid into a three-neck flask, heating to 110-.
5. The method for preparing the rust-proof paint for protecting the iron-braided product according to claim 1 is characterized by comprising the following steps of:
firstly, adding iron oxide red powder, an antirust composite filler and xylene into deionized water, stirring at a high speed of 500r/min for 30min at a speed of 450-;
and secondly, ball-milling the prepared slurry to 50-60 mu m, adding the slurry into modified epoxy resin, dispersing for 30-45min, adding a defoaming agent, continuously dispersing for 10min, dropwise adding ammonia water with the mass fraction of 10% to adjust the pH until the pH is 8-9, and thus obtaining the antirust spray paint for protecting the iron knitted product.
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