CN111334178A - Hydrophobic anti-corrosion material of carbon nano tube modified polyurethane and preparation method thereof - Google Patents
Hydrophobic anti-corrosion material of carbon nano tube modified polyurethane and preparation method thereof Download PDFInfo
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Abstract
The invention relates to the technical field of polyurethane, and discloses a hydrophobic anti-corrosion material of carbon nano tube modified polyurethane, which comprises the following formula raw materials and components: modified carbon nano tube, epoxy resin, hexamethylene diisocyanate, 2-dimethylolpropionic acid, 1, 4-butanediol, dibutyltin dilaurate and alkylated polyester dihydric alcohol. According to the hydrophobic anti-corrosion material of the carbon nano tube modified polyurethane, the alkylated polyester diol with the long alkyl chain and extremely strong hydrophobicity is used as a diol monomer, 2, 2-dimethylolpropionic acid reacts with an epoxy group of epoxy resin, and the epoxy group reacts with amino groups in the modified carbon nano tube to obtain the carbon nano tube modified polyurethane material with chemical bond crosslinking, so that the compatibility of the carbon nano tube and polyurethane is improved, the carbon nano tube enters pores of the polyurethane material to play a role in isolating oxygen and water molecules, and the polyurethane material is endowed with excellent super-hydrophobic performance, antifouling, chemical resistance and chemical corrosion resistance.
Description
Technical Field
The invention relates to the technical field of polyurethane, in particular to a hydrophobic anti-corrosion material of carbon nano tube modified polyurethane and a preparation method thereof.
Background
The process of generating loss and damage of metal and non-metal materials under the action of surrounding environment media such as water, air, acid, alkali, salt and the like is called corrosion phenomenon, the corrosion can be divided into chemical corrosion and electrochemical corrosion, which are generally accompanied with physical, mechanical and microbial actions, the chemical corrosion is generated on the surface of metal, no current is generated in the corrosion process, when a corrosion product is not firmly contacted with the surface of the material, the corrosion product can fall off to cause the loss and damage of the material, the electrochemical corrosion is the damage caused by the electrochemical action generated in a metal material and an electrolyte solution, and the current is generated in the corrosion process, so that the material corrosion has huge destructive power, and the corrosion harms are distributed throughout daily life and various industries, such as metallurgy, energy, mines, traffic, machinery, infrastructure and the like, and huge economic loss and disasters are caused.
The super-hydrophobic material has a stable surface contact angle of more than or equal to 150 degrees, a rolling contact angle of less than or equal to 10 degrees, excellent hydrophobic property and self-cleaning function, and has wide application in the aspects of outdoor building material rain and snow prevention, oil pipeline pollution prevention, metal material corrosion prevention and the like.
Technical problem to be solved
Aiming at the defects of the prior art, the invention provides a hydrophobic anti-corrosion material of carbon nano tube modified polyurethane and a preparation method thereof, and solves the problems that the polyurethane material does not have super-hydrophobic property and has poor antifouling and anti-corrosion properties.
(II) technical scheme
In order to achieve the purpose, the invention provides the following technical scheme: a hydrophobic anti-corrosion material of carbon nano tube modified polyurethane comprises the following formula raw materials in parts by weight: 2-8 parts of modified carbon nano tube, 5-10 parts of epoxy resin, 30-38 parts of hexamethylene diisocyanate, 2-4 parts of 2, 2-dimethylolpropionic acid, 2.5-6 parts of 1, 4-butanediol, 0.5-1 part of dibutyltin dilaurate and 33-58 parts of alkylated polyester diol.
Preferably, the preparation method of the alkylated polyester diol comprises the following steps:
(1) introducing nitrogen into an atmosphere reaction bottle to discharge air, adding glyceryl monostearate, placing the mixture in an oil bath pot, heating to 110-.
Preferably, the mass ratio of the glyceryl monostearate to the succinic anhydride is 1: 1.1-1.4.
Preferably, the atmosphere reaction bottle comprises a reaction bottle body, a bottle opening of the reaction bottle body is movably connected with a piston, the piston is movably connected with a sample inlet pipe, the bottom of the sample inlet pipe is fixedly connected with a sample injector, the left upper side of the reaction bottle body is fixedly connected with an air inlet pipe, the air inlet pipe is movably connected with an air inlet valve, the right upper side of the reaction bottle body is fixedly connected with an air outlet pipe, the air outlet pipe is movably connected with an air outlet valve, the right lower side of the reaction bottle body is fixedly connected with a discharge hole, and the discharge.
Preferably, the preparation method of the modified graphene comprises the following steps:
(1) adding a mixed solvent of distilled water and ethanol into a reaction bottle, wherein the volume ratio of the two solvents is 1:2-4, adding a hydroxylated carbon nano tube and N- (β -aminoethyl) -gamma-aminopropyltrimethoxysilane, uniformly dispersing by ultrasonic, adding acetic acid to adjust the pH value of the solution to 4-6, uniformly stirring and reacting at 30-40 ℃ for 40-60h, adding sodium hydroxide to adjust the pH value of the solution to 8-10, heating to 60-80 ℃, uniformly stirring and reacting for 1-3h, filtering the solution to remove the solvent, washing a solid product by using distilled water and ethanol, and fully drying to prepare the N- (β -aminoethyl) -gamma-aminopropyltrimethoxysilane grafted modified carbon nano tube.
Preferably, the mass ratio of the hydroxylated carbon nanotube to the N- (β -aminoethyl) -gamma-aminopropyltrimethoxysilane is 1: 5-8.
Preferably, the preparation method of the hydrophobic anti-corrosion material of the carbon nanotube modified polyurethane comprises the following steps:
(1) adding 30-38 parts of hexamethylene diisocyanate, 33-58 parts of alkylated polyester diol and 0.5-1 part of dibutyltin dilaurate into a reaction bottle, uniformly stirring at 70-75 ℃ for reaction for 2-4h, adding a toluene solvent, adding 2.5-6 parts of 1, 4-butanediol, heating to 80-85 ℃, reacting for 3-5h, adding 2-4 parts of 2, 2-dimethylolpropionic acid and 5-10 parts of epoxy resin, uniformly stirring for reaction for 1-3h, adding 2-8 parts of modified carbon nanotubes, uniformly dispersing by ultrasonic waves, uniformly stirring at 60-80 ℃ for reaction for 6-12h, pouring the solution into a film-forming mold, and fully drying to prepare the hydrophobic anticorrosive material of the carbon nanotube modified polyurethane.
(III) advantageous technical effects
Compared with the prior art, the invention has the following beneficial technical effects:
n- (β -aminoethyl) -gamma-aminopropyltrimethoxysilane reacts with a hydroxylated carbon nanotube to obtain an aminated modified carbon nanotube, glyceryl monostearate and succinic anhydride carry out ring-opening reaction to obtain long-alkyl-chain alkylated polyester diol with extremely strong hydrophobicity, the alkylated polyester diol is used as a diol monomer, 2, 2-dimethylolpropionic acid is used as a chain extender and simultaneously reacts with an epoxy group of epoxy resin to obtain super-hydrophobic epoxidized polyurethane, the epoxy group is introduced into a polyurethane molecular chain and then reacts with an amino group in the modified carbon nanotube to obtain a chemically-bond-crosslinked carbon nanotube modified polyurethane material, the compatibility of the carbon nanotube and the polyurethane is improved, the carbon nanotube is used as a filler and enters pores of the polyurethane material to play a role in isolating oxygen and water molecules, the modified polyurethane material is endowed with excellent super-hydrophobic performance and antifouling and chemical corrosion resistance under the synergistic action, the carbon nanotube has excellent conductivity, when the modified ester material is coated on the surface of a metal material, the electrochemical corrosion resistance of the polyurethane material can be enhanced, the contact angle can reach 149.2-gamma-aminopropyltrimethoxysilane and the salt-resistant aqueous solution has good salt resistance of 70-86h and good salt resistance.
Drawings
FIG. 1 is a schematic front view of an atmospheric resistance furnace.
1. A reaction flask body; 2. a piston; 3. a sample inlet pipe; 4. a sample injector; 5. an air inlet pipe; 6. an intake valve; 7. an air outlet pipe; 8. an air outlet valve; 9. a discharge port; 10. and a discharge valve.
Detailed Description
To achieve the above object, the present invention provides the following embodiments and examples: a hydrophobic anti-corrosion material of carbon nano tube modified polyurethane comprises the following formula raw materials in parts by weight: 2-8 parts of modified carbon nano tube, 5-10 parts of epoxy resin, 30-38 parts of hexamethylene diisocyanate, 2-4 parts of 2, 2-dimethylolpropionic acid, 2.5-6 parts of 1, 4-butanediol, 0.5-1 part of dibutyltin dilaurate and 33-58 parts of alkylated polyester diol.
The preparation method of the alkylated polyester diol comprises the following steps:
(1) introducing nitrogen into an atmosphere reaction bottle to discharge air, wherein the atmosphere reaction bottle comprises a reaction bottle body, a piston is movably connected with the bottle mouth of the reaction bottle body, the piston is movably connected with a sample inlet pipe, a sample injector is fixedly connected with the bottom of the sample inlet pipe, an air inlet pipe is fixedly connected with the upper part of the left side of the reaction bottle body, an air inlet pipe is movably connected with the air inlet pipe, an air outlet pipe is fixedly connected with the upper part of the right side of the reaction bottle body, the air outlet pipe is movably connected with an air outlet valve, a discharge port is fixedly connected with the lower part of the right side of the reaction bottle body, the discharge port is movably connected with a discharge valve, glycerol monostearate is added, the reaction bottle is placed in an oil bath pot to be heated to 110-, stirring at a constant speed for reaction, finishing the reaction when the pH value of a reaction system is 6-7, and cooling the solution to room temperature to prepare the alkylated polyester diol.
The preparation method of the modified graphene comprises the following steps:
(1) adding a mixed solvent of distilled water and ethanol into a reaction bottle, wherein the volume ratio of the two solvents is 1:2-4, adding a hydroxylated carbon nanotube and N- (β -aminoethyl) -gamma-aminopropyltrimethoxysilane, the mass ratio of the two solvents is 1:5-8, after uniform ultrasonic dispersion, adding acetic acid to adjust the pH value of the solution to 4-6, uniformly stirring and reacting at 30-40 ℃ for 40-60h, adding sodium hydroxide to adjust the pH value of the solution to 8-10, heating to 60-80 ℃, uniformly stirring and reacting for 1-3h, filtering the solution to remove the solvent, washing a solid product with distilled water and ethanol, and fully drying to obtain the N- (β -aminoethyl) -gamma-aminopropyltrimethoxysilane grafted modified carbon nanotube.
The preparation method of the hydrophobic anti-corrosion material of the carbon nano tube modified polyurethane comprises the following steps:
(1) adding 30-38 parts of hexamethylene diisocyanate, 33-58 parts of alkylated polyester diol and 0.5-1 part of dibutyltin dilaurate into a reaction bottle, uniformly stirring at 70-75 ℃ for reaction for 2-4h, adding a toluene solvent, adding 2.5-6 parts of 1, 4-butanediol, heating to 80-85 ℃, reacting for 3-5h, adding 2-4 parts of 2, 2-dimethylolpropionic acid and 5-10 parts of epoxy resin, uniformly stirring for reaction for 1-3h, adding 2-8 parts of modified carbon nanotubes, uniformly dispersing by ultrasonic waves, uniformly stirring at 60-80 ℃ for reaction for 6-12h, pouring the solution into a film-forming mold, and fully drying to prepare the hydrophobic anticorrosive material of the carbon nanotube modified polyurethane.
Example 1
(1) Preparation of alkylated polyester diol component 1: introducing nitrogen into an atmosphere reaction bottle to discharge air, wherein the atmosphere reaction bottle comprises a reaction bottle body, a bottle opening of the reaction bottle body is movably connected with a piston, the piston is movably connected with a sample inlet pipe, the bottom of the sample inlet pipe is fixedly connected with a sample injector, the upper part of the left side of the reaction bottle body is fixedly connected with an air inlet pipe, the upper part of the right side of the reaction bottle body is fixedly connected with an air outlet pipe, the air outlet pipe is movably connected with an air outlet valve, the lower part of the right side of the reaction bottle body is fixedly connected with a discharge port, the discharge port is movably connected with a discharge valve, glycerin monostearate is added, the reaction bottle is placed in an oil bath pot to be heated to 110 ℃, succinic anhydride is added, the mass ratio of the two substances is 1:1.1, the reaction bottle is stirred at constant speed for 30min, then the temperature is raised to 150, the solution was cooled to room temperature to prepare the alkylated polyester diol component 1.
(2) Adding a mixed solvent of distilled water and ethanol into a reaction bottle, wherein the volume ratio of the distilled water to the ethanol is 1:2, adding a hydroxylated carbon nanotube and N- (β -aminoethyl) -gamma-aminopropyltrimethoxysilane, wherein the mass ratio of the hydroxylated carbon nanotube to the N- (β -aminoethyl) -gamma-aminopropyltrimethoxysilane is 1:5, performing ultrasonic dispersion uniformly, adding acetic acid to adjust the pH of the solution to 6, performing uniform stirring reaction at 30 ℃ for 40 hours, adding sodium hydroxide to adjust the pH of the solution to 8, heating to 60 ℃, performing uniform stirring reaction for 1 hour, filtering the solution to remove the solvent, washing a solid product with distilled water and ethanol, and fully drying to obtain the N- (β -aminoethyl) -gamma-aminopropyltrimethoxysilane grafted modified carbon nanotube component 1.
(3) Preparing a hydrophobic anticorrosive material of carbon nanotube modified polyurethane 1: adding 30 parts of hexamethylene diisocyanate, 58 parts of alkylated polyester diol component 1 and 0.5 part of dibutyltin dilaurate into a reaction bottle, stirring at a constant speed at 70 ℃ for reaction for 2 hours, adding a toluene solvent, adding 2.5 parts of 1, 4-butanediol, heating to 80 ℃, reacting for 3 hours, adding 2 parts of 2, 2-dimethylolpropionic acid and 5 parts of epoxy resin, stirring at a constant speed for reaction for 1 hour, adding 2 parts of modified carbon nanotube component 1, uniformly dispersing by ultrasonic waves, stirring at a constant speed at 60 ℃ for reaction for 6 hours, pouring the solution into a film-forming mold, and fully drying to prepare the hydrophobic anticorrosive material 1 of the carbon nanotube modified polyurethane.
Example 2
(1) Preparation of alkylated polyester diol component 2: introducing nitrogen into an atmosphere reaction bottle to discharge air, wherein the atmosphere reaction bottle comprises a reaction bottle body, a bottle opening of the reaction bottle body is movably connected with a piston, the piston is movably connected with a sample inlet pipe, the bottom of the sample inlet pipe is fixedly connected with a sample injector, the upper part of the left side of the reaction bottle body is fixedly connected with an air inlet pipe, the upper part of the right side of the reaction bottle body is fixedly connected with an air outlet pipe, the air outlet pipe is movably connected with an air outlet valve, the lower part of the right side of the reaction bottle body is fixedly connected with a discharge port, the discharge port is movably connected with a discharge valve, glycerin monostearate is added, the reaction bottle is placed in an oil bath pot to be heated to 130 ℃, succinic anhydride is added, the mass ratio of the two substances is 1:1.1, the reaction bottle is stirred at constant speed for 60min, then the temperature is raised to 150, the solution was cooled to room temperature to prepare the alkylated polyester diol component 2.
(2) Adding a mixed solvent of distilled water and ethanol into a reaction bottle, wherein the volume ratio of the distilled water to the ethanol is 1:4, adding a hydroxylated carbon nanotube and N- (β -aminoethyl) -gamma-aminopropyltrimethoxysilane, the mass ratio of the hydroxylated carbon nanotube to the N- (β -aminoethyl) -gamma-aminopropyltrimethoxysilane is 1:5, performing ultrasonic dispersion uniformly, adding acetic acid to adjust the pH of the solution to 6, performing uniform stirring reaction at 40 ℃ for 40 hours, adding sodium hydroxide to adjust the pH of the solution to 8, heating to 80 ℃, performing uniform stirring reaction for 3 hours, filtering the solution to remove the solvent, washing a solid product by using distilled water and ethanol, and fully drying to obtain the N- (β -aminoethyl) -gamma-aminopropyltrimethoxysilane grafted modified carbon nanotube component 2.
(3) Preparing a hydrophobic anti-corrosion material of carbon nanotube modified polyurethane 2: adding 32 parts of hexamethylene diisocyanate, 52 parts of alkylated polyester diol component 2 and 0.6 part of dibutyltin dilaurate into a reaction bottle, stirring at a constant speed at 70 ℃ for reaction for 2 hours, adding a toluene solvent, adding 3.4 parts of 1, 4-butanediol, heating to 85 ℃, reacting for 3 hours, adding 3.5 parts of 2, 2-dimethylolpropionic acid and 6 parts of epoxy resin, stirring at a constant speed for reaction for 3 hours, adding 3 parts of modified carbon nanotube component 2, stirring at a constant speed at 60 ℃ for reaction for 12 hours after uniform ultrasonic dispersion, pouring the solution into a film-forming mold, and fully drying to prepare the hydrophobic anticorrosive material 2 of the carbon nanotube modified polyurethane.
Example 3
(1) Preparation of alkylated polyester diol component 3: introducing nitrogen into an atmosphere reaction bottle to discharge air, wherein the atmosphere reaction bottle comprises a reaction bottle body, a bottle opening of the reaction bottle body is movably connected with a piston, the piston is movably connected with a sample inlet pipe, the bottom of the sample inlet pipe is fixedly connected with a sample injector, the upper part of the left side of the reaction bottle body is fixedly connected with an air inlet pipe, the upper part of the right side of the reaction bottle body is fixedly connected with an air outlet pipe, the air outlet pipe is movably connected with an air outlet valve, the lower part of the right side of the reaction bottle body is fixedly connected with a discharge port, the discharge port is movably connected with a discharge valve, glycerin monostearate is added, the reaction bottle is placed in an oil bath pot to be heated to 120 ℃, succinic anhydride is added, the mass ratio of the two substances is 1:1.2, the reaction bottle is stirred at constant speed for 45min, then the temperature is raised to 160, the solution was cooled to room temperature to prepare the alkylated polyester diol component 3.
(2) Adding a mixed solvent of distilled water and ethanol into a reaction bottle, wherein the volume ratio of the two is 1:3, adding a hydroxylated carbon nanotube and N- (β -aminoethyl) -gamma-aminopropyltrimethoxysilane, the mass ratio of the two is 1:6.5, after uniform ultrasonic dispersion, adding acetic acid to adjust the pH of the solution to 5, uniformly stirring and reacting at 35 ℃ for 50 hours, adding sodium hydroxide to adjust the pH of the solution to 9, heating to 70 ℃, uniformly stirring and reacting for 2 hours, filtering the solution to remove the solvent, washing a solid product by using distilled water and ethanol, and fully drying to obtain the N- (β -aminoethyl) -gamma-aminopropyltrimethoxysilane grafted modified carbon nanotube component 3.
(3) Preparing a hydrophobic anticorrosive material of carbon nanotube modified polyurethane 3: adding 34 parts of hexamethylene diisocyanate, 47 parts of alkylated polyester diol component 3 and 0.8 part of dibutyltin dilaurate into a reaction bottle, stirring at a constant speed at 75 ℃ for reaction for 3 hours, adding a toluene solvent, adding 4.2 parts of 1, 4-butanediol, heating to 85 ℃, reacting for 4 hours, adding 3 parts of 2, 2-dimethylolpropionic acid and 7.5 parts of epoxy resin, stirring at a constant speed for reaction for 2 hours, adding 4.5 parts of modified carbon nanotube component 3, stirring at a constant speed at 70 ℃ for reaction for 9 hours after uniform ultrasonic dispersion, pouring the solution into a film-forming mold, and fully drying to prepare the hydrophobic anticorrosive material 3 of carbon nanotube modified polyurethane.
Example 4
(1) Preparation of alkylated polyester diol component 4: introducing nitrogen into an atmosphere reaction bottle to discharge air, wherein the atmosphere reaction bottle comprises a reaction bottle body, a bottle opening of the reaction bottle body is movably connected with a piston, the piston is movably connected with a sample inlet pipe, the bottom of the sample inlet pipe is fixedly connected with a sample injector, the upper part of the left side of the reaction bottle body is fixedly connected with an air inlet pipe, the upper part of the right side of the reaction bottle body is fixedly connected with an air outlet pipe, the air outlet pipe is movably connected with an air outlet valve, the lower part of the right side of the reaction bottle body is fixedly connected with a discharge port, the discharge port is movably connected with a discharge valve, glycerin monostearate is added, the reaction bottle is placed in an oil bath pot to be heated to 120 ℃, succinic anhydride is added, the mass ratio of the two substances is 1:1.2, the reaction bottle is stirred at constant speed for 45min, then the temperature is raised to 160, the solution was cooled to room temperature to prepare the alkylated polyester diol component 4.
(2) Adding a mixed solvent of distilled water and ethanol into a reaction bottle, wherein the volume ratio of the distilled water to the ethanol is 1:2, adding a hydroxylated carbon nanotube and N- (β -aminoethyl) -gamma-aminopropyltrimethoxysilane, wherein the mass ratio of the hydroxylated carbon nanotube to the N- (β -aminoethyl) -gamma-aminopropyltrimethoxysilane is 1:8, performing ultrasonic dispersion uniformly, adding acetic acid to adjust the pH of the solution to 4, performing uniform stirring reaction at 30 ℃ for 60 hours, adding sodium hydroxide to adjust the pH of the solution to 9, heating to 80 ℃, performing uniform stirring reaction for 3 hours, filtering the solution to remove the solvent, washing a solid product with distilled water and ethanol, and fully drying to obtain the N- (β -aminoethyl) -gamma-aminopropyltrimethoxysilane grafted modified carbon nanotube component 4.
(3) Preparing a hydrophobic anticorrosive material of carbon nanotube modified polyurethane 4: adding 36 parts of hexamethylene diisocyanate, 39 parts of alkylated polyester diol component 4 and 0.9 part of dibutyltin dilaurate into a reaction bottle, stirring at a constant speed at 75 ℃ for reaction for 4 hours, adding a toluene solvent, adding 5.1 parts of 1, 4-butanediol, heating to 85 ℃, reacting for 3 hours, adding 3.5 parts of 2, 2-dimethylolpropionic acid and 9 parts of epoxy resin, stirring at a constant speed for reaction for 3 hours, adding 6.5 parts of modified carbon nanotube component 4, stirring at a constant speed at 60 ℃ for reaction for 12 hours after uniform ultrasonic dispersion, pouring the solution into a film-forming mold, and fully drying to prepare the hydrophobic anticorrosive material 4 of carbon nanotube modified polyurethane.
Example 5
(1) Preparation of alkylated polyester diol component 5: introducing nitrogen into an atmosphere reaction bottle to discharge air, wherein the atmosphere reaction bottle comprises a reaction bottle body, a bottle mouth of the reaction bottle body is movably connected with a piston, the piston is movably connected with a sample inlet pipe, the bottom of the sample inlet pipe is fixedly connected with a sample injector, the upper part of the left side of the reaction bottle body is fixedly connected with an air inlet pipe, the upper part of the right side of the reaction bottle body is fixedly connected with an air outlet pipe, the air outlet pipe is movably connected with an air outlet valve, the lower part of the right side of the reaction bottle body is fixedly connected with a discharge port, the discharge port is movably connected with a discharge valve, glycerin monostearate is added, the reaction bottle is placed in an oil bath pot to be heated to 130 ℃, succinic anhydride is added, the mass ratio of the two substances is 1:1.4, the reaction bottle is stirred at a constant speed for 60min, then the temperature is raised to, the solution was cooled to room temperature to prepare the alkylated polyester diol component 5.
(2) Adding a mixed solvent of distilled water and ethanol into a reaction bottle, wherein the volume ratio of the distilled water to the ethanol is 1:4, adding a hydroxylated carbon nanotube and N- (β -aminoethyl) -gamma-aminopropyltrimethoxysilane, the mass ratio of the hydroxylated carbon nanotube to the N- (β -aminoethyl) -gamma-aminopropyltrimethoxysilane is 1:8, performing ultrasonic dispersion uniformly, adding acetic acid to adjust the pH of the solution to 6, performing uniform stirring reaction at 40 ℃ for 60 hours, adding sodium hydroxide to adjust the pH of the solution to 10, heating to 80 ℃, performing uniform stirring reaction for 3 hours, filtering the solution to remove the solvent, washing a solid product by using distilled water and ethanol, and fully drying to obtain the N- (β -aminoethyl) -gamma-aminopropyltrimethoxysilane grafted modified carbon nanotube component 5.
(3) Preparing a hydrophobic anti-corrosion material of carbon nanotube modified polyurethane 5: adding 38 parts of hexamethylene diisocyanate, 33 parts of alkylated polyester diol component 5 and 1 part of dibutyltin dilaurate into a reaction bottle, uniformly stirring and reacting for 4 hours at 75 ℃, adding a toluene solvent, adding 6 parts of 1, 4-butanediol, heating to 85 ℃, reacting for 5 hours, adding 4 parts of 2, 2-dimethylolpropionic acid and 10 parts of epoxy resin, uniformly stirring and reacting for 3 hours, adding 8 parts of modified carbon nanotube component 5, uniformly dispersing by ultrasonic, uniformly stirring and reacting for 12 hours at 80 ℃, pouring the solution into a film-forming mold, and fully drying to prepare the hydrophobic anticorrosive material 5 of the carbon nanotube modified polyurethane.
The hydrophobic anticorrosive materials 1 to 5 of the carbon nanotube-modified polyurethane in examples 1 to 5 were measured for water contact angle and water rolling angle using XG-CMAC3 full-automatic contact angle measuring instrument, respectively.
Placing 1-5 hydrophobic anti-corrosion materials of carbon nano tube modified polyurethane in a ZH-SH-90 touch screen salt spray test box for testing salt spray resistance and corrosion resistance, wherein the standard is GB/T2423.17-2008; respectively placing the materials in NaCl solution with the mass fraction of 3% to test the salt-tolerant solution, and observing the phenomena of foaming, cracking, corrosion and falling off of the appearance of the materials.
In summary, the hydrophobic anticorrosion material of the carbon nanotube modified polyurethane comprises N- (β -aminoethyl) -gamma-aminopropyltrimethoxysilane and a hydroxylated carbon nanotube, wherein the N- (β -aminoethyl) -gamma-aminopropyltrimethoxysilane reacts with the hydroxylated carbon nanotube to obtain an aminated modified carbon nanotube, glyceryl monostearate and succinic anhydride carry out a ring-opening reaction to obtain an alkylated polyester diol with a long alkyl chain with extremely strong hydrophobicity, the alkylated polyester diol is used as a diol monomer, 2, 2-dimethylolpropionic acid is used as a chain extender and simultaneously reacts with an epoxy group of epoxy resin to obtain super-hydrophobic epoxidized polyurethane, the epoxy group is introduced into a polyurethane molecular chain and then reacts with amino groups in the modified carbon nanotube to obtain a carbon nanotube modified polyurethane material with chemical bond crosslinking, the compatibility of the carbon nanotube and polyurethane is improved, the carbon nanotube is used as a filler and enters pores of the polyurethane material to play a role in isolating oxygen and water molecules, the modified polyurethane material is endowed with excellent super-hydrophobic performance and antifouling and chemical corrosion resistance under the synergistic action, the carbon nanotube has excellent conductivity, and when the modified ester material is used as a coating on the surface of a metal material, the electrochemical anticorrosion performance of the polyurethane material can be enhanced, the iron-based salt spray resistance can reach 149.2-86.2 and the salt spray resistance can be good.
Claims (7)
1. The hydrophobic anti-corrosion material of the carbon nano tube modified polyurethane comprises the following formula raw materials and components in parts by weight, and is characterized in that: 2-8 parts of modified carbon nano tube, 5-10 parts of epoxy resin, 30-38 parts of hexamethylene diisocyanate, 2-4 parts of 2, 2-dimethylolpropionic acid, 2.5-6 parts of 1, 4-butanediol, 0.5-1 part of dibutyltin dilaurate and 33-58 parts of alkylated polyester diol.
2. The hydrophobic anticorrosion material of carbon nanotube modified polyurethane as claimed in claim 1, wherein: the preparation method of the alkylated polyester diol comprises the following steps:
(1) introducing nitrogen into an atmosphere reaction bottle to discharge air, adding glyceryl monostearate, heating to 110-.
3. The hydrophobic anticorrosion material of carbon nanotube modified polyurethane as claimed in claim 2, wherein: the mass ratio of the glyceryl monostearate to the succinic anhydride is 1: 1.1-1.4.
4. The hydrophobic anticorrosion material of carbon nanotube modified polyurethane as claimed in claim 2, wherein: atmosphere reaction bottle has piston, piston and injection pipe swing joint including the bottleneck swing joint of reaction bottle, and injection pipe bottom fixedly connected with sample injector, the left side top fixedly connected with intake pipe of reaction bottle, intake pipe swing joint have the admission valve, the right side top fixedly connected with outlet duct, outlet duct and the air outlet valve swing joint of reaction bottle, the right side below fixedly connected with discharge gate, discharge gate and discharge valve swing joint of reaction bottle.
5. The hydrophobic anticorrosion material of carbon nanotube modified polyurethane as claimed in claim 1, wherein: the preparation method of the modified graphene comprises the following steps:
(1) adding a hydroxylated carbon nanotube and N- (β -aminoethyl) -gamma-aminopropyltrimethoxysilane into a mixed solvent of distilled water and ethanol with the volume ratio of 1:2-4, uniformly dispersing by ultrasonic waves, adding acetic acid to adjust the pH value of the solution to 4-6, reacting at 30-40 ℃ for 40-60h, adding sodium hydroxide to adjust the pH value of the solution to 8-10, heating to 60-80 ℃, reacting for 1-3h, filtering, washing and drying to obtain the N- (β -aminoethyl) -gamma-aminopropyltrimethoxysilane grafted modified carbon nanotube.
6. The hydrophobic anticorrosion material of carbon nanotube modified polyurethane as claimed in claim 5, wherein the mass ratio of the hydroxylated carbon nanotube to the N- (β -aminoethyl) - γ -aminopropyltrimethoxysilane is 1: 5-8.
7. The hydrophobic anticorrosion material of carbon nanotube modified polyurethane as claimed in claim 1, wherein: the preparation method of the hydrophobic anti-corrosion material of the carbon nano tube modified polyurethane comprises the following steps:
(1) adding 33-58 parts of alkylated polyester diol and 0.5-1 part of dibutyltin dilaurate into 30-38 parts of hexamethylene diisocyanate, reacting at 70-75 ℃ for 2-4h, adding a toluene solvent, adding 2.5-6 parts of 1, 4-butanediol, heating to 80-85 ℃, reacting for 3-5h, adding 2-4 parts of 2, 2-dimethylolpropionic acid and 5-10 parts of epoxy resin, reacting for 1-3h, adding 2-8 parts of modified carbon nano tubes, uniformly dispersing by ultrasonic waves, reacting at 60-80 ℃ for 6-12h, pouring the solution into a film forming mold, and fully drying to prepare the hydrophobic anticorrosive material of the carbon nano tube modified polyurethane.
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