CN112574655B - Preparation method of surface coating for glass fiber reinforced plastics with anti-ultraviolet effect - Google Patents
Preparation method of surface coating for glass fiber reinforced plastics with anti-ultraviolet effect Download PDFInfo
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Abstract
The invention discloses a preparation method of a surface coating for glass fiber reinforced plastics with an anti-ultraviolet effect; relates to the technical field of glass fiber reinforced plastic, comprising the following steps: (1) preparing a polymer emulsion; (2) preparing a filler; (3) preparing a coating; the coating prepared by the method has excellent ultraviolet resistance, and the ultraviolet resistance of the coating can be greatly improved by introducing the modified cellulose, so that when a coating formed by coating the glass fiber reinforced plastic with the coating is used outdoors, the coating can better resist the irradiation of ultraviolet light, and the service life of the coating is obviously prolonged.
Description
Technical Field
The invention belongs to the technical field of glass fiber reinforced plastics, and particularly relates to a preparation method of a surface coating for glass fiber reinforced plastics with an anti-ultraviolet effect.
Background
The glass fiber Reinforced plastic is known as Fiber Reinforced Plastic (FRP), i.e., fiber Reinforced composite plastic. The fiber is classified into glass fiber reinforced composite plastic (GFRP), carbon fiber reinforced composite plastic (CFRP), boron fiber reinforced composite plastic, and the like according to the difference of the adopted fiber. It is a composite material using glass fibre and its products (glass cloth, band, felt and yarn, etc.) as reinforcing material and synthetic resin as base material. The fiber reinforced composite material is composed of reinforcing fibers and a matrix. The diameter of the fiber (or whisker) is very small, generally below 10 mu m, the defects are few and small, the fracture strain is about thirty thousandths of a thousand, and the fiber (or whisker) is a brittle material and is easily damaged, fractured and corroded. The matrix is much lower in strength and modulus than the fibers, but can withstand large strains, tends to be viscoelastic and elastoplastic, and is a tough material.
The light wave range of the sunlight irradiating the ground is about 290-3000 nm. Most of the light is visible light (light wave is 400-800 nm, about 40%) and infrared light (light wave is 800-3000 nm, about 55%), and a small amount of ultraviolet light (light wave is 290-400 nm, about 5%). This few UV rays have a tremendous damaging effect on polymers. The ultraviolet ray has an energy of about (3.14 to 4.19) x 105J/mol, autoxidation of the majority of polymersThe activation energy is (0.42-1.67) x 105J/mol, and the dissociation energy of various chemical bonds is (1.67-4.18) x 105J/mol, and therefore the energy of the ultraviolet rays contained in the sunlight reaching the ground is sufficient to break the chemical bonds of the polymer, initiating autoxidation reactions leading to aged degradation.
However, after the paint prepared by the prior art is applied to the surface of glass fiber reinforced plastic, especially when the paint is applied to outdoor work, the paint can be irradiated by strong ultraviolet rays for a long time, and the aging performance of the paint is greatly accelerated.
Disclosure of Invention
The invention aims to provide a preparation method of a surface coating for glass fiber reinforced plastics, which has an anti-ultraviolet effect and aims to overcome the defects in the prior art.
The technical scheme adopted by the invention is as follows:
a preparation method of a surface coating for glass fiber reinforced plastics with an anti-ultraviolet effect comprises the following steps:
(1) preparing a polymer emulsion;
sequentially mixing sorbitol, isopropanol and 1, 4-butanediol, adding into a reaction kettle, heating to 72-78 ℃, keeping the temperature and stirring for 30min, then adding isophorone diisocyanate, adding an initiator, continuing to keep the temperature and stirring for reaction for 4-5 hours, and then adjusting the temperature value to 50-55 ℃ to obtain a reaction solution; adding ethylenediamine ethanesulfonic acid sodium salt solution, and stirring at high speed for 1-2 hr to obtain;
(2) preparing a filler:
mixing montmorillonite with an ethanol solution, and adding the mixture into a ball mill for ball milling treatment to obtain montmorillonite mixed solution;
adding alkali liquor into the montmorillonite mixed liquor, adjusting the pH to 10.5-11, stirring for 1 hour, adding sodium maleate, continuing stirring for 40min, standing for 2 hours, performing suction filtration, and drying to constant weight to obtain the filler;
(3) preparing the coating:
and sequentially adding the polymer emulsion, the filler, the cellulose, the defoaming agent, the nano titanium dioxide and the flatting agent into a stirrer, stirring at the rotating speed of 1500r/min for 30-35min, and then stirring at the rotating speed of 2500r/min for 40-44 min.
The mixing molar ratio of the sorbitol to the isopropanol to the 1, 4-butanediol is as follows: 0.3-0.5:3: 3;
the molar ratio of the isophorone diisocyanate to the 1, 4-butanediol is 1.25: 1.
The initiator is dibutyltin dilaurate;
the adding amount of the dibutyltin dilaurate is 2.5 percent of the mass of isophorone diisocyanate.
The mixing mass ratio of the ethylenediamine ethanesulfonic acid sodium salt solution to the reaction solution is 1: 3;
the mass fraction of the ethylenediamine ethanesulfonic acid sodium salt solution is 12.5%.
The mixing mass ratio of the montmorillonite to the ethanol solution is 1: 5-6;
the mass fraction of the ethanol solution is 30 percent;
the ball milling speed is 1500r/min, and the ball milling time is 1 hour.
The alkali liquor is a sodium hydroxide solution with the mass fraction of 12%;
the mass ratio of the sodium maleate to the montmorillonite is 1: 10-12.
The weight part ratio of the polymer emulsion to the filler to the cellulose to the defoaming agent to the nano titanium dioxide to the flatting agent is 78-85:26-30:6-10:2-3:0.5-0.8: 0.55-0.58.
The cellulose is subjected to modification treatment:
adding cellulose into deionized water, and uniformly stirring to obtain a cellulose dispersion liquid;
the mass fraction of the cellulose dispersion liquid is 35-40%;
adding nitric acid into cellulose dispersion, stirring uniformly, adding chitosan, stirring for 30min, filtering, cleaning to neutrality, and drying at 50 deg.C for 1.5 hr to obtain intermediate material;
the mixing mass ratio of the nitric acid to the cellulose dispersion liquid is 0.12: 100;
the mass ratio of the chitosan to the cellulose is 1: 10-13;
adding the intermediate material into the sodium phytate solution again, soaking for 1 hour, filtering, cleaning to be neutral, and drying at 50 ℃ for 1.5 hours to obtain a secondary intermediate material;
the mass fraction of the sodium phytate solution is 8-9%;
the mixing mass ratio of the intermediate material to the sodium phytate solution is 1: 5;
then immersing the secondary intermediate material into the nano ferroferric oxide particle dispersion liquid, performing immersion treatment for 2 hours in vacuum, then filtering, cleaning to be neutral, and drying for 1.5 hours at the temperature of 50 ℃ to obtain modified cellulose;
the mixing mass ratio of the secondary intermediate material to the nano ferroferric oxide particle dispersion liquid is 1: 5;
the mass fraction of the nano ferroferric oxide particle dispersion liquid is 12-13%.
The invention can greatly improve the mechanical property and the ultraviolet aging resistance of the coating by introducing the modified cellulose, the surface of the cellulose contains a large amount of hydroxyl groups, the cellulose can show negative charges in aqueous solution, the invention prepares the cellulose into dispersion liquid, then introduces nitric acid and chitosan solution, the chitosan has positive charges, polycations are combined to the surface of the cellulose by the attraction of the positive and negative of charged particles to obtain an intermediate material, and then the intermediate material is immersed into sodium phytate solution, and the sodium phytate solution has negative charges to promote the polyanions to be gradually combined to the surface of the cellulose to obtain a secondary intermediate material. The secondary intermediate material is immersed into the nano ferroferric oxide particle dispersion liquid, the nano ferroferric oxide particles are combined on the surface of cellulose through electrostatic adsorption to form multilayer modified cellulose with a complex structure, and the multilayer modified cellulose is introduced into polymer emulsion to absorb certain ultraviolet rays, reduce the influence of the ultraviolet rays on polymer molecules and improve the ultraviolet resistance of a coating.
Has the advantages that:
the coating prepared by the method has excellent ultraviolet resistance, and the ultraviolet resistance of the coating can be greatly improved by introducing the modified cellulose, so that when a coating formed by coating the glass fiber reinforced plastic with the coating is used outdoors, the coating can better resist the irradiation of ultraviolet light, and the service life of the coating is obviously prolonged.
Detailed Description
A preparation method of a surface coating for glass fiber reinforced plastics with an anti-ultraviolet effect comprises the following steps:
(1) preparing a polymer emulsion;
sequentially mixing sorbitol, isopropanol and 1, 4-butanediol, adding into a reaction kettle, heating to 72-78 ℃, keeping the temperature and stirring for 30min, then adding isophorone diisocyanate, adding an initiator, continuing to keep the temperature and stirring for reaction for 4-5 hours, and then adjusting the temperature value to 50-55 ℃ to obtain a reaction solution; adding ethylenediamine ethanesulfonic acid sodium salt solution, and stirring at high speed for 1-2 hr to obtain;
(2) preparing a filler:
mixing montmorillonite with an ethanol solution, and adding the mixture into a ball mill for ball milling treatment to obtain montmorillonite mixed solution;
adding alkali liquor into the montmorillonite mixed liquor, adjusting the pH to 10.5-11, stirring for 1 hour, adding sodium maleate, continuing stirring for 40min, standing for 2 hours, performing suction filtration, and drying to constant weight to obtain the filler;
(3) preparing the coating:
and sequentially adding the polymer emulsion, the filler, the cellulose, the defoaming agent, the nano titanium dioxide and the flatting agent into a stirrer, stirring at the rotating speed of 1500r/min for 30-35min, and then stirring at the rotating speed of 2500r/min for 40-44 min.
The mixing molar ratio of the sorbitol to the isopropanol to the 1, 4-butanediol is as follows: 0.3-0.5:3: 3;
the molar ratio of the isophorone diisocyanate to the 1, 4-butanediol is 1.25: 1.
The initiator is dibutyltin dilaurate;
the adding amount of the dibutyltin dilaurate is 2.5 percent of the mass of isophorone diisocyanate.
The mixing mass ratio of the ethylenediamine ethanesulfonic acid sodium salt solution to the reaction solution is 1: 3;
the mass fraction of the ethylenediamine ethanesulfonic acid sodium salt solution is 12.5%.
The mixing mass ratio of the montmorillonite to the ethanol solution is 1: 5-6;
the mass fraction of the ethanol solution is 30 percent;
the ball milling speed is 1500r/min, and the ball milling time is 1 hour.
The alkali liquor is a sodium hydroxide solution with the mass fraction of 12%;
the mass ratio of the sodium maleate to the montmorillonite is 1: 10-12.
The weight part ratio of the polymer emulsion to the filler to the cellulose to the defoaming agent to the nano titanium dioxide to the flatting agent is 78-85:26-30:6-10:2-3:0.5-0.8: 0.55-0.58.
The cellulose is subjected to modification treatment:
adding cellulose into deionized water, and uniformly stirring to obtain a cellulose dispersion liquid;
the mass fraction of the cellulose dispersion liquid is 35-40%;
adding nitric acid into cellulose dispersion, stirring uniformly, adding chitosan, stirring for 30min, filtering, cleaning to neutrality, and drying at 50 deg.C for 1.5 hr to obtain intermediate material;
the mixing mass ratio of the nitric acid to the cellulose dispersion liquid is 0.12: 100;
the mass ratio of the chitosan to the cellulose is 1: 10-13;
adding the intermediate material into the sodium phytate solution again, soaking for 1 hour, filtering, cleaning to be neutral, and drying at 50 ℃ for 1.5 hours to obtain a secondary intermediate material;
the mass fraction of the sodium phytate solution is 8-9%;
the mixing mass ratio of the intermediate material to the sodium phytate solution is 1: 5;
then immersing the secondary intermediate material into the nano ferroferric oxide particle dispersion liquid, performing immersion treatment for 2 hours in vacuum, then filtering, cleaning to be neutral, and drying for 1.5 hours at the temperature of 50 ℃ to obtain modified cellulose;
the mixing mass ratio of the secondary intermediate material to the nano ferroferric oxide particle dispersion liquid is 1: 5;
the mass fraction of the nano ferroferric oxide particle dispersion liquid is 12-13%.
The following will clearly and completely describe the technical solutions of 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 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
A preparation method of a surface coating for glass fiber reinforced plastics with an anti-ultraviolet effect comprises the following steps:
(1) preparing a polymer emulsion;
sequentially mixing sorbitol, isopropanol and 1, 4-butanediol, adding into a reaction kettle, heating to 72 ℃, keeping the temperature and stirring for 30min, then adding isophorone diisocyanate, adding an initiator, continuing to keep the temperature and stirring for reaction for 4 hours, and then adjusting the temperature value to 50 ℃ to obtain a reaction solution; adding ethylenediamine ethanesulfonic acid sodium salt solution, and stirring at high speed for 1 hr to obtain;
(2) preparing a filler:
mixing montmorillonite with an ethanol solution, and adding the mixture into a ball mill for ball milling treatment to obtain montmorillonite mixed solution; adding alkali liquor into the montmorillonite mixed liquor, adjusting the pH to 10.5, stirring for 1 hour, adding sodium maleate, continuing stirring for 40min, standing for 2 hours, performing suction filtration, and drying to constant weight to obtain the filler;
(3) preparing the coating:
and sequentially adding the polymer emulsion, the filler, the cellulose, the defoaming agent, the nano titanium dioxide and the flatting agent into a stirrer, stirring at the rotating speed of 1500r/min for 30min, and then stirring at the rotating speed of 2500r/min for 40 min. The mixing molar ratio of the sorbitol to the isopropanol to the 1, 4-butanediol is as follows: 0.3:3: 3; the molar ratio of the isophorone diisocyanate to the 1, 4-butanediol is 1.25: 1. The initiator is dibutyltin dilaurate; the adding amount of the dibutyltin dilaurate is 2.5 percent of the mass of isophorone diisocyanate. The mixing mass ratio of the ethylenediamine ethanesulfonic acid sodium salt solution to the reaction solution is 1: 3; the mass fraction of the ethylenediamine ethanesulfonic acid sodium salt solution is 12.5%. The mixing mass ratio of the montmorillonite to the ethanol solution is 1: 5; the mass fraction of the ethanol solution is 30 percent; the ball milling speed is 1500r/min, and the ball milling time is 1 hour. The alkali liquor is a sodium hydroxide solution with the mass fraction of 12%; the mass ratio of the sodium maleate to the montmorillonite is 1: 10. The weight ratio of the polymer emulsion to the filler to the cellulose to the defoaming agent to the nano titanium dioxide to the flatting agent is 78:26:6:2:0.5: 0.55.
Example 2
A preparation method of a surface coating for glass fiber reinforced plastics with an anti-ultraviolet effect comprises the following steps:
(1) preparing a polymer emulsion;
sequentially mixing sorbitol, isopropanol and 1, 4-butanediol, adding into a reaction kettle, heating to 78 ℃, keeping the temperature and stirring for 30min, then adding isophorone diisocyanate, adding an initiator, continuing to keep the temperature and stirring for reaction for 5 hours, and then adjusting the temperature value to 55 ℃ to obtain a reaction solution; adding ethylenediamine ethanesulfonic acid sodium salt solution, and stirring at high speed for 2 hr to obtain the final product;
(2) preparing a filler:
mixing montmorillonite with an ethanol solution, and adding the mixture into a ball mill for ball milling treatment to obtain montmorillonite mixed solution; adding alkali liquor into the montmorillonite mixed liquor, adjusting the pH to 11, stirring for 1 hour, adding sodium maleate, continuing stirring for 40min, standing for 2 hours, performing suction filtration, and drying to constant weight to obtain a filler;
(3) preparing the coating:
and sequentially adding the polymer emulsion, the filler, the cellulose, the defoaming agent, the nano titanium dioxide and the flatting agent into a stirrer, stirring at the rotating speed of 1500r/min for 35min, and then stirring at the rotating speed of 2500r/min for 44 min. The mixing molar ratio of the sorbitol to the isopropanol to the 1, 4-butanediol is as follows: 0.5:3: 3; the molar ratio of the isophorone diisocyanate to the 1, 4-butanediol is 1.25: 1. The initiator is dibutyltin dilaurate; the adding amount of the dibutyltin dilaurate is 2.5 percent of the mass of isophorone diisocyanate. The mixing mass ratio of the ethylenediamine ethanesulfonic acid sodium salt solution to the reaction solution is 1: 3; the mass fraction of the ethylenediamine ethanesulfonic acid sodium salt solution is 12.5%. The mixing mass ratio of the montmorillonite to the ethanol solution is 1: 6; the mass fraction of the ethanol solution is 30 percent; the ball milling speed is 1500r/min, and the ball milling time is 1 hour. The alkali liquor is a sodium hydroxide solution with the mass fraction of 12%; the mass ratio of the sodium maleate to the montmorillonite is 1: 12. The weight ratio of the polymer emulsion to the filler to the cellulose to the defoaming agent to the nano titanium dioxide to the flatting agent is 85:30:10:3:0.8: 0.58.
Example 3
A preparation method of a surface coating for glass fiber reinforced plastics with an anti-ultraviolet effect comprises the following steps:
(1) preparing a polymer emulsion;
sequentially mixing sorbitol, isopropanol and 1, 4-butanediol, adding into a reaction kettle, heating to 75 ℃, keeping the temperature and stirring for 30min, then adding isophorone diisocyanate, adding an initiator, continuing to keep the temperature and stirring for reaction for 4.5 hours, and then adjusting the temperature value to 52 ℃ to obtain a reaction solution; adding ethylenediamine ethanesulfonic acid sodium salt solution, and stirring at high speed for 1.5 hr to obtain;
(2) preparing a filler:
mixing montmorillonite with an ethanol solution, and adding the mixture into a ball mill for ball milling treatment to obtain montmorillonite mixed solution; adding alkali liquor into the montmorillonite mixed liquor, adjusting the pH to 10.7, stirring for 1 hour, adding sodium maleate, continuing stirring for 40min, standing for 2 hours, performing suction filtration, and drying to constant weight to obtain the filler;
(3) preparing the coating:
and sequentially adding the polymer emulsion, the filler, the cellulose, the defoaming agent, the nano titanium dioxide and the flatting agent into a stirrer, stirring at the rotating speed of 1500r/min for 32min, and then stirring at the rotating speed of 2500r/min for 42 min. The mixing molar ratio of the sorbitol to the isopropanol to the 1, 4-butanediol is as follows: 0.4:3: 3; the molar ratio of the isophorone diisocyanate to the 1, 4-butanediol is 1.25: 1. The initiator is dibutyltin dilaurate; the adding amount of the dibutyltin dilaurate is 2.5 percent of the mass of isophorone diisocyanate. The mixing mass ratio of the ethylenediamine ethanesulfonic acid sodium salt solution to the reaction solution is 1: 3; the mass fraction of the ethylenediamine ethanesulfonic acid sodium salt solution is 12.5%. The mixing mass ratio of the montmorillonite to the ethanol solution is 1: 5.3; the mass fraction of the ethanol solution is 30 percent; the ball milling speed is 1500r/min, and the ball milling time is 1 hour. The alkali liquor is a sodium hydroxide solution with the mass fraction of 12%; the mass ratio of the sodium maleate to the montmorillonite is 1: 11. The weight ratio of the polymer emulsion to the filler to the cellulose to the defoaming agent to the nano titanium dioxide to the flatting agent is 82:28:7.2:2.5:0.53: 0.56.
Example 4
A preparation method of a surface coating for glass fiber reinforced plastics with an anti-ultraviolet effect comprises the following steps:
(1) preparing a polymer emulsion;
sequentially mixing sorbitol, isopropanol and 1, 4-butanediol, adding into a reaction kettle, heating to 75 ℃, keeping the temperature and stirring for 30min, then adding isophorone diisocyanate, adding an initiator, continuing to keep the temperature and stirring for reaction for 4.5 hours, and then adjusting the temperature value to 52 ℃ to obtain a reaction solution; adding ethylenediamine ethanesulfonic acid sodium salt solution, and stirring at high speed for 1.5 hr to obtain;
(2) preparing a filler:
mixing montmorillonite with an ethanol solution, and adding the mixture into a ball mill for ball milling treatment to obtain montmorillonite mixed solution; adding alkali liquor into the montmorillonite mixed liquor, adjusting the pH to 10.7, stirring for 1 hour, adding sodium maleate, continuing stirring for 40min, standing for 2 hours, performing suction filtration, and drying to constant weight to obtain the filler;
(3) preparing the coating:
and sequentially adding the polymer emulsion, the filler, the cellulose, the defoaming agent, the nano titanium dioxide and the flatting agent into a stirrer, stirring at the rotating speed of 1500r/min for 32min, and then stirring at the rotating speed of 2500r/min for 42 min. The mixing molar ratio of the sorbitol to the isopropanol to the 1, 4-butanediol is as follows: 0.4:3: 3; the molar ratio of the isophorone diisocyanate to the 1, 4-butanediol is 1.25: 1. The initiator is dibutyltin dilaurate; the adding amount of the dibutyltin dilaurate is 2.5 percent of the mass of isophorone diisocyanate. The mixing mass ratio of the ethylenediamine ethanesulfonic acid sodium salt solution to the reaction solution is 1: 3; the mass fraction of the ethylenediamine ethanesulfonic acid sodium salt solution is 12.5%. The mixing mass ratio of the montmorillonite to the ethanol solution is 1: 5.3; the mass fraction of the ethanol solution is 30 percent; the ball milling speed is 1500r/min, and the ball milling time is 1 hour. The alkali liquor is a sodium hydroxide solution with the mass fraction of 12%; the mass ratio of the sodium maleate to the montmorillonite is 1: 11. The weight part ratio of the polymer emulsion to the filler to the cellulose to the defoaming agent to the nano titanium dioxide to the flatting agent is 82:28:7.2:2.5:0.53: 0.56; the cellulose is subjected to modification treatment: adding cellulose into deionized water, and uniformly stirring to obtain a cellulose dispersion liquid; the mass fraction of the cellulose dispersion is 35%; adding nitric acid into cellulose dispersion, stirring uniformly, adding chitosan, stirring for 30min, filtering, cleaning to neutrality, and drying at 50 deg.C for 1.5 hr to obtain intermediate material; the mixing mass ratio of the nitric acid to the cellulose dispersion liquid is 0.12: 100; the mass ratio of the chitosan to the cellulose is 1: 10; adding the intermediate material into the sodium phytate solution again, soaking for 1 hour, filtering, cleaning to be neutral, and drying at 50 ℃ for 1.5 hours to obtain a secondary intermediate material; the mass fraction of the sodium phytate solution is 8%; the mixing mass ratio of the intermediate material to the sodium phytate solution is 1: 5; then immersing the secondary intermediate material into the nano ferroferric oxide particle dispersion liquid, performing immersion treatment for 2 hours in vacuum, then filtering, cleaning to be neutral, and drying for 1.5 hours at the temperature of 50 ℃ to obtain modified cellulose; the mixing mass ratio of the secondary intermediate material to the nano ferroferric oxide particle dispersion liquid is 1: 5; the mass fraction of the nano ferroferric oxide particle dispersion liquid is 12%.
Example 5
A preparation method of a surface coating for glass fiber reinforced plastics with an anti-ultraviolet effect comprises the following steps:
(1) preparing a polymer emulsion;
sequentially mixing sorbitol, isopropanol and 1, 4-butanediol, adding into a reaction kettle, heating to 75 ℃, keeping the temperature and stirring for 30min, then adding isophorone diisocyanate, adding an initiator, continuing to keep the temperature and stirring for reaction for 4.5 hours, and then adjusting the temperature value to 52 ℃ to obtain a reaction solution; adding ethylenediamine ethanesulfonic acid sodium salt solution, and stirring at high speed for 1.5 hr to obtain;
(2) preparing a filler:
mixing montmorillonite with an ethanol solution, and adding the mixture into a ball mill for ball milling treatment to obtain montmorillonite mixed solution; adding alkali liquor into the montmorillonite mixed liquor, adjusting the pH to 10.7, stirring for 1 hour, adding sodium maleate, continuing stirring for 40min, standing for 2 hours, performing suction filtration, and drying to constant weight to obtain the filler;
(3) preparing the coating:
and sequentially adding the polymer emulsion, the filler, the cellulose, the defoaming agent, the nano titanium dioxide and the flatting agent into a stirrer, stirring at the rotating speed of 1500r/min for 32min, and then stirring at the rotating speed of 2500r/min for 42 min. The mixing molar ratio of the sorbitol to the isopropanol to the 1, 4-butanediol is as follows: 0.4:3: 3; the molar ratio of the isophorone diisocyanate to the 1, 4-butanediol is 1.25: 1. The initiator is dibutyltin dilaurate; the adding amount of the dibutyltin dilaurate is 2.5 percent of the mass of isophorone diisocyanate. The mixing mass ratio of the ethylenediamine ethanesulfonic acid sodium salt solution to the reaction solution is 1: 3; the mass fraction of the ethylenediamine ethanesulfonic acid sodium salt solution is 12.5%. The mixing mass ratio of the montmorillonite to the ethanol solution is 1: 5.3; the mass fraction of the ethanol solution is 30 percent; the ball milling speed is 1500r/min, and the ball milling time is 1 hour. The alkali liquor is a sodium hydroxide solution with the mass fraction of 12%; the mass ratio of the sodium maleate to the montmorillonite is 1: 11. The weight part ratio of the polymer emulsion to the filler to the cellulose to the defoaming agent to the nano titanium dioxide to the flatting agent is 82:28:7.2:2.5:0.53: 0.56; the cellulose is subjected to modification treatment: adding cellulose into deionized water, and uniformly stirring to obtain a cellulose dispersion liquid; the mass fraction of the cellulose dispersion is 40%; adding nitric acid into cellulose dispersion, stirring uniformly, adding chitosan, stirring for 30min, filtering, cleaning to neutrality, and drying at 50 deg.C for 1.5 hr to obtain intermediate material; the mixing mass ratio of the nitric acid to the cellulose dispersion liquid is 0.12: 100; the mass ratio of the chitosan to the cellulose is 1: 13; adding the intermediate material into the sodium phytate solution again, soaking for 1 hour, filtering, cleaning to be neutral, and drying at 50 ℃ for 1.5 hours to obtain a secondary intermediate material; the mass fraction of the sodium phytate solution is 9 percent; the mixing mass ratio of the intermediate material to the sodium phytate solution is 1: 5; then immersing the secondary intermediate material into the nano ferroferric oxide particle dispersion liquid, performing immersion treatment for 2 hours in vacuum, then filtering, cleaning to be neutral, and drying for 1.5 hours at the temperature of 50 ℃ to obtain modified cellulose; the mixing mass ratio of the secondary intermediate material to the nano ferroferric oxide particle dispersion liquid is 1: 5; the mass fraction of the nano ferroferric oxide particle dispersion liquid is 13%.
Example 6
A preparation method of a surface coating for glass fiber reinforced plastics with an anti-ultraviolet effect comprises the following steps:
(1) preparing a polymer emulsion;
sequentially mixing sorbitol, isopropanol and 1, 4-butanediol, adding into a reaction kettle, heating to 75 ℃, keeping the temperature and stirring for 30min, then adding isophorone diisocyanate, adding an initiator, continuing to keep the temperature and stirring for reaction for 4.5 hours, and then adjusting the temperature value to 52 ℃ to obtain a reaction solution; adding ethylenediamine ethanesulfonic acid sodium salt solution, and stirring at high speed for 1.5 hr to obtain;
(2) preparing a filler:
mixing montmorillonite with an ethanol solution, and adding the mixture into a ball mill for ball milling treatment to obtain montmorillonite mixed solution; adding alkali liquor into the montmorillonite mixed liquor, adjusting the pH to 10.7, stirring for 1 hour, adding sodium maleate, continuing stirring for 40min, standing for 2 hours, performing suction filtration, and drying to constant weight to obtain the filler;
(3) preparing the coating:
and sequentially adding the polymer emulsion, the filler, the cellulose, the defoaming agent, the nano titanium dioxide and the flatting agent into a stirrer, stirring at the rotating speed of 1500r/min for 32min, and then stirring at the rotating speed of 2500r/min for 42 min. The mixing molar ratio of the sorbitol to the isopropanol to the 1, 4-butanediol is as follows: 0.4:3: 3; the molar ratio of the isophorone diisocyanate to the 1, 4-butanediol is 1.25: 1. The initiator is dibutyltin dilaurate; the adding amount of the dibutyltin dilaurate is 2.5 percent of the mass of isophorone diisocyanate. The mixing mass ratio of the ethylenediamine ethanesulfonic acid sodium salt solution to the reaction solution is 1: 3; the mass fraction of the ethylenediamine ethanesulfonic acid sodium salt solution is 12.5%. The mixing mass ratio of the montmorillonite to the ethanol solution is 1: 5.3; the mass fraction of the ethanol solution is 30 percent; the ball milling speed is 1500r/min, and the ball milling time is 1 hour. The alkali liquor is a sodium hydroxide solution with the mass fraction of 12%; the mass ratio of the sodium maleate to the montmorillonite is 1: 11. The weight part ratio of the polymer emulsion to the filler to the cellulose to the defoaming agent to the nano titanium dioxide to the flatting agent is 82:28:7.2:2.5:0.53: 0.56; the cellulose is subjected to modification treatment: adding cellulose into deionized water, and uniformly stirring to obtain a cellulose dispersion liquid; the mass fraction of the cellulose dispersion is 38%; adding nitric acid into cellulose dispersion, stirring uniformly, adding chitosan, stirring for 30min, filtering, cleaning to neutrality, and drying at 50 deg.C for 1.5 hr to obtain intermediate material; the mixing mass ratio of the nitric acid to the cellulose dispersion liquid is 0.12: 100; the mass ratio of the chitosan to the cellulose is 1: 12; adding the intermediate material into the sodium phytate solution again, soaking for 1 hour, filtering, cleaning to be neutral, and drying at 50 ℃ for 1.5 hours to obtain a secondary intermediate material; the mass fraction of the sodium phytate solution is 8.5%; the mixing mass ratio of the intermediate material to the sodium phytate solution is 1: 5; then immersing the secondary intermediate material into the nano ferroferric oxide particle dispersion liquid, performing immersion treatment for 2 hours in vacuum, then filtering, cleaning to be neutral, and drying for 1.5 hours at the temperature of 50 ℃ to obtain modified cellulose; the mixing mass ratio of the secondary intermediate material to the nano ferroferric oxide particle dispersion liquid is 1: 5; the mass fraction of the nano ferroferric oxide particle dispersion liquid is 12.6%.
Test of
Preparing coating films on the surfaces of epoxy resin glass fiber reinforced plastics according to the coatings of examples and comparative examples by a method of GB 1765-79, drying at normal temperature under the conditions of constant temperature and constant humidity, and testing the physical and chemical properties;
(5 experiments per group, average);
gloss (60 °) according to GB/T1728-89;
TABLE 1
| Gloss (60 degree) | |
| Example 1 | 77 |
| Example 2 | 77 |
| Example 3 | 78 |
| Example 4 | 78 |
| Example 5 | 78 |
| Example 6 | 78 |
As can be seen from Table 1, the coating prepared by the method of the present invention has good glossiness, and the surface glossiness of the coating is not affected by the modification treatment of the fiber.
Impact resistance (GB/T1732-93)
TABLE 2
| Impact resistance kg cm | |
| Example 1 | 52 |
| Example 2 | 51 |
| Example 3 | 53 |
| Example 4 | 55 |
| Example 5 | 55 |
| Example 6 | 56 |
| Comparative example 1 | 46 |
Comparative example 1: the difference from example 4 is that no cellulose is added;
as can be seen from Table 2, the coating prepared by the method of the present invention has excellent impact resistance, and the impact resistance of the coating can be improved to some extent by introducing the modified cellulose.
Ultraviolet resistance: (GB/T14522-
TABLE 3
| Ultraviolet resistance (UVA-313 fluorescent ultraviolet lamp, 2500 h)/grade | |
| Example 1 | 2 |
| Example 2 | 2 |
| Example 3 | 2 |
| Example 4 | 1 |
| Example 5 | 1 |
| Example 6 | 1 |
| Comparative example 1 | 3 |
Comparative example 1: the difference from example 4 is that no cellulose is added;
as can be seen from Table 3, the coating prepared by the method has excellent ultraviolet resistance, and the ultraviolet resistance of the coating can be greatly improved by introducing the modified cellulose, so that when a coating formed by coating the glass fiber reinforced plastic with the coating disclosed by the invention is used outdoors, the coating can better resist ultraviolet irradiation, and the service life of the coating is remarkably prolonged.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention, and the present invention is not limited to the illustrated embodiments, and all the modifications and equivalents of the embodiments may be made without departing from the spirit of the present invention.
Claims (8)
1. A preparation method of a surface coating for glass fiber reinforced plastics with an anti-ultraviolet effect is characterized by comprising the following steps:
(1) preparing a polymer emulsion;
sequentially mixing sorbitol, isopropanol and 1, 4-butanediol, adding into a reaction kettle, heating to 72-78 ℃, keeping the temperature and stirring for 30min, then adding isophorone diisocyanate, adding an initiator, continuing to keep the temperature and stirring for reaction for 4-5 hours, and then adjusting the temperature value to 50-55 ℃ to obtain a reaction solution; adding ethylenediamine ethanesulfonic acid sodium salt solution, and stirring at high speed for 1-2 hr to obtain;
(2) preparing a filler:
mixing montmorillonite with an ethanol solution, and adding the mixture into a ball mill for ball milling treatment to obtain montmorillonite mixed solution;
adding alkali liquor into the montmorillonite mixed liquor, adjusting the pH to 10.5-11, stirring for 1 hour, adding sodium maleate, continuing stirring for 40min, standing for 2 hours, performing suction filtration, and drying to constant weight to obtain the filler;
(3) preparing the coating:
adding the polymer emulsion, the filler, the cellulose, the defoaming agent, the nano titanium dioxide and the flatting agent into a stirrer in sequence, stirring at the rotating speed of 1500r/min for 30-35min, and then stirring at the rotating speed of 2500r/min for 40-44 min.
2. The method for preparing the surface coating for the glass fiber reinforced plastic with the ultraviolet ray resisting effect according to claim 1, wherein the method comprises the following steps: the mixing molar ratio of the sorbitol to the isopropanol to the 1, 4-butanediol is as follows: 0.3-0.5:3: 3;
the molar ratio of the isophorone diisocyanate to the 1, 4-butanediol is 1.25: 1.
3. The method for preparing the surface coating for the glass fiber reinforced plastic with the ultraviolet ray resisting effect according to claim 1, wherein the method comprises the following steps: the initiator is dibutyltin dilaurate;
the adding amount of the dibutyltin dilaurate is 2.5 percent of the mass of isophorone diisocyanate.
4. The method for preparing the surface coating for the glass fiber reinforced plastic with the ultraviolet ray resisting effect according to claim 1, wherein the method comprises the following steps: the mixing mass ratio of the ethylenediamine ethanesulfonic acid sodium salt solution to the reaction solution is 1: 3;
the mass fraction of the ethylenediamine ethanesulfonic acid sodium salt solution is 12.5%.
5. The method for preparing the surface coating for the glass fiber reinforced plastic with the ultraviolet ray resisting effect according to claim 1, wherein the method comprises the following steps: the mixing mass ratio of the montmorillonite to the ethanol solution is 1: 5-6;
the mass fraction of the ethanol solution is 30 percent;
the ball milling speed is 1500r/min, and the ball milling time is 1 hour.
6. The method for preparing the surface coating for glass fiber reinforced plastics with the ultraviolet ray resisting effect according to claim 1 or 5, wherein the method comprises the following steps: the alkali liquor is a sodium hydroxide solution with the mass fraction of 12%;
the mass ratio of the sodium maleate to the montmorillonite is 1: 10-12.
7. The method for preparing the surface coating for the glass fiber reinforced plastic with the ultraviolet ray resisting effect according to claim 1, wherein the method comprises the following steps: the weight part ratio of the polymer emulsion to the filler to the cellulose to the defoaming agent to the nano titanium dioxide to the flatting agent is 78-85:26-30:6-10:2-3:0.5-0.8: 0.55-0.58.
8. The method for preparing the surface coating material for glass fiber reinforced plastics with the ultraviolet ray resisting effect according to claim 1 or 7, wherein the method comprises the following steps: the cellulose is subjected to modification treatment:
adding cellulose into deionized water, and uniformly stirring to obtain a cellulose dispersion liquid;
the mass fraction of the cellulose dispersion liquid is 35-40%;
adding nitric acid into cellulose dispersion, stirring uniformly, adding chitosan, stirring for 30min, filtering, cleaning to neutrality, and drying at 50 deg.C for 1.5 hr to obtain intermediate material;
the mixing mass ratio of the nitric acid to the cellulose dispersion liquid is 0.12: 100;
the mass ratio of the chitosan to the cellulose is 1: 10-13;
adding the intermediate material into the sodium phytate solution again, soaking for 1 hour, filtering, cleaning to be neutral, and drying at 50 ℃ for 1.5 hours to obtain a secondary intermediate material;
the mass fraction of the sodium phytate solution is 8-9%;
the mixing mass ratio of the intermediate material to the sodium phytate solution is 1: 5;
then immersing the secondary intermediate material into the nano ferroferric oxide particle dispersion liquid, performing immersion treatment for 2 hours in vacuum, then filtering, cleaning to be neutral, and drying for 1.5 hours at the temperature of 50 ℃ to obtain modified cellulose;
the mixing mass ratio of the secondary intermediate material to the nano ferroferric oxide particle dispersion liquid is 1: 5;
the mass fraction of the nano ferroferric oxide particle dispersion liquid is 12-13%.
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