Background
In the 21 st century, the total mileage of roads in China exceeds 125 kilometers, and the passenger and freight volume borne by the roads in China accounts for 88.7 percent and 99 percent of the total freight volume in China, so that the highway is the basis and the life line of national economic development. However, the amount of traffic facilities in China is still significantly insufficient compared to developed countries, and traffic management is still significantly weak. In terms of road markings, except for large and medium-sized cities and high-grade roads, most of the roads have no markings, and 90% of the coating used on the marked roads is a normal-temperature drying solvent-type coating which mainly adopts a hot-melt type using C5 petroleum resin as a base material and a normal-temperature solvent type using acrylic resin as a base material. However, both solvent-type and hot-melt type marking paints suffer from the disadvantage of releasing volatile substances to contaminate the air to a greater or lesser extent, and also from the disadvantage of being inconvenient to use and handle with hot-melt type marking paints.
The water-based marking paint mainly uses water as a diluent, has obvious advantages compared with a hot-melt type paint and a solvent type paint in terms of environmental protection, but simultaneously uses water as the diluent, and aims to improve the performance of the water-based marking paint in the aspects of curing surface drying rate, wear resistance, water resistance, bonding adhesion with the ground and the like of a coating film. In order to better enhance the adhesion between the conventional water-based marking paint and the road surface, various conditions such as the cleanness degree of the road surface, construction temperature, humidity, wind speed and the like are generally required to be ensured in the construction process, and the construction is generally not suitable under the conditions of high humidity, low temperature and the like. Therefore, innovative research and adjustment on the formula of the water-based marking paint are needed, and it is desirable to prepare a water-based marking paint which can still be normally constructed under the environmental conditions of high humidity, low temperature and the like, so that the construction convenience of the water-based marking paint is improved, and the adhesive force between the coating and the ground is obviously improved. In addition, there is a need to improve the water resistance of aqueous marking paints. The water-soluble property of the film-forming substance adopted in the water-based paint enables the water-based paint to have natural hydrophilic property, and after a coating film formed by the traditional water-based marking paint is soaked in water for a long time, the volume of the coating film is greatly expanded due to the swelling of a base material, so that stress is generated on the interface between a road surface and the coating film, and when the stress reaches a certain degree, the coating film can be peeled from the road surface. In addition, most urban roads are drained by using the ditches, once the ditches are blocked, water cannot be drained, the marked lines can be soaked for a long time, hollowing and bubbling are generated, and the marked lines are peeled off in a large scale. Furthermore, cement pavements have many capillaries which are not visible to the naked eye, and a large amount of water is present in the capillaries, which can erode the markings for a long period of time. Once the water is evaporated, a certain pressure is generated to promote the coating to fall off. Therefore, the performance of improving the water resistance, permeability, bonding force with a road surface and the like of the water-based marking paint has important significance for improving the use value of the water-based marking paint. Meanwhile, no matter what type of marking paint is used for road marking, the marking paint can be continuously rolled by vehicles and the like, so that the marking paint needs to have good wear resistance and mechanical strength, and the marking paint also needs to have antifouling and easy-to-clean performance in order to prolong the service life of the marking. Therefore, innovative improvement is carried out on the formula of the water-based marking paint to improve the film forming and curing performance, the penetration and adhesion performance with the pavement, the water resistance, the wear resistance, the mechanical strength and the antifouling and easy-to-clean performance of the traditional water-based marking paint, and the water-based marking paint has important significance for popularization and application of the water-based marking paint.
Disclosure of Invention
In order to solve the technical problems, the invention provides a water-based marking paint and a preparation method thereof, and aims to provide the water-based marking paint, the self-made graphene oxide modified benzophenone UV anti-ultraviolet agent is added, so that the mechanical property of the paint after coating is enhanced, and meanwhile, under the irradiation of strong ultraviolet rays, the paint is not deformed, discolored, cracked, aged and long in service life; 1, 8-naphthalimide modified acrylic resin is added to change the photoelectric property of the compound, so that the prepared coating has strong and lasting light reflecting capacity after being coated; therefore, the composite material has better comprehensive performance.
The invention provides a water-based marking paint which is characterized by being prepared from the following raw materials in parts by weight: 300-350 parts of HD-21A resin, 50-100 parts of titanium dioxide, 580 parts of 800-mesh calcium powder, 1-10 parts of water-based dispersant, 1-5 parts of water-based wetting agent, 15-25 parts of methanol, 10-20 parts of fluorescence modified water-soluble acrylic resin, 1-10 parts of 2% cellulose, 1-10 parts of Tween, 1-5 parts of graphene oxide modified benzophenone UV (ultraviolet) anti-ultraviolet agent and 40-70 parts of deionized water;
the graphene oxide modified benzophenone UV anti-ultraviolet agent is prepared by the following method:
(1) preparing graphene oxide by adopting an improved Hummers method;
(2) weighing graphene oxide, adding ethanol into the graphene oxide, performing ultrasonic dispersion uniformly, adding 2mol/L NaOH solution, mechanically stirring for 2 hours, washing a reaction product with distilled water until the pH is 7, then performing acid pickling on the reaction product with 0.1-0.5M HCL until the pH of supernatant is 1, washing the reaction product with distilled water until the pH is neutral, drying the reaction product at 70 ℃, adding the obtained solid into a benzophenone methanol solution, performing ultrasonic oscillation for 1-2 hours, adding distilled water, filtering, and repeatedly washing the solid with distilled water to obtain a graphene oxide modified benzophenone UV (ultraviolet) anti-ultraviolet agent;
the mass ratio of the graphene oxide to the NaOH solution is 1: (50-70);
the quantity ratio of the graphene oxide to the benzophenone is (0.2-1): 10.
as a further improvement of the invention, the health-care food is prepared from the following raw materials in parts by weight: 332 parts of HD-21A resin, 71 parts of titanium dioxide, 540 parts of 800-mesh calcium powder, 5 parts of a water-based dispersing agent, 2.1 parts of a water-based wetting agent, 21 parts of methanol, 16.3 parts of a fluorescence modified water-soluble acrylic resin, 8 parts of 2% cellulose, 5 parts of tween, 3 parts of a graphene oxide modified benzophenone UV (ultraviolet) anti-ultraviolet agent and 55 parts of deionized water.
As a further improvement of the invention, the fluorescence modified water-soluble acrylic resin is prepared by the following method: adding acrylic acid, butyl acrylate, methyl methacrylate, hydroxyethyl methacrylate and azobisisobutyronitrile into a reaction kettle, uniformly mixing, adding propylene glycol methyl ether accounting for 50% of the weight of the acrylic acid, stirring, heating to 75 ℃, reacting for 3-5 hours under the protection of nitrogen, adding 1, 8-naphthalene imide in batches, reacting at 80 ℃, stirring at constant temperature for 2 hours, stopping the reaction, cooling to 40 ℃, filtering, washing with ethanol, and drying the product to obtain the fluorescence modified water-soluble acrylic resin;
the mass ratio of the acrylic acid, the butyl acrylate, the methyl methacrylate, the hydroxyethyl methacrylate, the azodiisobutyronitrile and the 1, 8-naphthalimide substance is 1:2:1:5:0.2 (0.5-0.7).
As a further improvement of the invention, the aqueous dispersant is one or more selected from the group consisting of alkenyl bisstearamide, glyceryl monostearate, glyceryl tristearate, polycarboxylic acid ammonium salt, acrylic acid sodium salt copolymer, polyethylene glycol 200, polyethylene glycol 400, styrene-maleic anhydride and CT-136.
As a further improvement of the invention, the water-based wetting agent is selected from one or more of octylphenol polyoxyethylene ether series and polyether modified siloxane series.
As a further improvement of the invention, the aqueous defoaming agent is selected from one or more of GPE type defoaming agent, organic silicon defoaming agent and BYK 024.
As a further improvement of the invention, 1.2 parts of ammonia water is added into the water-based marking paint.
The invention further protects the preparation method of the water-based marking paint, which comprises the following steps: adding HD-21A resin and deionized water into a stirring barrel, and mechanically stirring at the rotating speed of 300-400rpm for about 2-5 min; adding a water-based dispersing agent, a water-based wetting agent and a water-based defoaming agent into the stirred resin, continuously stirring at the original speed for 10min, adding titanium dioxide and a graphene oxide modified benzophenone UV (ultraviolet) anti-ultraviolet agent, stirring for 5min, gradually adding 800-mesh calcium powder, adjusting the rotating speed to 500rpm, stirring for 15min, adding methanol, fluorescence modified water-soluble acrylic resin, 2% cellulose and tween, continuously stirring for 3.5min, barreling the stirred coating, and isolating the coating from contacting with air to obtain the coating.
As a further improvement of the invention, the coating is filtered by a 100-mesh filtering device before being barreled.
As a further improvement of the invention, ammonia is added at the time of addition of methanol.
The invention has the following beneficial effects:
1. the self-made graphene oxide modified benzophenone UV anti-ultraviolet agent is added into the water-based marking paint prepared by the invention, so that the mechanical property of the paint after coating is enhanced, the paint has better tensile property, elasticity and ductility, meanwhile, the graphene oxide modified benzophenone UV anti-ultraviolet agent can well prevent the coating from aging, and the coating does not deform, discolor, crack or age under the irradiation of strong ultraviolet rays, has long service life and better comprehensive performance;
2. the fluorescence modified water-soluble acrylic resin added into the water-based marking paint disclosed by the invention is 1, 8-naphthalimide modified acrylic resin, has water solubility, is an excellent film-forming aid, and has good fluorescence performance because of having unsaturated groups such as conjugated heterocycles, e.g. benzene rings, and the like, so that the photoelectric property of the compound is changed, and the prepared paint has strong and lasting light reflecting capacity after being coated;
3. the water-based marking paint prepared by the invention has the advantages of quick film forming, high mechanical strength, antifouling property, easy cleaning, good water resistance and wear resistance after film forming and curing, easy construction, good permeability with a road surface, strong adhesive force, no emission of harmful organic gases, safety and environmental protection.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below in conjunction with the embodiments of the present invention, and it is obvious that the embodiments described are only some representative embodiments of the present invention, rather than all embodiments, and all other embodiments obtained by a person skilled in the art without creative efforts belong to the protection scope of the present invention.
Example 1 preparation of aqueous marking paint
The raw materials comprise the following components in parts by weight: 300 parts of HD-21A resin (produced by Dow corporation), 50 parts of titanium dioxide, 500 parts of 800-mesh calcium powder, 1 part of stearic acid monoglyceride, 1 part of polyether modified siloxane, 1 part of organic silicon defoamer, 15 parts of methanol, 10 parts of fluorescence modified water-soluble acrylic resin, 1 part of 2% cellulose, 1 part of tween, 1 part of graphene oxide modified benzophenone UV (ultraviolet) resistant agent and 40 parts of deionized water;
the graphene oxide modified benzophenone UV anti-ultraviolet agent is prepared by the following method:
(1) preparing graphene oxide by adopting an improved Hummers method;
weighing 10G of natural graphite powder, 4G of potassium persulfate and 10G of phosphorus pentoxide, adding the natural graphite powder, the potassium persulfate and the phosphorus pentoxide into a three-neck flask filled with 24 mL of sulfuric acid under the condition of stirring, firstly reacting in a constant-temperature water bath at 60 ℃ for 3h, then moving the three-neck flask into a constant-temperature water bath at 25 ℃ for reacting for 5h, performing suction filtration, washing the three-neck flask to be neutral by using ionized water, and drying the three-neck flask in the air to obtain pre-oxidized graphite (P-G);
step two, weighing l g pre-oxidized graphite, adding the pre-oxidized graphite into a three-neck flask filled with 25 mL of sulfuric acid under the condition of stirring, putting the three-neck flask into an ice water bath, and adding 3 after the pre-oxidized graphite is completely dissolvedg potassium permanganate, reacting for 2 hours, moving the three-neck flask into a constant-temperature water bath at 35 ℃ for reacting for 40min, finally adding deionized water, continuing to react for 1 hour at 35 ℃, and finally dropwise adding 30% of H2O2So that the solution turned bright yellow until no more gas was formed. The mixture was filtered by centrifugation while hot and washed to neutrality with a large amount of 5% hydrochloric acid and deionized water. Subjecting the final precipitate to l h ultrasonic vibration, pouring into a culture dish, and drying at 90 deg.C for 24 hr to obtain flake graphite oxide;
(2) weighing 1g of graphene oxide, adding ethanol, performing ultrasonic dispersion uniformly, adding 50g of 2mol/L NaOH solution, mechanically stirring for 2 hours, washing a reaction product with distilled water until the pH is 7, then washing the reaction product with 0.1mol/L HCL until the pH of supernatant is 1, washing the reaction product with distilled water until the pH is neutral, drying the reaction product at 70 ℃, adding the obtained solid into 50g of benzophenone methanol solution, performing ultrasonic oscillation for 1 hour, adding distilled water, filtering, and repeatedly washing the solid with distilled water to obtain the graphene oxide modified benzophenone UV (ultraviolet) anti-ultraviolet agent;
the fluorescence modified water-soluble acrylic resin is prepared by the following method: adding 1mol of acrylic acid, 2mol of butyl acrylate, 1mol of methyl methacrylate, 5mol of hydroxyethyl methacrylate and 0.2mol of azobisisobutyronitrile into a reaction kettle, uniformly mixing, adding propylene glycol methyl ether accounting for 50% of the weight of the acrylic acid, starting stirring, heating to 75 ℃, reacting for 3 hours under the protection of nitrogen, adding 0.5mol of 1, 8-naphthalimide in batches, reacting at 80 ℃, stirring at constant temperature for 2 hours, stopping the reaction, cooling to 40 ℃, filtering, washing with ethanol and drying the product to obtain the fluorescence modified water-soluble acrylic resin;
the preparation method of the water-based marking paint comprises the following steps: adding HD-21A resin and deionized water into a stirring barrel, and mechanically stirring at the rotating speed of 300rpm for about 2 min; adding stearic acid monoglyceride, polyether modified siloxane and an organic silicon defoaming agent into the stirred resin, continuously stirring at the original speed for 10min, adding titanium dioxide and graphene oxide modified benzophenone UV anti-ultraviolet agent, stirring for 5min, gradually adding 800-mesh calcium powder, adjusting the rotating speed to 500rpm, stirring for 15min, adding methanol, fluorescence modified water-soluble acrylic resin, 2% cellulose and tween, continuously stirring for 3.5min, barreling the stirred coating, and isolating the coating from contacting with air to obtain the coating.
Example 2 preparation of aqueous marking paint
The raw materials comprise the following components in parts by weight: 350 parts of HD-21A resin (produced by Dow corporation), 100 parts of titanium dioxide, 580 parts of 800-mesh calcium powder, 10 parts of styrene-maleic anhydride, 5 parts of octylphenol polyoxyethylene ether, 5 parts of GPE (general purpose olefin) defoamer, 25 parts of methanol, 20 parts of fluorescence modified water-soluble acrylic resin, 10 parts of 2% cellulose, 10 parts of Tween, 5 parts of graphene oxide modified benzophenone UV (ultraviolet) inhibitor and 70 parts of deionized water;
the graphene oxide modified benzophenone UV anti-ultraviolet agent is prepared by the following method:
(1) preparing graphene oxide by adopting an improved Hummers method;
(3) weighing 1g of graphene oxide, adding ethanol, performing ultrasonic dispersion uniformly, adding 70g of 2mol/L NaOH solution, mechanically stirring for 2 hours, washing a reaction product with distilled water until the pH is 7, then washing the reaction product with 0.5mol/L HCL until the pH of supernatant is 1, washing the reaction product with distilled water until the pH is neutral, drying the reaction product at 70 ℃, adding the obtained solid into 10g of benzophenone methanol solution, performing ultrasonic oscillation for 2 hours, adding distilled water, filtering, and repeatedly washing the solid with distilled water to obtain the graphene oxide modified benzophenone UV (ultraviolet) anti-ultraviolet agent;
the fluorescence modified water-soluble acrylic resin is prepared by the following method: adding 1mol of acrylic acid, 2mol of butyl acrylate, 1mol of methyl methacrylate, 5mol of hydroxyethyl methacrylate and 0.2mol of azobisisobutyronitrile into a reaction kettle, uniformly mixing, adding propylene glycol methyl ether accounting for 50% of the weight of the acrylic acid, starting stirring, heating to 75 ℃, reacting for 5 hours under the protection of nitrogen, adding 0.7mol of 1, 8-naphthalimide in batches, reacting at 80 ℃, stirring at constant temperature for 2 hours, stopping the reaction, cooling to 40 ℃, filtering, washing with ethanol and drying the product to obtain the fluorescence modified water-soluble acrylic resin;
the preparation method of the water-based marking paint comprises the following steps: adding HD-21A resin and deionized water into a stirring barrel, and mechanically stirring at the rotating speed of 400rpm for about 5 min; adding styrene-maleic anhydride, octylphenol polyoxyethylene ether and GPE type defoaming agent into the stirred resin, continuously stirring for 10min at the original speed, adding titanium dioxide and graphene oxide modified benzophenone UV anti-ultraviolet agent, stirring for 5min, gradually adding 800 mesh calcium powder, adjusting the rotating speed to 500rpm, stirring for 15min, adding methanol, fluorescence modified water-soluble acrylic resin, 2% cellulose and tween, continuously stirring for 3.5min, barreling the stirred coating, and isolating the coating from contacting with air to obtain the coating.
Example 3 preparation of aqueous marking paint
The raw materials comprise the following components in parts by weight: 332 parts of HD-21A resin (produced by Dow corporation), 71 parts of titanium dioxide, 540 parts of 800-mesh calcium powder, CT-1365 parts, 2 parts of octylphenol polyoxyethylene ether, BYK 0242.1 parts, 21 parts of methanol, 16.3 parts of fluorescence modified water-soluble acrylic resin, 8 parts of 2% cellulose, 5 parts of Tween, 3 parts of graphene oxide modified benzophenone UV (ultraviolet) resistant agent and 55 parts of deionized water;
the graphene oxide modified benzophenone UV anti-ultraviolet agent is prepared by the following method:
(1) preparing graphene oxide by adopting an improved Hummers method;
(2) weighing 1g of graphene oxide, adding ethanol, performing ultrasonic dispersion uniformly, adding 60g of 2mol/L NaOH solution, mechanically stirring for 2 hours, washing a reaction product with distilled water until the pH is 7, then washing the reaction product with 0.35mol/L HCL until the pH of supernatant is 1, washing the reaction product with distilled water until the pH is neutral, drying the reaction product at 70 ℃, adding the obtained solid into 30g of benzophenone methanol solution, performing ultrasonic oscillation for 1.5 hours, adding distilled water, filtering, and repeatedly washing the solid with distilled water to obtain the graphene oxide modified benzophenone UV (ultraviolet) anti-ultraviolet agent;
the fluorescence modified water-soluble acrylic resin is prepared by the following method: adding 1mol of acrylic acid, 2mol of butyl acrylate, 1mol of methyl methacrylate, 5mol of hydroxyethyl methacrylate and 0.2mol of azobisisobutyronitrile into a reaction kettle, uniformly mixing, adding propylene glycol methyl ether accounting for 50% of the weight of the acrylic acid, starting stirring, heating to 75 ℃, reacting for 3-5h under the protection of nitrogen, adding 0.6mol of 1, 8-naphthalimide in batches, reacting at 80 ℃, stirring at constant temperature for 2h, stopping the reaction, cooling to 40 ℃, filtering, washing with ethanol and drying the product to obtain the fluorescence modified water-soluble acrylic resin;
the preparation method of the water-based marking paint comprises the following steps: adding HD-21A resin and deionized water into a stirring barrel, and mechanically stirring at the rotating speed of 350rpm for about 3 min; adding CT-136, octylphenol polyoxyethylene ether and BYK024 into the stirred resin, continuously stirring at the original speed for 10min, adding titanium dioxide and graphene oxide modified benzophenone UV anti-ultraviolet agent, stirring for 5min, gradually adding 800-mesh calcium powder, adjusting the rotating speed to 500rpm, stirring for 15min, adding methanol, fluorescence modified water-soluble acrylic resin, 2% cellulose and tween, continuously stirring for 3.5min, separately barreling the stirred coating, and isolating the coating from contacting with air to obtain the coating.
Test example 1 Performance test
The water-based reticle coatings prepared in examples 1-3 of the present invention were subjected to performance tests and the results are shown in table 1.
Table 1 table of performance test results
Item
| Example 1
| Example 2
| Example 3
|
Reticle thickness (mm)
| 2.4
| 2.5
| 2.5
|
Curing time (min)
| 15min
| 15min
| 15min
|
Reflection at night
| Reflecting light
| Reflecting light
| Reflecting light
|
Luminance factor
| 1.31
| 1.30
| 1.32
|
Water resistance (soaking in water for 24 h)
| No abnormality
| No abnormality
| No abnormality
|
Compressive strength (MPa)
| 24.7
| 24.5
| 25.1
|
Abrasion resistance (rubber grinding wheel 200/1000 g)
| 59.5
| 59.7
| 60.2
|
Impact Strength (kg/cm)
| 64
| 63
| 65
|
Service life (sky)
| 500-520
| 500-520
| 500-520 |
As can be seen from the table above, the water-based marking paint prepared by the invention has the advantages of short film-forming curing time, good water resistance and wear resistance, excellent mechanical property, excellent light reflection property, high light reflection strength and long service life, so that the water-based marking paint has excellent comprehensive performance and wide application prospect.
Various modifications may be made to the above without departing from the spirit and scope of the invention as defined by the appended claims. The scope of the invention is therefore intended to be limited not by the above description, but rather by the scope of the appended claims.