Two-component heat-resistant marking paint and preparation method thereof

Abstract

The invention provides a double-group heat-resistant marking coating and a preparation method thereof. A component A is prepared from the following raw materials in parts by mass: 30 to 50 parts of active acrylic resin, 7 to 10 parts of functional diluent, 20 to 30 parts of glass beads, 10 to 30 parts of pigment, 0.5 to 1.5 parts of anti-settling agent and the balance of filler; the functional diluent is prepared by the following steps: reacting a hydroxyphthalic anhydride derivative with a fluorine-containing phenylenediamine derivative to generate an intermediate compound with phenolic hydroxyl groups at two ends, and then blocking the intermediate compound with acryloyl chloride; the component B is an initiator; the use amount of the component B meets the condition that the initiator accounts for 1.5-2.5 wt% of the total mass of the active acrylic resin and the functional diluent in the component A. And the cured marking paint has good heat resistance and relatively low abrasion mass loss.

Description

Technical Field

[0001] The invention belongs to the technical field of road marking paints, and in particular relates to a double-group heat-resistant road marking paint and a preparation method thereof. Background Art

[0002] Road traffic markings are safety facilities that are marked on the road surface or other facilities with prescribed lines, arrows, words, etc. to control and guide traffic. They have become an important part of highway construction and maintenance management. Road markings should provide guidance with high brightness during the day and be sufficiently recognizable at night.

[0003] Two-component road marking paint is a chemical reaction type of marking paint, which is currently mostly acrylates, also known as MMA two-component, with reactive low molecular weight acrylate prepolymers, acrylates or styrene monomers and multifunctional acrylate monomers as binders and solvents, supplemented with pigments and additives as the main agent, and dibenzoyl peroxide is often used as a curing agent. For example, patent CN108102024B discloses an active resin and a two-component solventless airless spray road marking paint, wherein the active resin is composed of the following components: methyl methacrylate, butyl acrylate, functional monomers and OPE wax. The two-component solventless airless spray road marking paint is composed of coating A and coating B in a ratio of 1-3:1, wherein coating A is composed of the following components: active resin, titanium dioxide, composite anti-settling agent, calcium carbonate, modified glass microspheres, initiator and other additives. Patent CN101805552B discloses a highly anti-fouling road marking paint and a preparation method thereof. The invention comprises two components, A and B. The formula of component A is: 30-50 parts of active MMA reactive acrylate resin; 10-20 parts of titanium dioxide; 1-5 parts of plasticizer; 0.1-0.3 parts of antistatic agent; 0.1-1 parts of antifouling agent; the rest is filler; the total number of parts is 100 parts; the formula of component B is: 30-50 parts of active MMA reactive acrylate resin; 10-20 parts of titanium dioxide; 1-5 parts of plasticizer; 0.1-0.3 parts of antistatic agent; 0.1-1 parts of antifouling agent; 0.5-5 parts of curing agent; the rest is filler; the total number of parts is 100 parts; the two components A and B are mixed according to a weight ratio of 1-4:1 when used.

[0004] All of the above are durable coatings formed by mixing two or more components in a certain proportion and reacting evenly. They have the advantages of strong adhesion to glass beads, excellent continuous reflection and good environmental benefits. However, polymethacrylate resin partially degrades after being exposed to high temperatures. Although there is no blistering or wrinkling on the surface, its wear resistance is greatly reduced, and the quality loss in the wear resistance test is relatively large. Therefore, it is very necessary to develop a two-component road marking paint with good heat resistance. Summary of the invention

[0005] In order to solve the above problems, the present invention provides a double-group heat-resistant road marking paint and a preparation method thereof. The double-group heat-resistant road marking paint includes a functional diluent. The functional diluent is firstly prepared by reacting a hydroxyphthalic anhydride derivative and a fluorinated phenylenediamine derivative to generate an intermediate compound with phenolic hydroxyl groups at both ends, and then end-capping the intermediate compound with acryloyl chloride. The molecular structure of the functional diluent contains polar imide bonds and unsaturated bonds. Through the reaction between the unsaturated bonds and the active acrylic resin, on the one hand, the crosslinking degree of the coating is improved, thereby improving the heat resistance of the coating. On the other hand, polar imide bonds are introduced into the coating to improve the interaction force between molecules and reduce the wear quality loss.

[0006] To achieve the above object, the present invention adopts the following technical solutions:

[0007] A two-component heat-resistant road marking paint, comprising components A and B, wherein the component A comprises the following raw materials in parts by weight: 30-50 parts of active acrylic resin, 7-10 parts of functional diluent, 20-30 parts of glass microspheres, 10-30 parts of pigment, 0.5-1.5 parts of anti-settling agent, and the filler is supplemented to 100 parts; the functional diluent is firstly prepared by reacting a hydroxyphthalic anhydride derivative and a fluorinated phenylenediamine derivative to generate an intermediate compound having phenolic hydroxyl groups at both ends, and then end-capping the intermediate compound with acryloyl chloride;

[0008] The B component is an initiator; the amount of the B component is such that the initiator is 1.5-2.5 wt % of the total mass of the active acrylic resin and the functional diluent in the A component.

[0009] Furthermore, the molar ratio of the hydroxyphthalic anhydride derivative to the fluorinated phenylenediamine derivative is 2.08-2.12:1, and the molar ratio of the acryloyl chloride to the hydroxyphthalic anhydride derivative is 1:0.95-1.

[0010] Furthermore, the fluorinated benzene diamine derivative is selected from one or a combination of two or more of 5-fluorobenzene-1,3-diamine, 2-fluorobenzene-1,4-diamine, 4-fluoro-1,2-phenylenediamine, 4-fluoro-1,3-diaminobenzene, and 3-fluoro-1,2-phenylenediamine; and the hydroxyphthalic anhydride derivative is selected from one or a combination of two of 3-hydroxyphthalic anhydride and 4-hydroxyphthalic anhydride.

[0011] Furthermore, the functional diluent is prepared by a method comprising the following steps:

[0012] 1) adding a catalyst to an organic solvent, raising the temperature to a reflux state, and simultaneously dropping a hydroxyphthalic anhydride derivative solution and a fluorinated phenylenediamine derivative solution, reacting at a constant temperature after the dropwise addition, during which water is continuously separated by a water separator, cooling after the reaction is completed, adding an alkaline solution to adjust the pH to neutral, standing, separating the organic phase, drying, filtering, and distilling under reduced pressure to obtain an intermediate with phenolic hydroxyl groups at both ends;

[0013] 2) Under an inert atmosphere, the intermediate obtained in step 1) and the acid-binding agent are dissolved in an organic solvent under ice bath conditions, and the acryloyl chloride solution is added dropwise. After the addition, the reaction is carried out. After the reaction is completed, the mixture is filtered and distilled under reduced pressure. The crude product is dissolved in an organic solvent, washed, dried, filtered, and distilled under reduced pressure to obtain a functional diluent.

[0014] Furthermore, in step 1), the organic solvent is selected from one or a combination of toluene and benzene. The catalyst is selected from one or a combination of two or more of phosphoric acid, sulfuric acid, p-toluenesulfonic acid, and phosphorus pentoxide, and the amount of the catalyst is 3-5wt% of the sum of the hydroxyphthalic anhydride derivative and the fluorinated phenylenediamine derivative. The temperature is raised to 90-120°C, and the dropwise addition time is 1-3h. The molar ratio of the hydroxyphthalic anhydride derivative to the fluorinated phenylenediamine derivative is 2.08-2.12:1, the concentration of the hydroxyphthalic anhydride derivative solution is 1-3mol / L, and the solvent is selected from one or a combination of acetone and methyl ethyl ketone. The concentration of the fluorinated phenylenediamine derivative solution is 1-3mol / L, and the solvent is selected from one or a combination of chloroform and dichloromethane. The constant temperature reaction time is 1-3h, the alkaline solution is selected from one or a combination of sodium bicarbonate solution and sodium carbonate solution, the concentration of the alkaline solution is 5-10wt%, and the standing time is 1-2h.

[0015] Furthermore, in step 2), the organic solvent is selected from one or a combination of two or more of toluene, benzene, and DMF. The acid binding agent is selected from one or a combination of two or more of triethylamine, N,N-dimethylacetamide, pyridine, N,N-diisopropylethylamine, and 4-dimethylaminopyridine. The molar ratio of the acid binding agent to acryloyl chloride is 1.5-2:1, and the molar ratio of acryloyl chloride to the hydroxyphthalic anhydride derivative in step 1) is 1:0.95-1. The concentration of the acryloyl chloride solution is 1-3 mol / L, and the dropping time is 1-2h. The reaction time is 1-5h. The solvent of the acryloyl chloride solution is selected from one or a combination of two or more of ethanol, chloroform, ether, and petroleum ether. The reduced pressure distillation is to remove the organic solvent, and the washing is to wash with water.

[0016] Furthermore, the viscosity of the reactive acrylic resin at 25° C. is 10,000-30,000 mPa·s, and the reactive acrylic resin comprises 25-50wt% of a reactive diluent and 50-75wt% of an acrylic resin oligomer. The functionality of the reactive diluent is 1-2, and the reactive diluent includes but is not limited to one or a combination of two of tripropylene glycol diacrylate and 1,6-hexanediol diacrylate.

[0017] Furthermore, the reactive acrylic resin is selected from one or a combination of two or more of Cytec EB705, Cytec EB745, and Cytec EB1710.

[0018] Furthermore, the anti-settling agent is selected from one or a combination of two or more of organic bentonite, fumed silica, and hydrogenated castor oil.

[0019] Furthermore, the initiator is selected from one or a combination of two or more of dibenzoyl peroxide and benzoyl peroxide.

[0020] Furthermore, the glass microspheres have a particle size of 0.1-1.5 mm, a roundness of ≥90%, and a refractive index of 1.9-2.1.

[0021] Furthermore, the pigment is not particularly limited and may be any pigment commonly used in the art, and may be selected from one or a combination of two or more of titanium dioxide, ultramarine, lead chrome yellow, and zinc chrome yellow.

[0022] Furthermore, the filler is selected from one or a combination of two or more of heavy calcium carbonate, light calcium carbonate, silica powder, talcum powder, mica powder, barium sulfate, and double fly ash.

[0023] Furthermore, the two-component heat-resistant road marking paint may also include 0.5-5 parts of an auxiliary agent.

[0024] Furthermore, the auxiliary agent is not particularly limited and can be selected from one or a combination of two or more of an anti-ultraviolet agent and an antioxidant.

[0025] The present invention also provides a method for preparing the above-mentioned double-group heat-resistant road marking paint, comprising the following steps:

[0026] Prepare component A: add functional diluent and anti-settling agent to active acrylic resin and mix evenly, add glass micro beads, pigment and filler and mix evenly;

[0027] Prepare component B: add functional diluent, initiator, anti-settling agent to active acrylic resin and mix evenly, add glass micro beads, pigment, and filler and mix evenly;

[0028] Mix component A and component B in proportion and apply them on the road surface by spraying or scraping.

[0029] Compared with the prior art, the present invention has the following beneficial effects:

[0030] The double-group heat-resistant road marking paint of the present invention includes a functional diluent. The functional diluent is firstly prepared by reacting a hydroxyphthalic anhydride derivative with a fluorinated phenylenediamine derivative to generate an intermediate compound with phenolic hydroxyl groups at both ends, and then end-capping the intermediate compound with acryloyl chloride. The molecular structure of the functional diluent contains polar imide bonds and unsaturated bonds. Through the reaction between the unsaturated bonds and the active acrylic resin, on the one hand, the crosslinking degree of the paint is improved, thereby improving the heat resistance of the paint. On the other hand, polar imide bonds are introduced into the paint to improve the interaction force between molecules and reduce the wear quality loss. DETAILED DESCRIPTION

[0031] The present invention will be further described below in conjunction with specific embodiments, but is not limited to the contents of the specification. Unless otherwise specified, the "parts" described in the embodiments of the present invention are all parts by weight. The reagents used are all commercially available reagents in the art.

[0032] Example 1

[0033] 1) Add 1.45 g of p-toluenesulfonic acid to 0.7 L of toluene, raise the temperature to 112° C., and simultaneously dropwise add 0.208 L of 1 mol / L 4-hydroxyphthalic anhydride solution (solvent: acetone) and 0.1 L of 1 mol / L 2-fluorobenzene-1,4-diamine solution (solvent: chloroform), and continue to react at a constant temperature for 2 h. During this period, water is continuously separated by a water separator. After the reaction is completed, cool to room temperature, add 5 wt % sodium bicarbonate solution to adjust the pH to neutral, stand for 0.5 h, separate the organic phase, add anhydrous magnesium sulfate to dry the organic phase to remove water, filter, remove the solvent under reduced pressure, and distill to obtain an intermediate with phenolic hydroxyl groups at both ends.

[0034] 2) Under nitrogen atmosphere, the intermediate obtained in step 1) and 0.32 mol of triethylamine were dissolved in 0.5 L of toluene under ice bath conditions, and 0.208 L of 1 mol / L acryloyl chloride solution (solvent ether) was added dropwise for 2 h, and the reaction was carried out for 3 h. After the reaction was completed, the reaction was filtered and distilled under reduced pressure. The crude product was dissolved in toluene, washed with water, and the organic phase was separated. The organic phase was dried over anhydrous magnesium sulfate, filtered, and distilled under reduced pressure to obtain a functional diluent.

[0035] 3) Preparation of component A: 10g of the functional diluent obtained in step 2) and 0.8g of anti-settling agent hydrogenated castor oil are added to 50g of active acrylic resin cyanote EB745 and mixed evenly, and 20g of glass microspheres, 10g of titanium dioxide and 1250 mesh double fly ash are added to make up to 100g and mixed evenly. The glass microspheres are glass microspheres with a particle size of 0.1-0.5mm, glass microspheres with a particle size of 0.2-0.65mm, and glass microspheres with a particle size of 0.8-1.5mm, mixed in a mass ratio of 1:4:6, with a roundness of ≥90% and a refractive index of 2.0.

[0036] 4) Preparation of component B: Weigh 1.5 g of curing agent benzoyl peroxide, which is 2.5 wt% of the sum of the mass of the functional diluent and the reactive acrylic resin Cytec EB745 in component A.

[0037] 5) Mix component A and component B in a mass ratio of 1:1 and spray them on the road surface with a spraying thickness of 1.5 mm.

[0038] Example 2

[0039] The rest is the same as Example 1, except that in step 1), an equal molar amount of 4-fluoro-1,3-diaminobenzene is used to replace 2-fluorobenzene-1,4-diamine.

[0040] Example 3

[0041] The rest is the same as Example 1, except that in step 1), an equimolar amount of 3-hydroxyphthalic anhydride is used to replace 4-hydroxyphthalic anhydride.

[0042] Example 4

[0043] The rest is the same as Example 1, except that the amount of the functional diluent in component A is 7 g.

[0044] Example 5

[0045] The rest is the same as Example 1, except that:

[0046] 1) Add 1.45 g of p-toluenesulfonic acid to 0.7 L of toluene, raise the temperature to 120° C., and simultaneously dropwise add 0.212 L of 1 mol / L 3-hydroxyphthalic anhydride solution (solvent: acetone) and 0.1 L of 1 mol / L 5-fluorobenzene-1,3-diamine solution (solvent: chloroform), and continue to react at a constant temperature for 2 h. During this period, water is continuously separated by a water separator. After the reaction is completed, cool to room temperature, add 5 wt % sodium bicarbonate solution to adjust the pH to neutral, stand for 0.5 h, separate the organic phase, add anhydrous magnesium sulfate to dry the organic phase to remove water, filter, remove the solvent under reduced pressure, and distill to obtain an intermediate with phenolic hydroxyl groups at both ends.

[0047] 2) Under nitrogen atmosphere, the intermediate obtained in step 1) and 0.32 mol triethylamine were dissolved in 0.5 L toluene under ice bath condition, and 0.223 L of 1 mol / L acryloyl chloride solution (solvent ether) was added dropwise, and the reaction was carried out for 3 h after the addition was completed for 2 h. After the reaction was completed, the reaction was filtered and distilled under reduced pressure. The crude product was dissolved in toluene, washed with water, and the organic phase was separated. The organic phase was dried over anhydrous magnesium sulfate, filtered, and distilled under reduced pressure to obtain a functional diluent.

[0048] Steps 3) to 5) are the same.

[0049] Example 6

[0050] Steps 1) to 2) are the same as those in Example 1, except that:

[0051] 3) preparing component A: adding 10g of the functional diluent obtained in step 2) and 1.5g of anti-settling agent hydrogenated castor oil to 30g of active acrylic resin cyanote EB745 and mixing evenly, adding 20g of glass microspheres, 20g of titanium dioxide and 1250 mesh double fly ash as filler to make up to 100g, and mixing evenly; the glass microspheres are prepared by mixing glass microspheres with a particle size of 0.1-0.5mm, glass microspheres with a particle size of 0.2-0.65mm and glass microspheres with a particle size of 0.8-1.5mm in a mass ratio of 1:4:6, with a roundness of ≥90% and a refractive index of 2.0.

[0052] 4) Prepare component B: weigh 1 g of curing agent benzoyl peroxide.

[0053] 5) Mix component A and component B in a mass ratio of 1:1 and spray them on the road surface with a spraying thickness of 1.5 mm.

[0054] Comparative Example 1

[0055] The rest is the same as Example 1, except that the functional diluent is replaced by an equal mass of 1,6-hexanediol diacrylate.

[0056] The double-group heat-resistant road marking paint prepared in the above examples and comparative examples was cured at room temperature for 8-12 minutes, and then the following performance tests were performed:

[0057] 1. Wear resistance test: Refer to the standard GB / T 1768-2006 Determination of wear resistance of paint and varnish, the rotating rubber grinding wheel method is used for testing, and a 100mm×100mm mold is used. Glycerin is applied to the mold cavity before the test. Prepare 1000g of coating and pour it into the mold to make it level, and open a test hole with a diameter of about 6.35mm in the center when the coating is not completely cured. The wear resistance test is carried out with an abrasion tester at room temperature. The mass loss after the cycle of the rubber grinding wheel with a load of 1kg is used to characterize the wear resistance of the coating. The turntable speed is 60r / min. After 5min, the mass is weighed and the data is recorded. The target value of mass loss before and after wear is ≤40mg. The less mass loss, the better the wear resistance.

[0058] 2. Heat aging: Place the above wear resistance samples in an oven at 100°C for 168 hours and then retest the wear resistance.

[0059] 3. Adhesion: Tested in accordance with the standard GB / T5210-2006 paint and varnish pull-off adhesion test.

[0060] Table 1

[0061]

[0062] From the wear resistance test results of the embodiments and comparative examples in Table 1 and the wear resistance test results after thermal aging, it can be seen that the functional diluent prepared by the present invention can not only improve the wear resistance of the road marking paint, but also significantly improve the wear resistance of the road marking paint after thermal aging. From the adhesion test results, it can be seen that the functional diluent is beneficial to improving the adhesion of the coating, presumably because the imide bond is conducive to improving the cohesive force of the resin after curing.

[0063] The above detailed description is a specific description of one feasible embodiment of the present invention. The embodiment is not intended to limit the patent scope of the present invention. Any equivalent implementation or modification that does not deviate from the present invention should be included in the scope of the technical solution of the present invention.

Claims

1. A two-component heat-resistant road marking paint, comprising components A and B, characterized in that: The component A comprises the following raw materials in parts by weight: 30-50 parts of active acrylic resin, 7-10 parts of functional diluent, 20-30 parts of glass microspheres, 10-30 parts of pigment, 0.5-1.5 parts of anti-settling agent, and 100 parts of filler; the functional diluent is firstly prepared by reacting a hydroxyphthalic anhydride derivative with a fluorinated phenylenediamine derivative to generate an intermediate compound with phenolic hydroxyl groups at both ends, and then end-capping the intermediate compound with acryloyl chloride; The B component is an initiator; the amount of the B component is such that the initiator is 1.5-2.5 wt % of the total mass of the active acrylic resin and the functional diluent in the A component.

2. The double-group heat-resistant road marking paint according to claim 1, characterized in that: The molar ratio of the hydroxyphthalic anhydride derivative to the fluorinated phenylenediamine derivative is 2.08-2.12:1, and the molar ratio of the acryloyl chloride to the hydroxyphthalic anhydride derivative is 1:0.95-1.

3. The double-group heat-resistant road marking paint according to claim 1, characterized in that: The fluorinated benzene diamine derivative is selected from one or a combination of two or more of 5-fluorobenzene-1,3-diamine, 2-fluorobenzene-1,4-diamine, 4-fluoro-1,2-phenylenediamine, 4-fluoro-1,3-diaminobenzene, and 3-fluoro-1,2-phenylenediamine; the hydroxyphthalic anhydride derivative is selected from one or a combination of two of 3-hydroxyphthalic anhydride and 4-hydroxyphthalic anhydride.

4. The double-group heat-resistant road marking paint according to claim 1, characterized in that: The functional diluent is prepared by a method comprising the following steps: 1) adding a catalyst to an organic solvent, raising the temperature to a reflux state, and simultaneously dropping a hydroxyphthalic anhydride derivative solution and a fluorinated phenylenediamine derivative solution, reacting at a constant temperature after the dropwise addition, during which water is continuously separated by a water separator, cooling after the reaction is completed, adding an alkaline solution to adjust the pH to neutral, standing, separating the organic phase, drying, filtering, and distilling under reduced pressure to obtain an intermediate with phenolic hydroxyl groups at both ends; 2) Under an inert atmosphere, the intermediate obtained in step 1) and the acid-binding agent are dissolved in an organic solvent under ice bath conditions, and the acryloyl chloride solution is added dropwise. After the addition, the reaction is carried out. After the reaction is completed, the mixture is filtered and distilled under reduced pressure. The crude product is dissolved in an organic solvent, washed, dried, filtered, and distilled under reduced pressure to obtain a functional diluent.

5. The double-group heat-resistant road marking paint according to claim 4, characterized in that: In step 1), the catalyst is selected from one or a combination of two or more of phosphoric acid, sulfuric acid, p-toluenesulfonic acid, and phosphorus pentoxide, and the amount of the catalyst is 3-5wt% of the sum of the hydroxyphthalic anhydride derivative and the fluorinated phenylenediamine derivative.

6. The double-group heat-resistant road marking paint according to claim 4, characterized in that: In step 1), the temperature is raised to 90-120° C., the dropwise addition time is 1-3 h, and the constant temperature reaction time is 1-3 h.

7. The double-group heat-resistant road marking paint according to claim 4, characterized in that: In step 2), the concentration of the acryloyl chloride solution is 1-3 mol / L, and the dropping time is 1-2 h; the reaction time is 1-5 h.

8. The double-group heat-resistant road marking paint according to claim 1, characterized in that: The viscosity of the reactive acrylic resin at 25° C. is 10,000-30,000 mPa·s. The reactive acrylic resin comprises 25-50 wt % of a reactive diluent and 50-75 wt % of an acrylic resin oligomer. The functionality of the reactive diluent is 1-2.

9. The double-group heat-resistant road marking paint according to claim 8, characterized in that: The reactive acrylic resin is selected from one of Cytec EB705, Cytec EB745, and Cytec EB1710, or a combination of two or more thereof.

10. A method for preparing the double-component heat-resistant road marking paint according to any one of claims 1 to 9, characterized in that: The steps include: Prepare component A: add functional diluent and anti-settling agent to active acrylic resin and mix evenly, add glass micro beads, pigment and filler and mix evenly; Prepare component B: add functional diluent, initiator, anti-settling agent to active acrylic resin and mix evenly, add glass micro beads, pigment, and filler and mix evenly; Mix component A and component B in proportion and apply them on the road surface by spraying or scraping.

Images