CN111205726A - Water-based acrylic acid water-resistant road marking paint and preparation method thereof - Google Patents
Water-based acrylic acid water-resistant road marking paint and preparation method thereof Download PDFInfo
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- CN111205726A CN111205726A CN202010179534.0A CN202010179534A CN111205726A CN 111205726 A CN111205726 A CN 111205726A CN 202010179534 A CN202010179534 A CN 202010179534A CN 111205726 A CN111205726 A CN 111205726A
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D151/00—Coating compositions based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Coating compositions based on derivatives of such polymers
- C09D151/08—Coating compositions based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Coating compositions based on derivatives of such polymers grafted on to macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- C09D151/085—Coating compositions based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Coating compositions based on derivatives of such polymers grafted on to macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds on to polysiloxanes
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- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
- C08F283/12—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polysiloxanes
- C08F283/122—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polysiloxanes on to saturated polysiloxanes containing hydrolysable groups, e.g. alkoxy-, thio-, hydroxy-
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- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/08—Anti-corrosive paints
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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
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- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
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Abstract
The invention provides a water-based acrylic acid water-resistant road marking paint which is prepared from the following raw materials in parts by weight: 100-200 parts of modified acrylic resin, 1-3 parts of diacetone acrylamide, 1-3 parts of adipic dihydrazine, 5-10 parts of neopentyl glycol, 10-15 parts of maleic anhydride, 3-7 parts of adipate, 10-20 parts of a film-forming assistant, 5-10 parts of a dispersant and 5-10 parts of a defoaming agent. The preparation method is simple, the prepared coating is water-based, has good environmental protection and low VOC emission, has good gloss retention, water resistance, acid resistance and chemical corrosion resistance, is quick, fine and uniform in film formation, has good strength and mechanical property after film formation, and has wide application prospect.
Description
Technical Field
The invention relates to the technical field of road marking paint, in particular to water-based acrylic water-resistant road marking paint and a preparation method thereof.
Background
With the continuous acceleration of global industrialization progress, the consumption of petrochemical raw materials is continuously increased, the emission to the atmosphere is increased sharply, and the environment is worsened, generally, solvent-based coatings contain nearly 50% of organic volatile matters, the production of the coatings in China is about 100 ten thousand tons, the total production of the world is about ten million tons, and millions of tons of organic volatile matters exist, the organic volatile matters are completely released into the atmosphere in the use process of the coatings, and many volatile matters are photoactive matters, which destroy the ozone layer, cause the radiation enhancement of ultraviolet rays, and worsen the living environment of human beings. Therefore, in the developed countries in the western world, a plurality of environmental regulations for limiting the emission of toxic and harmful gases to the environment have been provided in the seventh and eighty years of the last century, and China also sets the regulations for controlling indoor coating pollution in the beginning of the century, such as: GB 18581-2001 and GB 18582-2001. These relevant regulations strongly alter and influence the direction of development of the coating industry. Therefore, the water-based coating becomes one of the development directions of the coating industry.
Some of the properties of water-based coatings have been comparable to solvent-based coatings after years of research by some foreign major companies such as Shell, American gas chemistry, CIBA, etc., and their major products are EPI-REZ3521-WY-5, EPIKURE 8545-W-5, EPI-REZ3520-WY-55, and Waterpoxy140 by Henkel, PZ 3961 and HZ340 by CIBA, etc. In the united states, many waterborne coatings meet the U.S. military coating specifications, waterborne corrosion resistant coatings have been used on primers for aircraft, and waterborne coatings have been used in nuclear power projects and rail vehicles in germany. In foreign countries, the water-based anticorrosive paint is also widely applied to ballast water tanks, drinking water tanks, cargo holds, seawater desalination plants, storage tanks, bridges and concrete base materials of municipal engineering. Compared with solvent-based coatings, water-based coatings also have low VOC content, less odor, safe use, water cleanability and the like. Despite the high price of water-based coatings, they are still attractive to industry and commerce and are being promoted. At present, in the field of industrial anticorrosion, a large amount of solvent-based coatings are still used, and with the increasing strictness and soundness of environmental protection regulations, the industrial anticorrosion coatings are inevitably in water-based trend and have good development prospects.
However, the aqueous acrylic coating also has some disadvantages such as uneven curing leading to a decrease in the strength and toughness of the paint film portion, thereby making the water resistance poor, and the like.
Disclosure of Invention
In order to solve the technical problems, the invention provides a water-based acrylic water-resistant road marking paint and a preparation method thereof, and aims to provide the water-based acrylic water-resistant road marking paint which is simple in preparation method, the prepared paint is a water-based paint, has good environmental protection and low VOC (volatile organic compounds) emission, has good gloss retention, water resistance, acid resistance and chemical corrosion resistance, is quick, fine and uniform in film formation, has good strength and mechanical properties after film formation, and has wide application prospect.
The invention provides a water-based acrylic water-resistant road marking paint which is prepared from the following raw materials: modified acrylic resin, diacetone acrylamide, adipic dihydrazine, neopentyl glycol, maleic anhydride, adipate, film forming assistant, dispersant and defoamer.
The modified acrylic resin is prepared from the following raw materials: methyl methacrylate, n-butyl acrylate, acrylic acid, hydroxyethyl acrylate, isocyanate, FEVE fluororesin, triethoxysilane, glycidyl versatate and initiator.
As a further improvement of the invention, the health-care food is prepared from the following raw materials in parts by weight: 100-200 parts of modified acrylic resin, 1-3 parts of diacetone acrylamide, 1-3 parts of adipic dihydrazine, 5-10 parts of neopentyl glycol, 10-15 parts of maleic anhydride, 3-7 parts of adipate, 10-20 parts of a film-forming assistant, 5-10 parts of a dispersant and 5-10 parts of a defoaming agent.
The modified acrylic resin is prepared from the following raw materials in parts by weight: 30-50 parts of methyl methacrylate, 10-30 parts of n-butyl acrylate, 15-35 parts of acrylic acid, 10-50 parts of hydroxyethyl acrylate, 15-55 parts of isocyanate, 10-30 parts of FEVE fluororesin, 5-10 parts of triethoxysilane, 50-100 parts of tertiary carboxylic acid glycidyl ester and 1-2 parts of initiator.
As a further improvement of the invention, the health-care food is prepared from the following raw materials in parts by weight: 170 parts of modified acrylic resin 130-one, 2-3 parts of diacetone acrylamide, 1-2 parts of adipic dihydrazine, 6-9 parts of neopentyl glycol, 8-12 parts of maleic anhydride, 4-6 parts of adipate, 12-17 parts of film-forming assistant, 6-9 parts of dispersant and 6-8 parts of defoaming agent.
The modified acrylic resin is prepared from the following raw materials in parts by weight: 35-45 parts of methyl methacrylate, 15-25 parts of n-butyl acrylate, 17-32 parts of acrylic acid, 20-40 parts of hydroxyethyl acrylate, 25-45 parts of isocyanate, 15-25 parts of FEVE fluororesin, 6-9 parts of triethoxysilane, 60-90 parts of tertiary carboxylic acid glycidyl ester and 1.2-1.7 parts of initiator.
As a further improvement of the invention, the health-care food is prepared from the following raw materials in parts by weight: 160 parts of modified acrylic resin, 2.5 parts of diacetone acrylamide, 1.5 parts of adipic dihydrazide, 7 parts of neopentyl glycol, 10 parts of maleic anhydride, 5 parts of adipate, 15 parts of film-forming assistant, 8 parts of dispersant and 7 parts of defoaming agent.
The modified acrylic resin is prepared from the following raw materials in parts by weight: 40 parts of methyl methacrylate, 20 parts of n-butyl acrylate, 25 parts of acrylic acid, 30 parts of hydroxyethyl acrylate, 35 parts of isocyanate, 20 parts of FEVE fluororesin, 8 parts of triethoxysilane, 75 parts of glycidyl versatate and 1.6 parts of initiator.
As a further improvement of the invention, the modified acrylic resin is prepared by the following method:
s1, dissolving hydroxyethyl acrylate and isocyanate in dimethylbenzene, adding a polymerization inhibitor DNBP accounting for 0.1 percent of the total mass of the isocyanate, heating to 70 ℃ and reacting for 2 hours to obtain a semi-finished product;
s2, adding ethyl acetate into a reaction kettle, heating the reaction kettle to 50 ℃ by using an oil bath heating device, adding tertiary carbonic acid glycidyl ester into the reaction kettle, sequentially adding monomers of methyl methacrylate, n-butyl acrylate and acrylic acid into the reaction kettle, uniformly stirring, adding a semi-finished product, adding hydroxyl-terminated fluorine-containing polyester polysiloxane after the temperature is raised to 70 ℃, uniformly stirring, adding an initiator, reacting for 4 hours, and removing the solvent under reduced pressure to obtain the modified acrylic resin.
The preparation principle is as follows:
and (3) reacting and connecting hydroxyl of hydroxyethyl acrylate with an isocyanate active site to generate a semi-finished product containing double bonds, and continuously adding the semi-finished product into an acrylate monomer for polymerization reaction to obtain the modified acrylic resin. The butyl acetate and water mixed solvent ensures that the reaction monomers react in a stable environment, avoids over violent reaction and improves the reaction efficiency; the purpose of adding the polymerization inhibitor is to prevent the isocyanate from self-polymerizing. The modified acrylic resin obtained by the method has good film forming property and weather resistance, and excellent mechanical property after film forming.
As a further improvement of the invention, the initiator is selected from one or more of tert-butyl peroxybenzoate, tert-butyl peroxypivalate, cumene hydroperoxide, tert-butyl hydroperoxide, benzoyl peroxide, lauroyl peroxide, potassium persulfate, sodium persulfate and ammonium persulfate.
As a further improvement of the invention, the dispersant is selected from one or more of hexenyl distearamide, 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 defoaming agent is selected from one or more of GPE type defoaming agent, organosilicon defoaming agent and BYK 024.
As a further improvement of the invention, the film-forming auxiliary agent comprises a silane coupling agent, an antioxidant, 800-mesh calcium powder, tween-80, span-80 and an anti-settling agent; the anti-settling agent is selected from one or more of modified hydrogenated castor oil, BYK-410, BYK-405, BYK-057, BYK-430, FP-100, polyolefin wax and polyamide wax.
The invention further provides a method for preparing the water-based acrylic water-resistant road marking paint, which comprises the following steps: adding neopentyl glycol and maleic anhydride into a reaction kettle, uniformly mixing, heating to 70 ℃ for reaction for 1h, heating a heating device to 70 ℃, adding modified acrylic resin, diacetone acrylamide and dihydrazine adipate into the reactor, stirring for reaction for 2-5h, cooling to room temperature, adding adipate, a film-forming assistant, a dispersant and a defoaming agent, uniformly stirring, filtering, and discharging to obtain the water-based acrylic water-resistant road marking paint.
The invention has the following beneficial effects:
according to the invention, the acrylic resin is modified by adopting organic fluorine, organic silicon and glycidyl versatate, wherein the organic fluorine and organic silicon modified acrylic resin can obviously improve the water resistance and stain resistance of the coating formed by the acrylic resin, the glycidyl versatate is an active solvent of synthetic resin in the acrylic resin, no solvent is required to be added in the synthesis of the modified acrylic resin, the safety and environmental protection performance of the modified acrylic resin are improved, and meanwhile, due to the steric effect of the glycidyl versatate, the final resin has good acid resistance, and is insensitive to UV (ultraviolet), so that the light retention performance of the coating is improved.
Maleic anhydride and neopentyl glycol are adopted to react to obtain an intermediate product containing double bonds, and the intermediate product reacts with acrylic resin, so that the density of a cross-linked product is increased, and the fineness of a formed film is improved; the paint film toughness and strength are improved by adopting adipate; diacetone acrylamide and adipic acid dihydrazine are self-crosslinking monomers, are added into acrylic resin, do not need to add a crosslinking agent additionally, can be self-crosslinked to form a film, and have short curing time and fine and uniform film formation; the paint film toughness and strength are improved by adopting adipate; the surface active agent is added to reduce the surface tension of the coating and enhance the adhesion of the coating.
The preparation method is simple, the prepared coating is water-based, has good environmental protection and low VOC emission, has good gloss retention, water resistance, acid resistance and chemical corrosion resistance, is quick, fine and uniform in film formation, has good strength and mechanical property after film formation, and has wide application prospect.
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.
FEVE fluororesin, OH value: 40-100mgKOH/g, acid value: 2-4mgKOH/g, solid content 50-70%, available from Dalibotai fluoro materials Co.
Example 1
The raw materials comprise the following components in parts by weight: 100 parts of modified acrylic resin, 1 part of diacetone acrylamide, 1 part of adipic acid dihydrazide, 5 parts of neopentyl glycol, 10 parts of maleic anhydride, 3 parts of adipate, 10 parts of film-forming assistant, 5 parts of glyceryl tristearate and 5 parts of defoaming agent BYK 0245. The film-forming assistant consists of the following raw materials in parts by weight: 12% of silane coupling agent, 15% of tea polyphenol, 43% of 800-mesh calcium powder, 8015% of tween-8010% of span-8010% and 5% of modified hydrogenated castor oil.
The modified acrylic resin is prepared from the following raw materials in parts by weight: 30 parts of methyl methacrylate, 10 parts of n-butyl acrylate, 15 parts of acrylic acid, 10 parts of hydroxyethyl acrylate, 20 parts of hydroxyethyl acrylate, 25 parts of isocyanate, 10 parts of FEVE fluororesin, 5 parts of triethoxysilane, 50 parts of glycidyl versatate and 1 part of potassium persulfate.
The modified acrylic resin is prepared by the following method:
s1, dissolving hydroxyethyl acrylate and isocyanate in dimethylbenzene, adding a polymerization inhibitor DNBP accounting for 0.1 percent of the total mass of the isocyanate, heating to 70 ℃ and reacting for 2 hours to obtain a semi-finished product;
s2, adding ethyl acetate into a reaction kettle, heating the reaction kettle to 50 ℃ by using an oil bath heating device, adding tertiary carbonic acid glycidyl ester into the reaction kettle, sequentially adding monomers of methyl methacrylate, n-butyl acrylate and acrylic acid into the reaction kettle, uniformly stirring, adding a semi-finished product, heating the reaction kettle to 70 ℃, adding hydroxyl-terminated fluorine-containing polyester polysiloxane, uniformly stirring, adding tert-butyl peroxybenzoate, reacting for 4 hours, and removing the solvent under reduced pressure to obtain the modified acrylic resin.
The preparation method of the water-based acrylic water-resistant road marking paint comprises the following steps:
adding neopentyl glycol and maleic anhydride into a reaction kettle, uniformly mixing, heating to 70 ℃ for reaction for 1h, heating a heating device to 70 ℃, adding modified acrylic resin, diacetone acrylamide and dihydrazine adipate into the reactor, stirring for reaction for 2h, cooling to room temperature, adding adipate, a film-forming assistant, glyceryl tristearate and a defoaming agent BYK024, uniformly stirring, filtering, and discharging to obtain the water-based acrylic water-resistant road marking paint.
Example 2
The raw materials comprise the following components in parts by weight: 200 parts of modified acrylic resin, 3 parts of diacetone acrylamide, 3 parts of adipic dihydrazide, 10 parts of neopentyl glycol, 15 parts of maleic anhydride, 7 parts of adipate, 20 parts of film-forming assistant, CT-13610 parts of dispersant and 10 parts of organic silicon defoamer. The film-forming assistant consists of the following raw materials in parts by weight: 12% of silane coupling agent, 101015% of antioxidant, 43% of 800-mesh calcium powder, 8015% of tween-8010% of span-8010% and 4305% of anti-settling agent BYK.
The modified acrylic resin is prepared from the following raw materials in parts by weight: 50 parts of methyl methacrylate, 30 parts of n-butyl acrylate, 35 parts of acrylic acid, 50 parts of hydroxyethyl acrylate, 55 parts of isocyanate, 30 parts of FEVE fluororesin, 10 parts of triethoxysilane, 100 parts of glycidyl versatate and 2 parts of tert-butyl hydroperoxide.
The modified acrylic resin is prepared by the following method:
s1, dissolving hydroxyethyl acrylate and isocyanate in dimethylbenzene, adding a polymerization inhibitor DNBP accounting for 0.1 percent of the total mass of the isocyanate, heating to 70 ℃ and reacting for 2 hours to obtain a semi-finished product;
s2, adding ethyl acetate into a reaction kettle, heating the reaction kettle to 50 ℃ by using an oil bath heating device, adding tertiary carbonic acid glycidyl ester into the reaction kettle, sequentially adding monomers of methyl methacrylate, n-butyl acrylate and acrylic acid into the reaction kettle, uniformly stirring, adding a semi-finished product, adding hydroxyl-terminated fluorine-containing polyester polysiloxane after the temperature is raised to 70 ℃, uniformly stirring, adding potassium persulfate, reacting for 4 hours, and removing the solvent under reduced pressure to obtain the modified acrylic resin.
The preparation method of the water-based acrylic water-resistant road marking paint comprises the following steps: adding neopentyl glycol and maleic anhydride into a reaction kettle, uniformly mixing, heating to 70 ℃ for reaction for 1h, heating a heating device to 70 ℃, adding modified acrylic resin, neopentyl glycol, maleic anhydride, diacetone acrylamide and dihydrazine adipate into the reactor, stirring for reaction for 5h, cooling to room temperature, adding adipate, a film-forming assistant, a dispersing agent CT-136 and an organic silicon defoamer, uniformly stirring, filtering, and discharging to obtain the water-based acrylic water-resistant road marking paint.
Example 3
The raw materials comprise the following components in parts by weight: 130 parts of modified acrylic resin, 2 parts of diacetone acrylamide, 1 part of adipic acid dihydrazide, 6 parts of neopentyl glycol, 8 parts of maleic anhydride, 4 parts of adipate, 12 parts of film-forming assistant, 6 parts of acrylic acid sodium salt copolymer and 6 parts of GPE type defoaming agent. The film-forming assistant consists of the following raw materials in parts by weight: 12% of silane coupling agent, 15% of tea polyphenol, 43% of 800-mesh calcium powder, 8015% of tween-8010% of span-8010% and 5% of modified hydrogenated castor oil.
The modified acrylic resin is prepared from the following raw materials in parts by weight: 35 parts of methyl methacrylate, 15 parts of n-butyl acrylate, 17 parts of acrylic acid, 20 parts of hydroxyethyl acrylate, 25 parts of isocyanate, 15 parts of FEVE fluororesin, 6 parts of triethoxysilane, 60 parts of glycidyl versatate and 1.2 parts of potassium persulfate.
The modified acrylic resin is prepared by the following method:
s1, dissolving hydroxyethyl acrylate and isocyanate in dimethylbenzene, adding a polymerization inhibitor DNBP accounting for 0.1 percent of the total mass of the isocyanate, heating to 70 ℃ and reacting for 2 hours to obtain a semi-finished product;
s2, adding ethyl acetate into a reaction kettle, heating the reaction kettle to 50 ℃ by using an oil bath heating device, adding tertiary carbonic acid glycidyl ester into the reaction kettle, sequentially adding monomers of methyl methacrylate, n-butyl acrylate and acrylic acid into the reaction kettle, uniformly stirring, adding a semi-finished product, adding hydroxyl-terminated fluorine-containing polyester polysiloxane after the temperature is raised to 70 ℃, uniformly stirring, adding sodium persulfate, reacting for 4 hours, and removing the solvent under reduced pressure to obtain the modified acrylic resin.
The preparation method of the water-based acrylic water-resistant road marking paint comprises the following steps: adding neopentyl glycol and maleic anhydride into a reaction kettle, uniformly mixing, heating to 70 ℃ for reaction for 1h, heating a heating device to 70 ℃, adding modified acrylic resin, neopentyl glycol, maleic anhydride, diacetone acrylamide and dihydrazine adipate into the reactor, stirring for reaction for 3h, cooling to room temperature, adding adipate, a film-forming assistant, an acrylic acid sodium salt copolymer and a GPE (general purpose olefin) type defoaming agent, uniformly stirring, filtering, and discharging to obtain the water-based acrylic acid water-resistant road marking paint.
Example 4
The raw materials comprise the following components in parts by weight: 170 parts of modified acrylic resin, 3 parts of diacetone acrylamide, 2 parts of adipic acid dihydrazide, 9 parts of neopentyl glycol, 12 parts of maleic anhydride, 6 parts of adipate, 17 parts of film-forming assistant, 9 parts of styrene-maleic anhydride and BYK 0248 parts of defoaming agent. The film-forming assistant consists of the following raw materials in parts by weight: 12% of silane coupling agent, 101015% of antioxidant, 43% of 800-mesh calcium powder, 8015% of tween-8010% of span-8010% and BYK-4055% of anti-settling agent.
The modified acrylic resin is prepared from the following raw materials in parts by weight: 45 parts of methyl methacrylate, 25 parts of n-butyl acrylate, 32 parts of acrylic acid, 40 parts of hydroxyethyl acrylate, 45 parts of isocyanate, 25 parts of FEVE fluororesin, 9 parts of triethoxysilane, 90 parts of glycidyl versatate and 1.7 parts of tert-butyl peroxybenzoate.
The modified acrylic resin is prepared by the following method:
s1, dissolving hydroxyethyl acrylate and isocyanate in dimethylbenzene, adding a polymerization inhibitor DNBP accounting for 0.1 percent of the total mass of the isocyanate, heating to 70 ℃ and reacting for 2 hours to obtain a semi-finished product;
s2, adding ethyl acetate into a reaction kettle, heating the reaction kettle to 50 ℃ by using an oil bath heating device, adding tertiary carbonic acid glycidyl ester into the reaction kettle, sequentially adding monomers of methyl methacrylate, n-butyl acrylate and acrylic acid into the reaction kettle, uniformly stirring, adding a semi-finished product, heating the reaction kettle to 70 ℃, adding hydroxyl-terminated fluorine-containing polyester polysiloxane, uniformly stirring, adding tert-butyl hydroperoxide, reacting for 4 hours, and removing the solvent under reduced pressure to obtain the modified acrylic resin.
The preparation method of the water-based acrylic water-resistant road marking paint comprises the following steps: adding neopentyl glycol and maleic anhydride into a reaction kettle, uniformly mixing, heating to 70 ℃ for reaction for 1h, heating a heating device to 70 ℃, adding modified acrylic resin, neopentyl glycol, maleic anhydride, diacetone acrylamide and dihydrazine adipate into the reactor, stirring for reaction for 4h, cooling to room temperature, adding adipate, a film-forming assistant, styrene-maleic anhydride and a defoaming agent BYK024, uniformly stirring, filtering, and discharging to obtain the water-based acrylic water-resistant road marking paint.
Example 5
The raw materials comprise the following components in parts by weight: 160 parts of modified acrylic resin, 2.5 parts of diacetone acrylamide, 1.5 parts of adipic dihydrazide, 7 parts of neopentyl glycol, 10 parts of maleic anhydride, 5 parts of adipate, 15 parts of film-forming assistant, 4008 parts of polyethylene glycol and 7 parts of organic silicon defoamer. The film-forming assistant consists of the following raw materials in parts by weight: 12% of silane coupling agent, 40515% of antioxidant, 43% of 800-mesh calcium powder, 8015% of tween, 8010% of span and 4105% of anti-settling agent BYK.
The modified acrylic resin is prepared from the following raw materials in parts by weight: 40 parts of methyl methacrylate, 20 parts of n-butyl acrylate, 25 parts of acrylic acid, 30 parts of hydroxyethyl acrylate, 35 parts of isocyanate, 20 parts of FEVE fluororesin, 8 parts of triethoxysilane, 75 parts of glycidyl versatate and 1.6 parts of lauroyl peroxide.
The modified acrylic resin is prepared by the following method:
s1, dissolving hydroxyethyl acrylate and isocyanate in dimethylbenzene, adding a polymerization inhibitor DNBP accounting for 0.1 percent of the total mass of the isocyanate, heating to 70 ℃ and reacting for 2 hours to obtain a semi-finished product;
s2, adding ethyl acetate into a reaction kettle, heating the reaction kettle to 50 ℃ by using an oil bath heating device, adding tertiary carbonic acid glycidyl ester into the reaction kettle, sequentially adding monomers of methyl methacrylate, n-butyl acrylate and acrylic acid into the reaction kettle, uniformly stirring, adding a semi-finished product, heating the reaction kettle to 70 ℃, adding hydroxyl-terminated fluorine-containing polyester polysiloxane, uniformly stirring, adding cumene hydroperoxide, reacting for 4 hours, and removing the solvent under reduced pressure to obtain the modified acrylic resin.
The preparation method of the water-based acrylic water-resistant road marking paint comprises the following steps: adding neopentyl glycol and maleic anhydride into a reaction kettle, uniformly mixing, heating to 70 ℃ for reaction for 1h, heating a heating device to 70 ℃, adding modified acrylic resin, neopentyl glycol, maleic anhydride, diacetone acrylamide and dihydrazine adipate into the reactor, stirring for reaction for 3.5h, cooling to room temperature, adding adipate, a film-forming assistant, polyethylene glycol 400 and an organic silicon defoamer, uniformly stirring, filtering, and discharging to obtain the water-based acrylic water-resistant road marking paint.
Comparative example 1
Compared with example 5, the modified acrylic resin was replaced with a general acrylic resin.
Comparative example 2
In contrast to example 5, no coalescent was added.
Test example 1
The examples 1 to 5 of the present invention, the comparative examples 1 to 2, and the commercially available water-based acrylic water-resistant road marking paint were subjected to performance tests according to the national standards, and the results are shown in table 1.
TABLE 1
As can be seen from the above table, the water-based acrylic water-resistant road marking paint prepared in the embodiments 1-5 of the present invention has similar comprehensive properties, and the properties are better than those of similar products sold in the market in comparison with the comparative examples. Compared with the comparative example 1, the coating adopting the common acrylic resin has reduced mechanical property, and obviously reduced water resistance and pollution resistance; compared with the comparative example 3, the addition of the film-forming assistant has better improvement on the wear resistance, the mechanical property and the like of the coating.
Compared with the prior art, the acrylic resin is modified by adopting the organic fluorine, the organic silicon and the tertiary carboxylic acid glycidyl ester, wherein the organic fluorine and organic silicon modified acrylic resin can obviously improve the water resistance and the stain resistance of the coating formed by the acrylic resin, the tertiary carboxylic acid glycidyl ester is an active solvent of synthetic resin in the acrylic resin, no solvent is required to be added in the synthesis of the modified acrylic resin, the safety and environmental protection performance of the modified acrylic resin are improved, and meanwhile, the final resin has good acid resistance due to the steric effect of the tertiary carboxylic acid glycidyl ester, is not sensitive to UV (ultraviolet), and improves the gloss retention performance of the coating;
maleic anhydride and neopentyl glycol are adopted to react to obtain an intermediate product containing double bonds, and the intermediate product reacts with acrylic resin, so that the density of a cross-linked product is increased, and the fineness of a formed film is improved; the paint film toughness and strength are improved by adopting adipate; diacetone acrylamide and adipic acid dihydrazine are self-crosslinking monomers, are added into acrylic resin, do not need to add a crosslinking agent additionally, can be self-crosslinked to form a film, and have short curing time and fine and uniform film formation; the paint film toughness and strength are improved by adopting adipate; the surface active agent is added to reduce the surface tension of the coating and enhance the adhesion of the coating.
The preparation method is simple, the prepared coating is water-based, has good environmental protection and low VOC emission, has good gloss retention, water resistance, acid resistance and chemical corrosion resistance, is quick, fine and uniform in film formation, has good strength and mechanical property after film formation, and has 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.
Claims (10)
1. The water-based acrylic water-resistant road marking paint is characterized by being prepared from the following raw materials: modified acrylic resin, diacetone acrylamide, dihydrazide adipate, neopentyl glycol, maleic anhydride, adipate, film-forming assistant, dispersant and defoamer;
the modified acrylic resin is prepared from the following raw materials: methyl methacrylate, n-butyl acrylate, acrylic acid, hydroxyethyl acrylate, isocyanate, FEVE fluororesin, triethoxysilane, glycidyl versatate and initiator.
2. The water-based acrylic water-resistant road marking paint as claimed in claim 1, which is prepared from the following raw materials in parts by weight: 100-200 parts of modified acrylic resin, 1-3 parts of diacetone acrylamide, 1-3 parts of adipic dihydrazine, 5-10 parts of neopentyl glycol, 10-15 parts of maleic anhydride, 3-7 parts of adipate, 10-20 parts of a film-forming assistant, 5-10 parts of a dispersant and 5-10 parts of a defoaming agent;
the modified acrylic resin is prepared from the following raw materials in parts by weight: 30-50 parts of methyl methacrylate, 10-30 parts of n-butyl acrylate, 15-35 parts of acrylic acid, 10-50 parts of hydroxyethyl acrylate, 15-55 parts of isocyanate, 10-30 parts of FEVE fluororesin, 5-10 parts of triethoxysilane, 50-100 parts of tertiary carboxylic acid glycidyl ester and 1-2 parts of initiator.
3. The water-based acrylic water-resistant road marking paint as claimed in claim 2, which is prepared from the following raw materials in parts by weight: 170 parts of modified acrylic resin 130-one, 2-3 parts of diacetone acrylamide, 1-2 parts of adipic dihydrazine, 6-9 parts of neopentyl glycol, 8-12 parts of maleic anhydride, 4-6 parts of adipate, 12-17 parts of film-forming assistant, 6-9 parts of dispersant and 6-8 parts of defoaming agent;
the modified acrylic resin is prepared from the following raw materials in parts by weight: 35-45 parts of methyl methacrylate, 15-25 parts of n-butyl acrylate, 17-32 parts of acrylic acid, 20-40 parts of hydroxyethyl acrylate, 25-45 parts of isocyanate, 15-25 parts of FEVE fluororesin, 6-9 parts of triethoxysilane, 60-90 parts of tertiary carboxylic acid glycidyl ester and 1.2-1.7 parts of initiator.
4. The water-based acrylic water-resistant road marking paint as claimed in claim 3, which is prepared from the following raw materials in parts by weight: 160 parts of modified acrylic resin, 2.5 parts of diacetone acrylamide, 1.5 parts of adipic dihydrazide, 7 parts of neopentyl glycol, 10 parts of maleic anhydride, 5 parts of adipate, 15 parts of film-forming assistant, 8 parts of dispersant and 7 parts of defoaming agent;
the modified acrylic resin is prepared from the following raw materials in parts by weight: 40 parts of methyl methacrylate, 20 parts of n-butyl acrylate, 25 parts of acrylic acid, 30 parts of hydroxyethyl acrylate, 35 parts of isocyanate, 20 parts of FEVE fluororesin, 8 parts of triethoxysilane, 75 parts of glycidyl versatate and 1.6 parts of initiator.
5. The water-based acrylic water-resistant road marking paint as claimed in claim 1, wherein the modified acrylic resin is prepared by the following method:
s1, dissolving hydroxyethyl acrylate and isocyanate in dimethylbenzene, adding a polymerization inhibitor DNBP accounting for 0.1 percent of the total mass of the isocyanate, heating to 70 ℃ and reacting for 2 hours to obtain a semi-finished product;
s2, adding ethyl acetate into a reaction kettle, heating the reaction kettle to 50 ℃ by using an oil bath heating device, adding tertiary carbonic acid glycidyl ester into the reaction kettle, sequentially adding monomers of methyl methacrylate, n-butyl acrylate and acrylic acid into the reaction kettle, uniformly stirring, adding a semi-finished product, adding hydroxyl-terminated fluorine-containing polyester polysiloxane after the temperature is raised to 70 ℃, uniformly stirring, adding an initiator, reacting for 4 hours, and removing the solvent under reduced pressure to obtain the modified acrylic resin.
6. The water-resistant aqueous acrylic road marking paint as claimed in claim 1, wherein the initiator is selected from one or more of tert-butyl peroxybenzoate, tert-butyl peroxypivalate, cumene hydroperoxide, tert-butyl hydroperoxide, benzoyl peroxide, lauroyl peroxide, potassium persulfate, sodium persulfate and ammonium persulfate.
7. The water-based acrylic water-resistant road marking paint as claimed in claim 1, wherein the dispersant is selected from one or more of hexenyl bis stearamide, stearic acid monoglyceride, tristearin, polycarboxylic acid ammonium salt, acrylic acid sodium salt copolymer, polyethylene glycol 200, polyethylene glycol 400, styrene-maleic anhydride and CT-136.
8. The water-based acrylic water-resistant road marking paint as claimed in claim 1, wherein the defoaming agent is one or more selected from GPE type defoaming agent, silicone defoaming agent and BYK 024.
9. The water-based acrylic water-resistant road marking paint as claimed in claim 1, wherein the film forming auxiliary agent comprises a silane coupling agent, an antioxidant, 800-mesh calcium powder, tween-80, span-80 and an anti-settling agent; the anti-settling agent is selected from one or more of modified hydrogenated castor oil, BYK-410, BYK-405, BYK-057, BYK-430, FP-100, polyolefin wax and polyamide wax.
10. A process for preparing the aqueous acrylic water resistant road marking paint of any one of claims 1 to 9 comprising the steps of: adding neopentyl glycol and maleic anhydride into a reaction kettle, uniformly mixing, heating to 70 ℃ for reaction for 1h, heating a heating device to 70 ℃, adding modified acrylic resin, diacetone acrylamide and dihydrazine adipate into the reactor, stirring for reaction for 2-5h, cooling to room temperature, adding adipate, a film-forming assistant, a dispersant and a defoaming agent, uniformly stirring, filtering, and discharging to obtain the water-based acrylic water-resistant road marking paint.
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| CN202010179534.0A CN111205726A (en) | 2020-02-28 | 2020-02-28 | Water-based acrylic acid water-resistant road marking paint and preparation method thereof |
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| Application Number | Priority Date | Filing Date | Title |
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| CN202010179534.0A CN111205726A (en) | 2020-02-28 | 2020-02-28 | Water-based acrylic acid water-resistant road marking paint and preparation method thereof |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112662261A (en) * | 2020-12-31 | 2021-04-16 | 山西中涂交通科技股份有限公司 | Self-cleaning road marking paint and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2007186582A (en) * | 2006-01-12 | 2007-07-26 | Asahi Kasei Chemicals Corp | Cross-linkable aqueous coating composition |
| CN110423547A (en) * | 2019-08-08 | 2019-11-08 | 山东路辰交通科技有限公司 | A kind of double-component aqueous road mark paint and preparation method thereof |
| CN110423497A (en) * | 2019-08-08 | 2019-11-08 | 山东路辰交通科技有限公司 | A kind of water soluble acrylic acid wear-resisting road gage mark coating and preparation method thereof |
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2020
- 2020-02-28 CN CN202010179534.0A patent/CN111205726A/en not_active Withdrawn
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2007186582A (en) * | 2006-01-12 | 2007-07-26 | Asahi Kasei Chemicals Corp | Cross-linkable aqueous coating composition |
| CN110423547A (en) * | 2019-08-08 | 2019-11-08 | 山东路辰交通科技有限公司 | A kind of double-component aqueous road mark paint and preparation method thereof |
| CN110423497A (en) * | 2019-08-08 | 2019-11-08 | 山东路辰交通科技有限公司 | A kind of water soluble acrylic acid wear-resisting road gage mark coating and preparation method thereof |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112662261A (en) * | 2020-12-31 | 2021-04-16 | 山西中涂交通科技股份有限公司 | Self-cleaning road marking paint and preparation method thereof |
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