CN113072872A - Anti-ultraviolet bright plastic paint coating and preparation method thereof - Google Patents
Anti-ultraviolet bright plastic paint coating and preparation method thereof Download PDFInfo
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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
- C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
- C09D175/04—Polyurethanes
- C09D175/14—Polyurethanes having carbon-to-carbon unsaturated bonds
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- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
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- C08G18/48—Polyethers
- C08G18/4833—Polyethers containing oxyethylene units
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- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/67—Unsaturated compounds having active hydrogen
- C08G18/671—Unsaturated compounds having only one group containing active hydrogen
- C08G18/672—Esters of acrylic or alkyl acrylic acid having only one group containing active hydrogen
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
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- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/71—Monoisocyanates or monoisothiocyanates
- C08G18/718—Monoisocyanates or monoisothiocyanates containing silicon
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- C08G18/00—Polymeric products of isocyanates or isothiocyanates
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- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
- C08G18/75—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic
- C08G18/751—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring
- C08G18/752—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group
- C08G18/753—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate group
- C08G18/755—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate group and at least one isocyanate or isothiocyanate group linked to a secondary carbon atom of the cycloaliphatic ring, e.g. isophorone diisocyanate
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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
- C09D7/60—Additives non-macromolecular
- C09D7/61—Additives non-macromolecular inorganic
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Abstract
The invention discloses an anti-ultraviolet bright plastic paint and a preparation method thereof, and the anti-ultraviolet bright plastic paint comprises the following raw materials, by weight, 20-60 parts of modified polyurethane acrylic hyperbranched polymer, 5-15 parts of active diluent, 0.1-3 parts of photoinitiator, 0.5-2 parts of modified nano titanium dioxide, 0.05-1 part of defoaming agent, 0.05-1 part of dispersing agent and 30-50 parts of deionized water. The invention synthesizes the modified polyurethane acrylic hyperbranched polymer by taking the hyperbranched polyester as a raw material, not only introduces a hyperbranched structure into the polymer to reduce the viscosity of the polymer and reduce the dosage of the reactive diluent, but also introduces a silica chain into the polymer, and the silica chain can carry out moisture curing reaction with water molecules in the air to form a polymer chain interpenetrating network structure, thereby increasing the curing mode of the coating and obtaining a paint film with excellent comprehensive properties such as thorough curing, good adhesion fastness, high hardness and the like.
Description
Technical Field
The invention belongs to the technical field of flour processing, and particularly relates to an anti-ultraviolet bright plastic paint and a preparation method thereof.
Background
In order to protect various material products from being corroded by external conditions (such as illumination, wind and rain, friction and the like), prolong the service life and beautify the products, the surfaces of the plastic products are often coated with plastic paint coatings, and plastic paint coatings with corresponding functions can be selected for coating according to the functions or defects of the products, for example, if plastic parts are easy to age, yellow and become brittle after being contacted with ultraviolet rays for a long time, ultraviolet-resistant coatings can be coated on the surfaces of the plastic parts, so that the aim of resisting the ultraviolet rays is fulfilled.
The plastic paint is prepared with thermoplastic acrylic resin as base material and high-grade assistant and pigment, and through monomer selection, compounding and polymerization to obtain the special acrylic resin. But the plastic is also a plastic, the ultraviolet resistance of the plastic is not very strong, and the plastic is discolored, faded and pulverized to peel off after long-time illumination.
Therefore, the invention provides an anti-ultraviolet bright plastic paint and a preparation method thereof.
Disclosure of Invention
The invention aims to provide an anti-ultraviolet bright plastic paint and a preparation method thereof, so as to improve the anti-ultraviolet performance and the brightness of the existing plastic paint.
The purpose of the invention can be solved by the following technical scheme:
an anti-ultraviolet bright plastic paint coating comprises the following raw materials, by weight, 20-60 parts of modified polyurethane acrylic hyperbranched polymer, 5-15 parts of active diluent, 0.1-3 parts of photoinitiator, 0.5-2 parts of modified nano titanium dioxide, 0.05-1 part of defoaming agent, 0.05-1 part of dispersant and 30-50 parts of deionized water;
the preparation method of the anti-ultraviolet bright plastic paint coating comprises the following steps:
step A, uniformly stirring part of deionized water, a defoaming agent and a dispersing agent, adding modified nano titanium dioxide at the rotating speed of 800r/min of 600-;
and step B, stirring the modified polyurethane acrylic hyperbranched polymer, the active diluent, the photoinitiator and the rest deionized water at normal temperature, adding the mixed solution obtained in the step A after uniformly mixing, and uniformly stirring to obtain the ultraviolet-resistant bright plastic paint coating.
Further, the modified polyurethane acrylic hyperbranched polymer is prepared by the following steps:
step C1, adding hyperbranched polyester, maleic anhydride and anhydrous dioxane into a reaction container in sequence, stirring to completely dissolve the hyperbranched polyester and the maleic anhydride, adding a transesterification catalyst tin chloride when obtaining a uniform solution, heating the reaction system to 95-100 ℃ under the stirring state, continuing stirring for constant temperature reaction for 24-36 hours, and then carrying out reduced pressure distillation on the reaction liquid to remove the solvent and a small amount of water to obtain carboxyl modified hyperbranched polyester;
step C2, adding anhydrous dioxane into a reaction container, introducing nitrogen for 10-15min to replace air in the reaction container, adding isophorone diisocyanate, stannous octoate and linear polyethylene glycol, reacting at 87-93 ℃ for 4-8h, cooling to 50-55 ℃, adding hydroxyl acrylate, and continuing to react for 5-8h to obtain isocyanate and methacrylate-based polyurethane prepolymer;
and C3, adding the carboxyl modified hyperbranched polyester obtained in the step C1 into the reaction system in the step C2, continuously keeping the temperature at 50-55 ℃, sampling every 0.5 hour to determine the content of NCO groups, adding 3-isocyanate propyl trimethoxy silane to continuously react when the weight content of the NCO groups changes to be less than or equal to 0.01 percent, sampling every 0.5 hour to determine the content of the NCO groups, stopping the reaction when the weight content of the NCO groups changes to be less than or equal to 0.01 percent, adding triethylamine to stir for 10 minutes, removing the solvent, and performing rotary evaporation to remove unreacted micromolecules to obtain the modified polyurethane acrylic hyperbranched polymer.
Further, in the step C1, the dosage ratio of the hyperbranched polyester, the maleic anhydride and the dioxane is 30-50g:5-15g:100-150ml, wherein the hyperbranched polyester is hyperbranched polyatomic alcohol, the average functionality of terminal hydroxyl is 32, and the number average molecular weight is 3000-4000.
Further, in the step C2, the molar mass ratio of the isophorone diisocyanate to the stannous octoate to the polyethylene glycol to the hydroxyl acrylate is 2-3:0.005-0.008:1:1, wherein the number average molecular weight of the polyethylene glycol is 800-1000.
Further, the adding mass of the carboxyl modified hyperbranched polyester in the step C3 is 3-6 times of that of the hydroxyl acrylate in the step C2, and the adding amount of the 3-isocyanate propyl trimethoxy silane is 20-40% of that of the carboxyl modified hyperbranched polyester.
Further, the active diluent is one or a mixture of more of pentaerythritol triacrylate, ethylene glycol diacrylate, neopentyl glycol diacrylate and 1, 6-hexanediol diacrylate in any ratio.
Further, the photoinitiator is one or a mixture of several of 1-hydroxycyclohexyl phenyl ketone, 2-methyl-2- (4-morpholinyl) -1- [4- (methylthio) phenyl ] -1-acetone, alpha' -dimethyl benzil ketal and 2, 4, 6-trimethyl benzoyl-diphenyl phosphine oxide in any ratio.
Further, the modified nano titanium dioxide is prepared by the following steps:
adjusting the pH value of the solution to 4-4.5 by using hydrochloric acid and sodium hydroxide solution, and uniformly stirring for 1h in a constant-temperature water bath kettle at 50-60 ℃ to obtain a mixed solution A; adding nano titanium dioxide into a mixed solution of deionized water and absolute ethyl alcohol, and performing ultrasonic dispersion for 5min to obtain a mixed solution B; and then uniformly mixing the mixed solution A and the mixed solution B, uniformly stirring and reacting for 1-2h at 50-60 ℃, centrifuging, filtering, cleaning a filter cake by using the mixed solution of deionized water and absolute ethyl alcohol, repeating for 3-4 times, drying the obtained filter cake for 5-7h at 100 ℃, and grinding to obtain the modified nano titanium dioxide, wherein the volume ratio of the deionized water to the absolute ethyl alcohol in the mixed solution of the deionized water and the absolute ethyl alcohol is 1: 1.
Further, the defoaming agent is a silicone defoaming agent.
Further, the dispersant is polyethylene glycol.
A preparation method of an anti-ultraviolet bright plastic paint coating comprises the following steps:
step A, uniformly stirring part of deionized water, a defoaming agent and a dispersing agent, adding modified nano titanium dioxide at the rotating speed of 800r/min of 600-;
and step B, stirring the modified polyurethane acrylic hyperbranched polymer, the active diluent, the photoinitiator and the rest deionized water at normal temperature, adding the mixed solution obtained in the step A after uniformly mixing, and uniformly stirring to obtain the ultraviolet-resistant bright plastic paint coating.
Has the advantages that:
1. the curing mode of the coating prepared by the invention mainly comprises the steps of polymerizing unsaturated double bonds of modified polyurethane acrylic hyperbranched polymer and active diluent under the irradiation of ultraviolet light through free radicals to form a net structure, in the method, the modified polyurethane acrylic hyperbranched polymer synthesized by taking hyperbranched polyester as a raw material not only introduces a hyperbranched structure into the polymer, reduces the viscosity of the polymer and the dosage of an active diluent, and a silicon-oxygen chain is introduced into the polymer, so that the silicon-oxygen chain exists in a coating system, the structure and water molecules in the air perform moisture curing reaction to form a polymer chain interpenetrating network structure, the curing mode of the coating is increased, so that the paint can form a paint film with excellent comprehensive properties such as thorough curing, good adhesion fastness, high hardness, chemical resistance and the like on a substrate.
2. According to the invention, aminopropyltriethoxysilane modified nano titanium dioxide is introduced into the coating, so that on one hand, the nano titanium dioxide is dispersed in a coating system more uniformly and stably, and on the other hand, an interpenetrating network structure is formed between the titanium dioxide containing amino and silica structures and the modified polyurethane acrylic hyperbranched polymer chain, so that the uniformity and stability of the distribution of the titanium dioxide in a coating film are increased, the agglomeration and the later migration of the titanium dioxide in the film forming process are reduced, the mechanical property and the ultraviolet resistance of the coating film are increased, and the brightness of the coating film is improved.
Detailed Description
The technical solutions in the embodiments of the present invention are clearly and completely described, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1:
the modified polyurethane acrylic hyperbranched polymer is prepared by the following steps:
step C1, adding hyperbranched polyester, maleic anhydride and anhydrous dioxane into a reaction container in sequence, stirring to completely dissolve the hyperbranched polyester and the maleic anhydride, adding a transesterification catalyst tin chloride when obtaining a uniform solution, heating a reaction system to 95 ℃ under the stirring state, continuously stirring and reacting at a constant temperature for 24 hours, and then carrying out reduced pressure distillation on the reaction liquid to remove a solvent and a small amount of water to obtain carboxyl modified hyperbranched polyester, wherein the adding amount ratio of the hyperbranched polyester, the maleic anhydride and the dioxane is 30g:5g:100ml, the hyperbranched polyester is hyperbranched polyatomic alcohol, the average functionality of terminal hydroxyl is 32, and the number average molecular weight is 3000;
step C2, adding anhydrous dioxane into a reaction container, introducing nitrogen for 10min to replace air in the reaction container, adding isophorone diisocyanate, stannous octoate and linear polyethylene glycol, reacting at 87 ℃ for 5h, reducing the temperature to 50 ℃, adding hydroxyl acrylate, and continuing to react for 5h to obtain isocyanate and methacrylate-based polyurethane prepolymer, wherein the molar mass ratio of the isophorone diisocyanate to the stannous octoate to the polyethylene glycol to the hydroxyl acrylate is 2:0.005:1:1, and the number average molecular weight of the polyethylene glycol is 800;
and C3, adding the carboxyl modified hyperbranched polyester obtained in the step C1 into the reaction system in the step C2, continuously keeping the temperature at 50 ℃, sampling every 0.5 hour to determine the content of NCO groups, adding 3-isocyanate propyl trimethoxy silane to continuously react when the weight content of the NCO groups changes to be less than or equal to 0.01 percent, sampling every 0.5 hour to determine the content of the NCO groups, stopping the reaction when the weight content of the NCO groups changes to be less than or equal to 0.01 percent, adding triethylamine to stir for 10 minutes, removing the solvent, and performing rotary evaporation to remove unreacted micromolecules to obtain the modified polyurethane acrylic hyperbranched polymer, wherein the adding mass of the carboxyl modified hyperbranched polyester is respectively 3 times of the adding mass of the hydroxy acrylate in the step C2, and the adding amount of the 3-isocyanate propyl trimethoxy silane is 20 percent of the adding mass of the carboxyl modified hyperbranched polyester.
Example 2:
the modified polyurethane acrylic hyperbranched polymer is prepared by the following steps:
step C1, adding hyperbranched polyester, maleic anhydride and anhydrous dioxane into a reaction container in sequence, stirring to completely dissolve the hyperbranched polyester and the maleic anhydride, adding a transesterification catalyst tin chloride when obtaining a uniform solution, heating a reaction system to 95 ℃ under the stirring state, continuously stirring and reacting at a constant temperature for 24 hours, and then carrying out reduced pressure distillation on the reaction liquid to remove a solvent and a small amount of water to obtain carboxyl modified hyperbranched polyester, wherein the adding amount ratio of the hyperbranched polyester, the maleic anhydride and the dioxane is 40g:10g:120ml, the hyperbranched polyester is hyperbranched polyatomic alcohol, the average functionality of terminal hydroxyl is 32, and the number average molecular weight is 3000;
step C2, adding anhydrous dioxane into a reaction container, introducing nitrogen for 10min to replace air in the reaction container, adding isophorone diisocyanate, stannous octoate and linear polyethylene glycol, reacting at 87 ℃ for 5h, cooling to 50 ℃, adding hydroxyl acrylate, and continuing to react for 5h to obtain an isocyanate and methacrylate-based polyurethane prepolymer, wherein the molar mass ratio of the isophorone diisocyanate to the stannous octoate to the polyethylene glycol to the hydroxyl acrylate is 2.5:0.006:1:1, and the number average molecular weight of the polyethylene glycol is 800;
and C3, adding the carboxyl modified hyperbranched polyester obtained in the step C1 into the reaction system in the step C2, continuously keeping the temperature at 50 ℃, sampling every 0.5 hour to determine the content of NCO groups, adding 3-isocyanate propyl trimethoxy silane to continuously react when the weight content of the NCO groups changes to be less than or equal to 0.01 percent, sampling every 0.5 hour to determine the content of the NCO groups, stopping the reaction when the weight content of the NCO groups changes to be less than or equal to 0.01 percent, adding triethylamine to stir for 10 minutes, removing the solvent, and performing rotary evaporation to remove unreacted micromolecules to obtain the modified polyurethane acrylic hyperbranched polymer, wherein the adding mass of the carboxyl modified hyperbranched polyester is respectively 4 times of the adding mass of the hydroxy acrylate in the step C2, and the adding amount of the 3-isocyanate propyl trimethoxy silane is 30 percent of the adding mass of the carboxyl modified hyperbranched polyester.
Example 3:
the modified polyurethane acrylic hyperbranched polymer is prepared by the following steps:
step C1, adding hyperbranched polyester, maleic anhydride and anhydrous dioxane into a reaction container in sequence, stirring to completely dissolve the hyperbranched polyester and the maleic anhydride, adding a transesterification catalyst tin chloride when obtaining a uniform solution, heating a reaction system to 95 ℃ under the stirring state, continuously stirring and reacting at a constant temperature for 24 hours, and then carrying out reduced pressure distillation on the reaction liquid to remove a solvent and a small amount of water to obtain carboxyl modified hyperbranched polyester, wherein the adding amount ratio of the hyperbranched polyester, the maleic anhydride and the dioxane is 50g:15g:150ml, the hyperbranched polyester is hyperbranched polyatomic alcohol, the average functionality of terminal hydroxyl is 32, and the number average molecular weight is 3000;
step C2, adding anhydrous dioxane into a reaction container, introducing nitrogen for 10min to replace air in the reaction container, adding isophorone diisocyanate, stannous octoate and linear polyethylene glycol, reacting at 87 ℃ for 5h, reducing the temperature to 50 ℃, adding hydroxyl acrylate, and continuing to react for 5h to obtain isocyanate and methacrylate-based polyurethane prepolymer, wherein the molar mass ratio of the isophorone diisocyanate to the stannous octoate to the polyethylene glycol to the hydroxyl acrylate is 3:0.008:1:1, and the number average molecular weight of the polyethylene glycol is 800;
and C3, adding the carboxyl modified hyperbranched polyester obtained in the step C1 into the reaction system in the step C2, continuously keeping the temperature at 50 ℃, sampling every 0.5 hour to determine the content of NCO groups, adding 3-isocyanate propyl trimethoxy silane to continuously react when the weight content of the NCO groups changes to be less than or equal to 0.01 percent, sampling every 0.5 hour to determine the content of the NCO groups, stopping the reaction when the weight content of the NCO groups changes to be less than or equal to 0.01 percent, adding triethylamine to stir for 10 minutes, removing the solvent, and performing rotary evaporation to remove unreacted micromolecules to obtain the modified polyurethane acrylic hyperbranched polymer, wherein the adding mass of the carboxyl modified hyperbranched polyester is respectively 6 times of the adding mass of the hydroxy acrylate in the step C2, and the adding amount of the 3-isocyanate propyl trimethoxy silane is 40 percent of the adding mass of the carboxyl modified hyperbranched polyester.
Example 4:
the anti-ultraviolet bright plastic paint coating comprises the following raw materials, by weight, 20 parts of modified polyurethane acrylic hyperbranched polymer, 5 parts of active diluent, 0.1 part of photoinitiator, 0.5 part of modified nano titanium dioxide, 0.05 part of defoaming agent, 0.05 part of dispersing agent and 30 parts of deionized water, wherein the active diluent is a mixture of pentaerythritol triacrylate and 1, 6-hexanediol diacrylate in a mass ratio of 1: 2; the photoinitiator is a mixture of 1-hydroxycyclohexyl phenyl ketone and 2-methyl-2- (4-morpholinyl) -1- [4- (methylthio) phenyl ] -1-acetone which are mixed according to the mass ratio of 1: 1; the defoaming agent is an organic silicon defoaming agent; the dispersant is polyethylene glycol, wherein the modified polyurethane acrylic hyperbranched polymer is prepared in example 1;
step A, uniformly stirring part of deionized water, a defoaming agent and a dispersing agent, adding modified nano titanium dioxide at the rotating speed of 600r/min, increasing the rotating speed to 2500r/min, and stirring for 30min to obtain a mixed solution, wherein the mass of the added part of deionized water accounts for 40% of the mass of all the deionized water;
and step B, stirring the modified polyurethane acrylic hyperbranched polymer, the active diluent, the photoinitiator and the rest deionized water at normal temperature, adding the mixed solution obtained in the step A after uniformly mixing, and uniformly stirring to obtain the ultraviolet-resistant bright plastic paint coating.
The modified nano titanium dioxide is prepared by the following steps:
adjusting the pH value of the solution to 4 by using hydrochloric acid and a sodium hydroxide solution, and uniformly stirring for 1h in a constant-temperature water bath kettle at 50 ℃ to obtain a mixed solution A; adding nano titanium dioxide into a mixed solution of deionized water and absolute ethyl alcohol, and performing ultrasonic dispersion for 5min to obtain a mixed solution B; and then uniformly mixing the mixed solution A and the mixed solution B, uniformly stirring and reacting for 1h at 50 ℃, centrifuging, filtering, washing a filter cake with the mixed solution of deionized water and absolute ethyl alcohol, repeating for 3 times, drying the obtained filter cake for 5h at 100 ℃, and grinding to obtain the modified nano titanium dioxide, wherein the volume ratio of the deionized water to the absolute ethyl alcohol in the mixed solution of the deionized water and the absolute ethyl alcohol is 1: 1.
Example 5:
the ultraviolet-resistant bright plastic paint coating comprises the following raw materials, by weight, 40 parts of modified polyurethane acrylic hyperbranched polymer, 10 parts of active diluent, 2 parts of photoinitiator, 1 part of modified nano titanium dioxide, 0.5 part of defoaming agent, 0.5 part of dispersant and 40 parts of deionized water, wherein the active diluent is a mixture of pentaerythritol triacrylate, ethylene glycol diacrylate and neopentyl glycol diacrylate which are mixed according to a mass ratio of 1:1: 1; the photoinitiator is a mixture of 2-methyl-2- (4-morpholinyl) -1- [4- (methylthio) phenyl ] -1-acetone and alpha, alpha' -dimethyl benzil ketal according to the mass ratio of 1: 1; the defoaming agent is an organic silicon defoaming agent; the dispersant is polyethylene glycol, wherein the modified polyurethane acrylic hyperbranched polymer is prepared in example 2;
the preparation method of the anti-ultraviolet bright plastic paint coating comprises the following steps:
step A, uniformly stirring part of deionized water, a defoaming agent and a dispersing agent, adding modified nano titanium dioxide at the rotating speed of 600r/min, increasing the rotating speed to 2500r/min, and stirring for 30min to obtain a mixed solution, wherein the mass of the added part of deionized water accounts for 40% of the mass of all the deionized water;
and step B, stirring the modified polyurethane acrylic hyperbranched polymer, the active diluent, the photoinitiator and the rest deionized water at normal temperature, adding the mixed solution obtained in the step A after uniformly mixing, and uniformly stirring to obtain the ultraviolet-resistant bright plastic paint coating.
The modified nano titanium dioxide is prepared by the following steps:
adjusting the pH value of the solution to 4 by using hydrochloric acid and a sodium hydroxide solution, and uniformly stirring for 1h in a constant-temperature water bath kettle at 50 ℃ to obtain a mixed solution A; adding nano titanium dioxide into a mixed solution of deionized water and absolute ethyl alcohol, and performing ultrasonic dispersion for 5min to obtain a mixed solution B; and then uniformly mixing the mixed solution A and the mixed solution B, uniformly stirring and reacting for 1h at 50 ℃, centrifuging, filtering, washing a filter cake with the mixed solution of deionized water and absolute ethyl alcohol, repeating for 3 times, drying the obtained filter cake for 5h at 100 ℃, and grinding to obtain the modified nano titanium dioxide, wherein the volume ratio of the deionized water to the absolute ethyl alcohol in the mixed solution of the deionized water and the absolute ethyl alcohol is 1: 1.
Example 6:
the ultraviolet-resistant bright plastic paint coating comprises the following raw materials, by weight, 60 parts of modified polyurethane acrylic hyperbranched polymer, 15 parts of active diluent, 3 parts of photoinitiator, 2 parts of modified nano titanium dioxide, 1 part of defoamer, 1 part of dispersant and 50 parts of deionized water, wherein the active diluent is 1, 6-hexanediol diacrylate; the photoinitiator is 2, 4, 6-trimethylbenzoyl-diphenyl phosphine oxide; the defoaming agent is an organic silicon defoaming agent; the dispersant is polyethylene glycol, wherein the modified polyurethane acrylic hyperbranched polymer is prepared in example 3;
the preparation method of the anti-ultraviolet bright plastic paint coating comprises the following steps:
step A, uniformly stirring part of deionized water, a defoaming agent and a dispersing agent, adding modified nano titanium dioxide at the rotating speed of 600r/min, increasing the rotating speed to 2500r/min, and stirring for 30min to obtain a mixed solution, wherein the mass of the added part of deionized water accounts for 50% of the mass of all the deionized water;
and step B, stirring the modified polyurethane acrylic hyperbranched polymer, the active diluent, the photoinitiator and the rest deionized water at normal temperature, adding the mixed solution obtained in the step A after uniformly mixing, and uniformly stirring to obtain the ultraviolet-resistant bright plastic paint coating.
The modified nano titanium dioxide is prepared by the following steps:
adjusting the pH value of the solution to 4 by using hydrochloric acid and a sodium hydroxide solution, and uniformly stirring for 1h in a constant-temperature water bath kettle at 50 ℃ to obtain a mixed solution A; adding nano titanium dioxide into a mixed solution of deionized water and absolute ethyl alcohol, and performing ultrasonic dispersion for 5min to obtain a mixed solution B; and then uniformly mixing the mixed solution A and the mixed solution B, uniformly stirring and reacting for 1h at 50 ℃, centrifuging, filtering, washing a filter cake with the mixed solution of deionized water and absolute ethyl alcohol, repeating for 3 times, drying the obtained filter cake for 7h at 100 ℃, and grinding to obtain the modified nano titanium dioxide, wherein the volume ratio of the deionized water to the absolute ethyl alcohol in the mixed solution of the deionized water and the absolute ethyl alcohol is 1: 1.
Comparative example 1:
ultraviolet-resistant bright plastic paint coating
Compared with example 4, the modified polyurethane acrylic hyperbranched polymer in the raw material is replaced by carboxyl modified hyperbranched polyester, and the rest is the same.
The carboxyl modified hyperbranched polyester is prepared by the following method:
adding hyperbranched polyester, maleic anhydride and anhydrous dioxane into a reaction container in sequence, stirring to completely dissolve the hyperbranched polyester and the maleic anhydride, adding a transesterification catalyst tin chloride when obtaining a uniform solution, heating a reaction system to 95 ℃ in a stirring state, continuously stirring and reacting at a constant temperature for 24 hours, and then carrying out reduced pressure distillation on the reaction liquid to remove a solvent and a small amount of water to obtain carboxyl modified hyperbranched polyester, wherein the adding amount ratio of the hyperbranched polyester, the maleic anhydride and the dioxane is 50g:15g:150ml, the hyperbranched polyester is hyperbranched polyester polyol, the average functionality of terminal hydroxyl is 32, and the number average molecular weight is 3000;
comparative example 2:
an ultraviolet-resistant bright plastic paint coating,
compared with the example 5, the modified polyurethane acrylic hyperbranched polymer in the raw material is replaced by hyperbranched polyester, the branched polyester is hyperbranched polyatomic alcohol, the average functionality of the terminal hydroxyl is 32, the number average molecular weight is 3000, and the rest are the same.
Comparative example 3:
ultraviolet-resistant bright plastic paint coating
Compared with example 6, the modified nano silica in the raw material is replaced by nano silica, and the rest is the same.
Example 7: the coatings obtained in examples 1 to 3 and comparative examples 1 to 3 were applied to glass test pieces (10 cm. times.10 cm. times.6 mm) of the same size, and the ultraviolet ray resistance test, adhesion and hardness test were conducted under the same curing conditions; the ultraviolet ray transmittance of the two different coating film samples is tested by taking the same uncoated glass sheet as reference contrast; the adhesion test adopts GB/T1998-1992 as a determination standard, and the degree of damage among fine scratches of a coating film is observed according to a circling method to judge the grade of the adhesion; hardness was measured according to the GB/T5739-1996 pencil method.
The coatings of the above examples 1 to 3 and comparative examples 1 to 3 were applied to tinplate, the coatings were quickly folded in half on steel columns of different diameters, and flexibility was tested using an OTX-type elasticity tester for paint films produced by Tianjin Yonglida materials testing machine, Inc.
The results of the above tests are shown below.
As can be seen from the above data, the coating film properties of examples 4-6 are superior to those of comparative examples 1-3.
In the description herein, references to the description of "one embodiment," "an example," "a specific example" or the like are intended to mean that a particular feature, structure, material, or characteristic described in connection with the embodiment or example is included in at least one embodiment or example of the invention. In this specification, the schematic representations of the terms used above do not necessarily refer to the same embodiment or example. Furthermore, the particular features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples.
The foregoing is merely exemplary and illustrative of the principles of the present invention and various modifications, additions and substitutions of the specific embodiments described herein may be made by those skilled in the art without departing from the principles of the present invention or exceeding the scope of the claims set forth herein.
Claims (6)
1. An anti-ultraviolet bright plastic paint is characterized by comprising the following raw materials, by weight, 20-60 parts of modified polyurethane acrylic hyperbranched polymer, 5-15 parts of active diluent, 0.1-3 parts of photoinitiator, 0.5-2 parts of modified nano titanium dioxide, 0.05-1 part of defoaming agent, 0.05-1 part of dispersant and 30-50 parts of deionized water;
the modified polyurethane acrylic hyperbranched polymer is prepared by the following steps:
step C1, adding hyperbranched polyester, maleic anhydride and anhydrous dioxane into a reaction container in sequence, stirring, adding a transesterification catalyst tin chloride when obtaining a uniform solution, heating the reaction system to 95-100 ℃ under the stirring state, continuing stirring and reacting at a constant temperature for 24-36 hours, and then carrying out reduced pressure distillation on the reaction liquid to remove the solvent and a small amount of water to obtain carboxyl modified hyperbranched polyester;
step C2, adding anhydrous dioxane into a reaction container, introducing nitrogen for 10-15min, adding isophorone diisocyanate, stannous octoate and linear polyethylene glycol, reacting at 87-93 ℃ for 4-8h, cooling to 50-55 ℃, adding hydroxyl acrylate, and continuing to react for 5-8h to obtain isocyanate and methacrylate-based polyurethane prepolymer;
and C3, adding the carboxyl modified hyperbranched polyester obtained in the step C1 into the reaction system in the step C2, continuously keeping the temperature at 50-55 ℃, sampling every 0.5 hour to determine the content of NCO groups, adding 3-isocyanate propyl trimethoxy silane to continuously react when the weight content of the NCO groups changes to be less than or equal to 0.01 percent, sampling every 0.5 hour to determine the content of the NCO groups, stopping the reaction when the weight content of the NCO groups changes to be less than or equal to 0.01 percent, adding triethylamine to stir for 10 minutes, removing the solvent, and performing rotary evaporation to remove unreacted micromolecules to obtain the modified polyurethane acrylic hyperbranched polymer.
2. The ultraviolet light resistant bright plastic paint as claimed in claim 1, wherein the amount ratio of the hyperbranched polyester, the maleic anhydride and the dioxane added in step C1 is 30-50g:5-15g: 100-4000 ml, wherein the hyperbranched polyester is hyperbranched polyatomic alcohol, the average functionality of the terminal hydroxyl groups is 32, and the number average molecular weight is 3000-4000.
3. The ultraviolet-resistant bright plastic paint coating as claimed in claim 1, wherein the molar mass ratio of isophorone diisocyanate, stannous octoate, polyethylene glycol and hydroxyl acrylate in step C2 is 2-3:0.005-0.008:1:1, wherein the number average molecular weight of polyethylene glycol is 800-1000-.
4. The UV resistant bright plastic paint coating of claim 1, wherein the added mass of the carboxyl modified hyperbranched polyester in the step C3 is 3-6 times of the added mass of the hydroxyl acrylate in the step C2, and the added mass of the 3-isocyanatopropyl trimethoxy silane is 20-40% of the added mass of the carboxyl modified hyperbranched polyester.
5. The ultraviolet-resistant bright plastic paint coating as claimed in claim 1, wherein the modified nano titanium dioxide is prepared by the following steps:
adjusting the pH value of the solution to 4-4.5 by using hydrochloric acid and sodium hydroxide solution, and uniformly stirring for 1h in a constant-temperature water bath kettle at 50-60 ℃ to obtain a mixed solution A; adding nano titanium dioxide into a mixed solution of deionized water and absolute ethyl alcohol, and performing ultrasonic dispersion for 5min to obtain a mixed solution B; and then uniformly mixing the mixed solution A and the mixed solution B, uniformly stirring and reacting for 1-2h at 50-60 ℃, centrifuging, filtering, cleaning a filter cake by using the mixed solution of deionized water and absolute ethyl alcohol, repeating for 3-4 times, drying the obtained filter cake for 5-7h at 100 ℃, and grinding to obtain the modified nano titanium dioxide, wherein the volume ratio of the deionized water to the absolute ethyl alcohol in the mixed solution of the deionized water and the absolute ethyl alcohol is 1: 1.
6. The method for preparing an anti-ultraviolet bright plastic paint coating according to claim 1, which is characterized by comprising the following steps:
step A, uniformly stirring part of deionized water, a defoaming agent and a dispersing agent, adding modified nano titanium dioxide at the rotating speed of 800r/min of 600-;
and step B, stirring the modified polyurethane acrylic hyperbranched polymer, the active diluent, the photoinitiator and the rest deionized water at normal temperature, adding the mixed solution obtained in the step A after uniformly mixing, and uniformly stirring to obtain the ultraviolet-resistant bright plastic paint coating.
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