CN114763437B - Preparation method and application of modified hydroxypropyl silicone oil - Google Patents
Preparation method and application of modified hydroxypropyl silicone oil Download PDFInfo
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- C08L83/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
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- C09D133/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
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- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
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- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
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- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
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- C08K2201/011—Nanostructured additives
Abstract
The invention relates to the technical field of coating additives, and discloses a preparation method and application of modified hydroxypropyl silicone oil, which comprises the following steps: (1) Ultrasonically dispersing nano silicon dioxide in liquid cage-type octa-epoxy silsesquioxane, dropwise adding the nano silicon dioxide into a mixed solution of 2, 2-dimethylolbutyric acid and a graphene oxide ethanol solution, and heating while stirring for reaction; (2) Adding dopamine and sodium phthalate into the product obtained in the step (1), and continuously heating and reacting under inert atmosphere; and adding the dopamine-coated nano silicon dioxide and the hydroxypropyl silicone oil, and then continuing to react to obtain the modified hydroxypropyl silicone oil. The modified hydroxypropyl silicone oil can maintain longer-acting anti-doodling and anti-fouling performance, and has better wear resistance, strength and weather resistance; the anti-doodling and anti-fouling paint prepared from the modified hydroxypropyl silicone oil has excellent anti-fouling performance, and simultaneously has better overall stability and substrate adhesion.
Description
Technical Field
The invention relates to the technical field of coating additives, in particular to a preparation method and application of modified hydroxypropyl silicone oil.
Background
In recent years, with the development of economy, the stop board walls and the like full of small advertisements can be seen everywhere in many cities, the stop board walls and the like are manually removed every year, the effect is not ideal, the phenomenon is called Graffiti abroad, the phenomenon not only affects the appearance of the cities, but also consumes the economic expenditure. In addition, the more PU synthetic leather, water-based paint and the like are applied to home furnishing and wall decoration, the problem that the home furnishing and wall decoration is not resistant to contamination and doodling is also solved. Therefore, the loss caused by the malicious graffiti pasting is more and more concerned by people, the city appearance and the landscape are influenced, the graffiti removal and various stickers are time-consuming and labor-consuming, the substrate is easy to damage, and a large amount of funds are consumed. The phenomenon of random scrawling and pasting happens occasionally and is difficult to avoid, so that the development of the coating with the scrawling prevention function is very necessary.
The realization mode of the anti-doodling coating mainly shows two aspects of resin and special auxiliary agent. The polysiloxane is widely applied as a special auxiliary agent, such as methyl silicone oil, polyether silicone oil and the like, but the addition of the auxiliary agent can only change the leveling property, the anti-sticking property and the slip property on the surface of a sheet, and cannot achieve the effects of scrawling prevention and stain resistance. For example, the Chinese patent publication No. CN105385342A discloses a water-based weather-resistant polysiloxane coating which comprises a component A and a component B, wherein the component A comprises modified polysiloxane resin.
In addition, the small-molecular silicone oil type auxiliary agent can be migrated along with time and graffiti cleaning, and the long-acting anti-fouling effect is poor. Although the crosslinking curing can be carried out through the curing agent, the crosslinking density of the obtained product is generally low, and fine stains easily penetrate into the coating and cannot be cleaned; meanwhile, the coating film has low hardness and poor surface wear resistance, and the self-cleaning effect of the coating surface is greatly reduced after the coating is worn by wind and sand; and the weather resistance is poor, and the anti-graffiti and anti-fouling effects gradually lose after long-term exposure to sunlight and rain.
Disclosure of Invention
The invention aims to provide a preparation method and application of modified hydroxypropyl silicone oil, which improves the wear resistance and weather resistance while improving the crosslinking density by adding an auxiliary agent and modifying crosslinking, so that the modified hydroxypropyl silicone oil has long-acting anti-graffiti and antifouling properties.
The purpose of the invention is realized by the following technical scheme:
in a first aspect, the invention provides a preparation method of modified hydroxypropyl silicone oil, which comprises the following steps:
(1) Ultrasonically dispersing nano silicon dioxide in liquid cage type octa-epoxy silsesquioxane, dropwise adding the nano silicon dioxide into a mixed solution of 2, 2-dimethylolbutyric acid and a graphene oxide ethanol solution, and heating while stirring for reaction;
(2) Adding dopamine and sodium phthalate into the product obtained in the step (1), and continuously heating and reacting under inert atmosphere; and adding the dopamine-coated nano silicon dioxide and the hydroxypropyl silicone oil, and then continuing to react to obtain the modified hydroxypropyl silicone oil.
The hydroxypropyl silicone oil has good water resistance and doodling resistance, but small molecular silicone oil substances can be migrated along with time and doodling cleaning, cannot be independently used as an anti-fouling auxiliary agent for the anti-doodling coating, and silane active groups in the hydroxypropyl silicone oil easily generate self-crosslinking and lose activity, so that the hydroxypropyl silicone oil needs to be modified to improve the doodling resistance. The nano silicon dioxide particles can endow the nano silicon dioxide particles with higher hardness, weather resistance and wear resistance, but the nano silicon dioxide particles have poorer dispersion uniformity in a polymer, the cage-type octa-epoxy silsesquioxane can realize the combination of organic groups and inorganic groups by covalent bonds, the inorganic cage-type structure has better affinity with the nano silicon dioxide, the cage-type octa-epoxy silsesquioxane has a flexible functional group chain segment which is in a liquid state, a good polymer molecular layer can be formed on the surface of the nano silicon dioxide, and the epoxy groups on the cage-type octa-epoxy silsesquioxane can be crosslinked with active groups of 2, 2-dimethylolbutyric acid and graphene oxide, so that the structural stability is effectively improved. The structure can also enlarge the lamella spacing and the specific surface area of the graphene oxide, has excellent mechanical property and strength, and can also provide more accommodating spaces for subsequent crosslinking and dopamine-coated nano silicon dioxide loading.
Active hydroxyl in the added hydroxypropyl silicone oil can further form a cross-linking structure, so that the cross-linking density is greatly improved, and the easy migration of small molecules is reduced. The dopamine can be subjected to crosslinking and self-polymerization, the amino group rich in the dopamine can enable the modified hydroxypropyl silicone oil to have excellent water solubility, and meanwhile, the main chain of the organic silicon enables the modified hydroxypropyl silicone oil to have low surface tension, so that the modified hydroxypropyl silicone oil has excellent smoothness and stain resistance. In addition, the added dopamine-coated nano-silica can form a special micro-coarse structure in a micron and nanometer range on a graphene oxide lamellar structure together with the added nano-silica and the added cross-linked polymer chain, so that the surface energy is reduced, the self-cleaning performance is improved, and the hydrophobic and oleophobic performance of the surface is improved.
Preferably, in the step (1), the mass ratio of the nano-silica to the liquid cage-type octaepoxysilsesquioxane is 0.05-0.15: 1; the particle size of the nano silicon dioxide is 10-30 nm; the power of the ultrasonic dispersion is 600-1000W, and the time is 10-50 min.
Preferably, in the step (1), the mass ratio of the liquid cage-type octaepoxysilsesquioxane to the 2, 2-dimethylolbutyric acid to the graphene oxide is 20-45: 1 to 7:0.01 to 0.1; the concentration of the graphene oxide ethanol solution is 0.5-1.5%; the heating reaction is carried out for 0.5-2 h at the temperature of 90-130 ℃.
The liquid cage type octa-epoxy silsesquioxane in the step (1) is excessive, unreacted epoxy groups can ensure that the epoxy groups and terminal hydroxyl groups of the hydroxypropyl silicone oil are further crosslinked, but the mass ratio is exceeded, so that excessive crosslinking and overlarge viscosity are caused, and the film forming property of the coating is poor.
Preferably, in the step (2), the particle size of the nano-silica in the dopamine-coated nano-silica is 100 to 500nm; the mass ratio of the nano silicon dioxide to the dopamine-coated nano silicon dioxide is 10:1 to 6.
The special micro-coarse structure in the micron and nanometer range is closely related to the particle size of the nano-silicon dioxide and the particle size of the dopamine-coated nano-silicon dioxide, and the mass ratio of the nano-silicon dioxide to the dopamine-coated nano-silicon dioxide can also influence the formation of a compact structure and has better anti-stain performance.
Preferably, in the step (2), the mass ratio of the 2, 2-dimethylolbutyric acid to the sodium phthalate is 1:0.1 to 0.3; the hydroxyl content of the hydroxypropyl silicone oil is 1-5%, and the molecular weight is 500-3500.
The 2, 2-dimethylolbutyric acid can prevent further crosslinking, excessive viscosity and poor processability due to acidity, and the sodium phthalate is added to promote more crosslinking reaction rather than self-polymerization reaction of dopamine, so as to improve the stability and the binding property of the polymer, and the proportion of the two needs to be limited to balance the comprehensive properties. The hydroxyl content and the molecular weight of the hydroxypropyl silicone oil determine the crosslinking efficiency and the reactivity of the hydroxypropyl silicone oil, and the higher the molecular weight is, the higher the viscosity is, the more adverse effect is on the combination with the reactive functional group, the more effective crosslinking reaction can be ensured to occur within the limited range, and the mobility of the micromolecular silicone oil is reduced.
Preferably, in the step (2), the mass ratio of the dopamine to the hydroxypropyl silicone oil to the liquid cage-type octaepoxy silsesquioxane is 0.3-0.5: 10 to 16:1; the continuous heating reaction is carried out for 1 to 3 hours at a temperature of between 80 and 110 ℃; the continuous reaction is carried out for 0.5 to 2 hours at the temperature of between 80 and 110 ℃.
In a second aspect, the invention also provides application of the modified hydroxypropyl silicone oil prepared by the preparation method in anti-doodling and anti-fouling coatings.
Preferably, the anti-doodling and anti-fouling coating comprises a component A and a component B; the component A comprises 50-70 parts of fluorine-containing acrylate, 5-15 parts of modified hydroxypropyl silicone oil, 0.5-1 part of silane coupling agent, 0.5-8 parts of auxiliary agent, 10-20 parts of pigment and filler and 5-10 parts of water by weight, and the component B comprises 10-20 parts of curing agent and 60-80 parts of solvent.
The fluorine-containing material has better scrawling resistance due to low surface energy, and fluorine atoms can form hydrogen bond combination with graphene oxide, so that the overall stability is improved, and the lower mechanical property of the fluorine-containing material is optimized. The addition of the nano silicon dioxide in the modified hydroxypropyl silicone oil can also improve the film forming strength, and the siloxy can improve the surface adhesive force of the coating and prolong the service life. Coupling reaction can occur in the silane coupling agent, and the bonding performance of the coating is improved.
Preferably, the auxiliary agent comprises one or more of a leveling agent, a dispersing agent and a defoaming agent; the pigment filler comprises one of red paste, white paste, titanium dioxide and white carbon black; the silane coupling agent comprises 3- (2, 3-epoxypropoxy) propyltrimethoxysilane; the curing agent is aliphatic isocyanate; the solvent is lipid or ketone organic solvent.
C-OH bonds in the hydroxypropyl silicone oil can react with NCO groups in the curing agent to form curing crosslinking, and the obtained coating has good hydrophobic and oleophobic properties and anti-graffiti antifouling properties.
Preferably, the use method of the anti-doodling and anti-fouling coating comprises the following steps of mixing the component A and the component B according to a mass ratio of 50:5 to 20 and stirring.
Compared with the prior art, the invention has the following beneficial effects:
(1) The micromolecule easy migration of the hydroxypropyl silicone oil is improved, the crosslinking density is improved by adding an auxiliary agent and modifying crosslinking, and the longer-acting anti-doodling and anti-fouling performance is maintained;
(2) The addition of the graphene oxide and the nano silicon dioxide can improve the wear resistance and strength of the coating; the nano silicon dioxide can also form a special micro-rough structure in a micron and nanometer range on the graphene oxide lamellar structure, so that the self-cleaning performance is improved while the surface energy is reduced, and the hydrophobic and oleophobic performance of the surface is improved;
(3) The anti-doodling and anti-fouling paint prepared from the modified hydroxypropyl silicone oil has excellent anti-fouling performance, and is also good in overall stability and substrate adhesion.
Detailed Description
The technical solution of the present invention is illustrated by the following specific examples, but the scope of the present invention is not limited thereto:
general examples
1. Preparing modified hydroxypropyl silicone oil:
(1) Dispersing nano-silica with the particle size of 10-30 nm in liquid cage type octa-epoxy silsesquioxane EP0435 for 10-50 min at the ultrasonic power of 600-1000W, wherein the mass ratio of the nano-silica to the liquid cage type octa-epoxy silsesquioxane is 0.05-0.15: 1; then dropwise adding the mixture into a mixed solution of 2, 2-dimethylolbutyric acid and 0.5-1.5% graphene oxide ethanol solution, wherein the mass ratio of the liquid cage octaepoxysilsesquioxane to the 2, 2-dimethylolbutyric acid to the graphene oxide is 20-45: 1 to 7:0.01 to 0.1, and heating and reacting for 0.5 to 2 hours at the temperature of between 90 and 130 ℃ while stirring;
(2) Adding dopamine and sodium phthalate into the product obtained in the step (1), reacting for 1-3 h at 80-110 ℃ under inert atmosphere, wherein the mass ratio of 2, 2-dimethylolbutyric acid to sodium phthalate is 1:0.1 to 0.3; adding dopamine-coated nano silicon dioxide with the particle size of 100-500 nm and hydroxypropyl silicone oil, and continuing to react at 80-110 ℃ for 0.5-2 h to obtain modified hydroxypropyl silicone oil; the dopamine-coated nano silicon dioxide is obtained by dispersing nano silicon dioxide in a Tris-HCl solution, adding dopamine hydrochloride, stirring at room temperature for reaction, and then carrying out centrifugal separation; the mass ratio of the nano silicon dioxide to the dopamine-coated nano silicon dioxide is 10:1 to 6; the mass ratio of the dopamine to the hydroxypropyl silicone oil to the liquid cage-type octa-epoxy silsesquioxane is 0.3-0.5: 10 to 16:1; the hydroxyl content of the hydroxypropyl silicone oil is 1-5%, and the molecular weight is 500-3500.
2. Anti-doodling and anti-fouling paint
The anti-doodling and anti-fouling coating comprises a component A and a component B; the component A comprises 50-70 parts of fluorine-containing acrylate, 5-15 parts of modified hydroxypropyl silicone oil, 0.5-1 part of silane coupling agent, 0.5-8 parts of auxiliary agent, 10-20 parts of pigment and filler and 5-10 parts of water by weight, and the component B comprises 10-20 parts of curing agent and 60-80 parts of solvent. When in use, the component A and the component B are mixed according to the mass ratio of 50:5 to 20 and stirring.
Wherein the auxiliary agent comprises one or more of a leveling agent, a dispersing agent and a defoaming agent; the pigment and the filler comprise one of red paste, white paste, titanium pigment and white carbon black; the curing agent is aliphatic isocyanate; the solvent is lipid or ketone organic solvent.
Example 1
1. Preparing modified hydroxypropyl silicone oil:
(1) 1g of nano silicon dioxide with the particle size of 15nm is dispersed in 10g of liquid cage octa-epoxy silsesquioxane EP0435 for 3min at the ultrasonic power of 800W; dropwise adding the mixed solution into a mixed solution of 1.7g of 2, 2-dimethylolbutyric acid and a graphene oxide ethanol solution with the concentration of 0.8%, wherein the graphene oxide ethanol solution is prepared by dispersing 0.02g of graphene oxide in the ethanol solution, and heating and reacting for 1h at the temperature of 120 ℃ while stirring;
(2) Adding 3.5g of dopamine and 0.34g of sodium phthalate into the obtained substance in the step (1) and reacting for 2 hours at 90 ℃ under a nitrogen atmosphere; then 0.4g of dopamine-coated nano silicon dioxide and 135g of hydroxypropyl silicone oil (the hydroxyl content of the hydroxypropyl silicone oil is 1.7 percent, the molecular weight is 2000) are added, and the reaction is continued for 1.5 hours at 100 ℃ to obtain modified hydroxypropyl silicone oil; the dopamine-coated nano-silicon dioxide is obtained by dispersing nano-silicon dioxide with the particle size of 250nm in a Tris-HCl solution, adding dopamine hydrochloride, stirring at room temperature for reaction, and then carrying out centrifugal separation.
2. Anti-doodling and anti-fouling paint
The anti-doodling and anti-fouling coating comprises a component A and a component B; the component A comprises 65 parts of fluorine-containing acrylate, 10 parts of modified hydroxypropyl silicone oil, 0.7 part of silane coupling agent, 0.5 part of fluorocarbon modified polymer flatting agent (basf), 10 parts of white slurry and 6 parts of water, and the component B comprises 15 parts of curing agent HDI and 65 parts of glycol monomethyl ether acetate. When in use, the component A and the component B are mixed according to the mass ratio of 50:15 and mixing and stirring.
Example 2
1. Preparing modified hydroxypropyl silicone oil:
(1) 1g of nano silicon dioxide with the particle size of 15nm is dispersed in 10g of liquid cage octa-epoxy silsesquioxane EP0435 for 3min at the ultrasonic power of 800W; dropwise adding the mixed solution into a mixed solution of 1.7g of 2, 2-dimethylolbutyric acid and a graphene oxide ethanol solution with the concentration of 0.8%, wherein the graphene oxide ethanol solution is prepared by dispersing 0.02g of graphene oxide in the ethanol solution, and heating and reacting for 1h at the temperature of 120 ℃ while stirring;
(2) Adding 3.5g of dopamine and 0.34g of sodium phthalate into the obtained product in the step (1) and reacting for 2 hours at 90 ℃ under a nitrogen atmosphere; then 0.4g of dopamine-coated nano silicon dioxide and 135g of hydroxypropyl silicone oil (the hydroxyl content of the hydroxypropyl silicone oil is 1.7 percent, and the molecular weight is 2000) are added, and the reaction is continued for 1.5 hours at 100 ℃ to obtain modified hydroxypropyl silicone oil; the dopamine-coated nano silicon dioxide is obtained by dispersing nano silicon dioxide with the particle size of 250nm in Tris-HCl solution, adding dopamine hydrochloride, stirring for reaction at room temperature, and then carrying out centrifugal separation.
2. Anti-doodling and anti-fouling paint
The anti-doodling and anti-fouling coating comprises a component A and a component B; the component A comprises 70 parts of fluorine-containing acrylate, 8 parts of modified hydroxypropyl silicone oil, 1 part of silane coupling agent, 3 parts of fluorocarbon modified polymer flatting agent (Basff), 10 parts of white slurry and 6 parts of water, and the component B comprises 12 parts of curing agent HDI and 70 parts of glycol monomethyl ether acetate. When in use, the component A and the component B are mixed according to the mass ratio of 50:10 and mixing and stirring.
Example 3
1. Preparing modified hydroxypropyl silicone oil:
(1) 1g of nano silicon dioxide with the particle size of 20nm is dispersed in 8.4g of liquid cage octa-epoxy silsesquioxane for 20min by ultrasonic power of 900W; dropwise adding the mixed solution into a mixed solution of 0.84g of 2, 2-dimethylolbutyric acid and a graphene oxide ethanol solution with the concentration of 1.0%, wherein the graphene oxide ethanol solution is prepared from 0.025g of graphene oxide pre-ethanol solution, and heating and reacting for 1h at 120 ℃ while stirring;
(2) Adding 4.2g of dopamine and 0.25g of sodium phthalate into the obtained product in the step (1) to react for 1.5h at 110 ℃ in a nitrogen atmosphere; then 0.5g of dopamine-coated nano silicon dioxide and 84g of hydroxypropyl silicone oil (the hydroxyl content of the hydroxypropyl silicone oil is 2.5 percent, the molecular weight is 1000) are added, and the reaction is continued for 1 hour at 90 ℃ to obtain modified hydroxypropyl silicone oil; the dopamine-coated nano silicon dioxide is obtained by dispersing nano silicon dioxide with the particle size of 350nm in Tris-HCl solution, adding dopamine hydrochloride, stirring for reaction at room temperature, and then carrying out centrifugal separation.
2. Anti-doodling and anti-fouling paint
The anti-doodling and anti-fouling coating comprises a component A and a component B; the component A comprises 65 parts of fluorine-containing acrylate, 10 parts of modified hydroxypropyl silicone oil, 0.7 part of silane coupling agent, 0.5 part of fluorocarbon modified polymer flatting agent (basf), 10 parts of white slurry and 6 parts of water, and the component B comprises 15 parts of curing agent HDI and 65 parts of glycol monomethyl ether acetate. When in use, the component A and the component B are mixed according to the mass ratio of 50:15 and mixing and stirring.
Comparative example 1
The difference from example 1 is that: the preparation of the modified hydroxypropyl silicone oil does not add liquid cage type octa-epoxy silsesquioxane.
1. Preparing modified hydroxypropyl silicone oil:
(1) Dispersing 1g of nano silicon dioxide with the particle size of 15nm in a mixed solution of 1.7g of 2, 2-dimethylolbutyric acid and a graphene oxide ethanol solution with the concentration of 0.8% for 3min at the ultrasonic power of 800W, dispersing 0.02g of graphene oxide in the ethanol solution to prepare the graphene oxide ethanol solution, and heating and reacting for 1h at the temperature of 120 ℃ while stirring;
(2) Adding 3.5g of dopamine and 0.34g of sodium phthalate into the obtained product in the step (1) and reacting for 2 hours at 90 ℃ under a nitrogen atmosphere; then 0.4g of dopamine-coated nano silicon dioxide and 135g of hydroxypropyl silicone oil (the hydroxyl content of the hydroxypropyl silicone oil is 1.7 percent, the molecular weight is 2000) are added, and the reaction is continued for 1.5 hours at 100 ℃ to obtain modified hydroxypropyl silicone oil; the dopamine-coated nano-silicon dioxide is obtained by dispersing nano-silicon dioxide with the particle size of 250nm in a Tris-HCl solution, adding dopamine hydrochloride, stirring at room temperature for reaction, and then carrying out centrifugal separation.
2. Anti-doodling and anti-fouling paint
The anti-doodling and anti-fouling coating comprises a component A and a component B; the component A comprises 65 parts of fluorine-containing acrylate, 10 parts of modified hydroxypropyl silicone oil, 0.7 part of silane coupling agent, 0.5 part of fluorocarbon modified polymer flatting agent (basf), 10 parts of white slurry and 6 parts of water, and the component B comprises 15 parts of curing agent HDI and 65 parts of glycol monomethyl ether acetate. When in use, the component A and the component B are mixed according to the mass ratio of 50:15 are mixed and stirred.
Comparative example 2
The difference from example 1 is that: the dopamine-coated nano silicon dioxide is not added in the preparation of the modified hydroxypropyl silicone oil.
1. Preparing modified hydroxypropyl silicone oil:
(1) 1g of nano silicon dioxide with the particle size of 15nm is dispersed in 10g of liquid cage octa-epoxy silsesquioxane EP0435 for 3min at the ultrasonic power of 800W; dropwise adding the mixed solution into a mixed solution of 1.7g of 2, 2-dimethylolbutyric acid and a 0.8% graphene oxide ethanol solution, wherein the graphene oxide ethanol solution is prepared by dispersing 0.02g of graphene oxide in the ethanol solution, and heating and reacting for 1 hour at 120 ℃ while stirring;
(2) Adding 3.5g of dopamine and 0.34g of sodium phthalate into the obtained product in the step (1) and reacting for 2 hours at 90 ℃ under a nitrogen atmosphere; adding 135g of hydroxypropyl silicone oil (the hydroxyl content of the hydroxypropyl silicone oil is 1.7 percent, the molecular weight is 2000) and continuing to react for 1.5h at 100 ℃ to obtain modified hydroxypropyl silicone oil; the dopamine-coated nano silicon dioxide is obtained by dispersing nano silicon dioxide with the particle size of 250nm in Tris-HCl solution, adding dopamine hydrochloride, stirring for reaction at room temperature, and then carrying out centrifugal separation.
2. Anti-doodling and anti-fouling paint
The anti-doodling and anti-fouling coating comprises a component A and a component B; the component A comprises 65 parts of fluorine-containing acrylate, 10 parts of modified hydroxypropyl silicone oil, 0.7 part of silane coupling agent, 0.5 part of fluorocarbon modified polymer flatting agent (basf), 10 parts of white slurry and 6 parts of water, and the component B comprises 15 parts of curing agent HDI and 65 parts of glycol monomethyl ether acetate. When in use, the component A and the component B are mixed according to the mass ratio of 50:15 are mixed and stirred.
Comparative example 3
The difference from example 1 is that: the particle size of the nano silicon dioxide in the dopamine-coated nano silicon dioxide is 600nm; the mass ratio of the nano silicon dioxide to the dopamine-coated nano silicon dioxide is 10:10.
1. preparing modified hydroxypropyl silicone oil:
(1) Dispersing 1g of nano silicon dioxide with the particle size of 15nm in 10g of liquid cage type octa-epoxy silsesquioxane EP0435 for 3min at the ultrasonic power of 800W; dropwise adding the mixed solution into a mixed solution of 1.7g of 2, 2-dimethylolbutyric acid and a 0.8% graphene oxide ethanol solution, wherein the graphene oxide ethanol solution is prepared by dispersing 0.02g of graphene oxide in the ethanol solution, and heating and reacting for 1 hour at 120 ℃ while stirring;
(2) Adding 3.5g of dopamine and 0.34g of sodium phthalate into the obtained substance in the step (1) and reacting for 2 hours at 90 ℃ under a nitrogen atmosphere; adding 1g of dopamine-coated nano silicon dioxide and 135g of hydroxypropyl silicone oil (the hydroxyl content of the hydroxypropyl silicone oil is 1.7 percent, the molecular weight is 2000), and continuously reacting at 100 ℃ for 1.5 hours to obtain modified hydroxypropyl silicone oil; the dopamine-coated nano silicon dioxide is obtained by dispersing nano silicon dioxide with the particle size of 600nm in Tris-HCl solution, adding dopamine hydrochloride, stirring for reaction at room temperature, and then carrying out centrifugal separation.
2. Anti-doodling and anti-fouling paint
The anti-doodling and anti-fouling coating comprises a component A and a component B; the component A comprises 65 parts of fluorine-containing acrylate, 10 parts of modified hydroxypropyl silicone oil, 0.7 part of silane coupling agent, 0.5 part of fluorocarbon modified polymer flatting agent (basf), 10 parts of white slurry and 6 parts of water, and the component B comprises 15 parts of curing agent HDI and 65 parts of glycol monomethyl ether acetate. When in use, the component A and the component B are mixed according to the mass ratio of 50:15 are mixed and stirred.
Comparative example 4
The difference from example 1 is that: the mass ratio of the 2, 2-dimethylolbutyric acid to the sodium phthalate is 1:1.
1. preparing modified hydroxypropyl silicone oil:
(1) 1g of nano silicon dioxide with the particle size of 15nm is dispersed in 10g of liquid cage octa-epoxy silsesquioxane EP0435 for 3min at the ultrasonic power of 800W; dropwise adding the mixed solution into a mixed solution of 1.7g of 2, 2-dimethylolbutyric acid and a graphene oxide ethanol solution with the concentration of 0.8%, wherein the graphene oxide ethanol solution is prepared by dispersing 0.02g of graphene oxide in the ethanol solution, and heating and reacting for 1h at the temperature of 120 ℃ while stirring;
(2) Adding 3.5g of dopamine and 1.7g of sodium phthalate into the obtained substance in the step (1) and reacting for 2 hours at 90 ℃ in a nitrogen atmosphere; then 0.4g of dopamine-coated nano silicon dioxide and 135g of hydroxypropyl silicone oil (the hydroxyl content of the hydroxypropyl silicone oil is 1.7 percent, the molecular weight is 2000) are added, and the reaction is continued for 1.5 hours at 100 ℃ to obtain modified hydroxypropyl silicone oil; the dopamine-coated nano silicon dioxide is obtained by dispersing nano silicon dioxide with the particle size of 250nm in Tris-HCl solution, adding dopamine hydrochloride, stirring for reaction at room temperature, and then carrying out centrifugal separation.
2. Anti-doodling and anti-fouling paint
The anti-doodling and anti-fouling coating comprises a component A and a component B; the component A comprises 65 parts of fluorine-containing acrylate, 10 parts of modified hydroxypropyl silicone oil, 0.7 part of silane coupling agent, 0.5 part of fluorocarbon modified polymer flatting agent (basf), 10 parts of white slurry and 6 parts of water, and the component B comprises 15 parts of curing agent HDI and 65 parts of glycol monomethyl ether acetate. When in use, the component A and the component B are mixed according to the mass ratio of 50:15 are mixed and stirred.
Comparative example 5
The difference from example 1 is that: the hydroxyl content of the hydroxypropyl silicone oil is 0.8%, and the molecular weight is 4300.
1. Preparing modified hydroxypropyl silicone oil:
(1) 1g of nano silicon dioxide with the particle size of 15nm is dispersed in 10g of liquid cage octa-epoxy silsesquioxane EP0435 for 3min at the ultrasonic power of 800W; dropwise adding the mixed solution into a mixed solution of 1.7g of 2, 2-dimethylolbutyric acid and a 0.8% graphene oxide ethanol solution, wherein the graphene oxide ethanol solution is prepared by dispersing 0.02g of graphene oxide in the ethanol solution, and heating and reacting for 1 hour at 120 ℃ while stirring;
(2) Adding 3.5g of dopamine and 0.34g of sodium phthalate into the obtained substance in the step (1) and reacting for 2 hours at 90 ℃ under a nitrogen atmosphere; then 0.4g of dopamine-coated nano silicon dioxide and 135g of hydroxypropyl silicone oil (the hydroxyl content of the hydroxypropyl silicone oil is 0.8 percent, and the molecular weight is 4300) are added to continue to react for 1.5 hours at 100 ℃ to obtain modified hydroxypropyl silicone oil; the dopamine-coated nano silicon dioxide is obtained by dispersing nano silicon dioxide with the particle size of 250nm in Tris-HCl solution, adding dopamine hydrochloride, stirring for reaction at room temperature, and then carrying out centrifugal separation.
2. Anti-doodling and anti-fouling paint
The anti-doodling and anti-fouling coating comprises a component A and a component B; the component A comprises 65 parts of fluorine-containing acrylate, 10 parts of modified hydroxypropyl silicone oil, 0.7 part of silane coupling agent, 0.5 part of fluorocarbon modified polymer flatting agent (basf), 10 parts of white slurry and 6 parts of water, and the component B comprises 15 parts of curing agent HDI and 65 parts of glycol monomethyl ether acetate. When in use, the component A and the component B are mixed according to the mass ratio of 50:15 and mixing and stirring.
Performance test
Adhesion force: performing an adhesion test according to the national standard GB/T9286-1998;
hardness: performing hardness test according to national standard GB/T6739-2006;
water contact angle: testing the water contact angle of the paint sprayed on the aluminum plate by using a water contact angle tester to represent the hydrophobic property of the paint;
anti-graffiti performance: the paint sprayed on the aluminum plate is written by using a doodling pen, then the cotton cloth is wiped by dipping water, and the doodling prevention performance is tested, wherein the doodling prevention performance is completely removed, slightly remained, partially remained, mostly remained and completely remained from good to bad.
Table 1 results of performance tests of anti-graffiti anti-fouling coatings
Specific results are shown in table 1, the anti-doodling and anti-fouling coating obtained in the invention has excellent anti-fouling performance mainly because the integral stability is better, the modified hydroxypropyl silicone oil cannot be migrated along with time and doodling cleaning, and the long-acting anti-doodling and anti-fouling effect can be realized. In addition, the addition amount of each substance in the preparation method needs to be strictly controlled, otherwise, the crosslinking curing and film forming property in the coating components are influenced too little or too much, and the anti-doodling performance of the coating is finally influenced. By combining the embodiment 1 and the comparative example 1, a good cross-linking structure cannot be formed without adding the liquid cage-type octa-epoxy silsesquioxane, and the compatibility between the nano-silica and the polymer is reduced, which affects the long-acting antifouling performance. By combining the example 1 and the comparative example 2, the special micro-rough structure in the micro-nanometer range cannot be formed without adding the dopamine-coated nano-silica, so that the anti-graffiti performance of the surface is reduced, and the film-forming strength of the coating is also reduced. Combining example 1 and comparative example 3, the micro-coarse structure is closely related to the particle size and mass ratio of the nano-silica and the dopamine coated nano-silica, and exceeding the range can influence the formation of the compact structure, and the anti-doodling performance and the film forming performance of the coating. Combining example 1 with comparative example 4, the imbalance of the ratio of 2-dimethylolbutyric acid to sodium phthalate caused a decrease in the overall properties, and in particular, the addition of an excessive amount of sodium phthalate caused an excessive viscosity of the cross-linking, which was detrimental to the subsequent dispersibility with the coating composition. In combination with example 1 and comparative example 5, the hydroxy group content of the hydroxypropyl silicone oil is small, the crosslinking efficiency is reduced, the viscosity is larger as the molecular weight is larger, the bonding with the reactive functional group is more unfavorable, the hydroxypropyl silicone oil cannot generate effective crosslinking reaction, and migration still occurs to cause the doodling prevention to lose effectiveness.
The above description is only a preferred embodiment of the present invention, and not intended to limit the scope of the present invention, and all modifications of equivalent structures and equivalent processes, which are made by the present specification, or directly or indirectly applied to other related technical fields, are included in the scope of the present invention.
Claims (7)
1. The preparation method of the modified hydroxypropyl silicone oil is characterized by comprising the following steps:
(1) Ultrasonically dispersing nano silicon dioxide in liquid cage-type octa-epoxy silsesquioxane, dropwise adding the nano silicon dioxide into a mixed solution of 2, 2-dimethylolbutyric acid and a graphene oxide ethanol solution, and heating while stirring for reaction;
(2) Adding dopamine and sodium phthalate into the product obtained in the step (1), and continuously heating and reacting under inert atmosphere; adding dopamine-coated nano silicon dioxide and hydroxypropyl silicone oil, and continuing to react to obtain modified hydroxypropyl silicone oil;
in the step (2), the particle size of nano silicon dioxide in the dopamine-coated nano silicon dioxide is 100 to 500nm; the mass ratio of the nano silicon dioxide to the dopamine-coated nano silicon dioxide is 10:1 to 6; the mass ratio of the 2, 2-dimethylolbutyric acid to the sodium phthalate is 1:0.1 to 0.3; the hydroxyl content of the hydroxypropyl silicone oil ranges from 1 to 5 percent, and the molecular weight ranges from 500 to 3500; the mass ratio of the dopamine to the hydroxypropyl silicone oil to the liquid cage-type octa-epoxy silsesquioxane is 0.3 to 0.5:10 to 16:1; the continuous heating reaction is carried out for 1 to 3h at the temperature of 80 to 110 ℃; the continuous reaction is carried out at the temperature of 80-110 ℃ for 0.5-2h.
2. The method for preparing modified hydroxypropyl silicone oil according to claim 1, wherein in the step (1), the mass ratio of the nano silicon dioxide to the liquid cage-type octaepoxysilsesquioxane is 0.05 to 0.15:1; the particle size of the nano silicon dioxide is 10 to 30nm.
3. The method for preparing modified hydroxypropyl silicone oil according to claim 1 or 2, wherein in the step (1), the mass ratio of the liquid cage-type octaepoxysilsesquioxane, 2-dimethylolbutyric acid and graphene oxide is 20 to 45:1 to 7:0.01 to 0.1; the concentration of the graphene oxide ethanol solution is 0.5 to 1.5 percent; the heating reaction is carried out at 90 to 130 ℃ for 0.5 to 2h.
4. Use of modified hydroxypropyl silicone oil prepared by the method of any one of claims 1 to 3 in an anti-graffiti anti-fouling coating.
5. The use of claim 4, wherein the anti-graffiti anti-fouling coating comprises two components A and B; the component A comprises 50 to 70 parts of fluorine-containing acrylate, 5 to 15 parts of modified hydroxypropyl silicone oil, 0.5 to 1 part of silane coupling agent, 0.5 to 8 parts of auxiliary agent, 10 to 20 parts of pigment and filler and 5 to 10 parts of water in parts by weight, and the component B comprises 10 to 20 parts of curing agent and 60 to 80 parts of solvent.
6. The use according to claim 5, wherein the auxiliaries comprise one or more of levelling agents, dispersing agents, antifoaming agents; the pigment filler comprises one of red paste, white paste, titanium dioxide and white carbon black; the curing agent is aliphatic isocyanate; the solvent is lipid or ketone organic solvent.
7. The use of claim 5, wherein the anti-doodling and anti-fouling coating is prepared by mixing the component A and the component B according to a mass ratio of 50:5 to 20, and stirring.
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| CN109266153B (en) * | 2018-09-19 | 2020-07-10 | 湖南凯斯利新材料有限公司 | Water-based anti-doodling self-cleaning coating and preparation method thereof |
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