CN114752292A - High-molecular coating liquid for self-cleaning glass and preparation method thereof - Google Patents
High-molecular coating liquid for self-cleaning glass and preparation method thereof Download PDFInfo
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Abstract
The scheme relates to a high-molecular coating liquid for self-cleaning glass, which comprises high-stability silicon dioxide sol, organic silicon polyurethane resin, a long-chain alkyl silane coupling agent, a solvent and an auxiliary agent; the high-stability silica sol is prepared by taking tetraethoxysilane as a precursor, taking a modifier with a hydrophilic main chain and a hydrophobic side chain as a core, taking absolute ethyl alcohol as a cosolvent and ammonia water as a catalyst through a sol-gel method, and then adding KH550 and stirring. The macromolecular coating solution provided by the invention is a coating compounded by polyurethane resin and silica sol, wherein the silica sol is core-shell sol particles prepared by taking a fluorine-containing modifier as a core, and has uniform size, difficult agglomeration in the coating, good compatibility and high storage stability; the film is easy to form, the formed coating has strong adhesive force, and a super-hydrophobic coating is formed on the surface of the substrate and has self-cleaning performance; the silica sol particles can improve the high temperature resistance and the wear resistance of the coating, and the durability of the coating is good.
Description
Technical Field
The invention relates to the technical field of high polymer materials, in particular to a high polymer coating liquid for self-cleaning glass and a preparation method thereof.
Background
The glass is an amorphous inorganic non-metallic material, the main component is silicon dioxide, and the glass is widely applied to buildings and plays a role in wind insulation and light transmission. However, with the rapid development of the industry, the environment deterioration is more and more serious, the air pollution degree is more and more serious, and the dust in the air is increased, so that the outer facade of the building is dusted and dirty, the transparent glass is particularly serious, and the cleaning and nursing problems are more and more prominent. On the other hand, the quality requirements of life of people are higher and higher, so that a novel glass which utilizes natural conditions to achieve the self-cleaning effect is urgently needed. Self-cleaning glass comes from the process of transportation, namely, a hydrophilic or hydrophobic film is covered on the surface of common glass, so that pollutants or dust falling on the self-cleaning glass can automatically fall off or be degraded under the action of gravity, rainwater and other external forces.
The construction of the surface of the super-hydrophobic coating needs to simultaneously satisfy two conditions, namely, the super-hydrophobic coating contains low surface energy substances and has a certain rough structure. However, the mechanical stability of the superhydrophobic coating is difficult to maintain stably, and the surface of the superhydrophobic coating is subjected to external impact, friction and the like for a long time due to long-term exposure in a polluted environment, so that the surface texture is damaged, and the water repellency is gradually reduced. If the mechanical property of the surface is simply improved, the light transmittance is deteriorated, and the original value of the glass is lost. And the coating formed by spraying silica sol on the glass surface is more and more fragile in the long-term exposure and dirty erosion, the adhesive force is reduced, and the loss of hydrophobicity is caused.
Disclosure of Invention
Aiming at the defects in the prior art, the coating formed by combining the silica sol and the polymer resin has durability and self-cleaning property, and has strong adhesive force with a glass substrate.
In order to achieve the purpose, the invention provides the following technical scheme:
a high-molecular coating liquid for self-cleaning glass comprises the following raw materials in parts by weight:
1-3 parts of high-stability silica sol, 5-10 parts of organic silicon polyurethane resin, 0.1-0.5 part of long-chain alkyl silane coupling agent, 1-6 parts of solvent and 0.2-1 part of auxiliary agent;
wherein the preparation process of the high-stability silica sol is as follows:
1) adding perfluoro n-octyl epoxypropane and epoxy resin E-03 into a reaction bottle, and opening ring reaction under the catalysis of CTAB to obtain fluorine-containing epoxy resin; then adding amine-terminated polyether, and directly heating to react to obtain a modifier with a hydrophilic main chain and a hydrophobic side chain;
2) preparing core-shell silica sol by using tetraethoxysilane as a precursor, a modifier as a core, absolute ethyl alcohol as a cosolvent and ammonia water as a catalyst through a sol-gel method, and then adding a certain amount of absolute ethyl alcohol and water to adjust the solid content of the core-shell silica sol to 4-6 wt%;
3) dissolving KH550 in absolute ethyl alcohol, dropwise adding into the system in the step 2), sealing and stirring for 4h, and standing overnight to obtain high-stability silica sol;
the main raw materials of the organic silicon polyurethane resin are isocyanate, polyalcohol and organic silicon diol.
Further, the mass ratio of the perfluoro-n-octyl epoxypropane to the epoxy resin E-03 is 2-8: 98-92; the amino-terminated polyether is amino-terminated polyoxyethylene ether polyoxypropylene ether, and the molecular weight of the amino-terminated polyether is 600-1000.
Further, the specific process of step 2) is as follows: dissolving a certain amount of modifier in 60ml of absolute ethyl alcohol, adding 5ml of ammonia water, and stirring and mixing uniformly at room temperature to obtain a solution A; adding a certain amount of tetraethoxysilane into 5ml of absolute ethyl alcohol, and stirring and mixing uniformly at room temperature to obtain a solution B; dropwise adding the solution B into the solution A which is continuously stirred, sealing and stirring for 4 hours after the dropwise adding is finished, standing overnight, and then adding a certain amount of absolute ethyl alcohol and water to adjust the solid content of the solution B to be 1-2 wt%.
Further, the use amount ratio of the modifier to the tetraethoxysilane is 0.10-0.14: 1.
Further, the addition amount of the KH550 is 30-60% of the mass of the tetraethoxysilane.
Further, the isocyanate in the organic silicon polyurethane resin is isophorone isocyanate, and the polyol is a mixture of polyester polyol and polyether polyol; preferably, the polyhydric alcohol is poly-1, 4-butanediol and poly-hexanediol adipate diol with the mass ratio of 1: 3-6, the weight average molecular weight of the polyhydric alcohol is preferably 2000, and a coating after film forming is hardened and embrittled due to too large molecular weight, and the light transmittance is reduced; if the molecular weight is too small, the compatibility of the prepared polyurethane resin and the silica sol is reduced, and the adhesive force of the coating is reduced.
Further, the organic silicon dihydric alcohol is prepared by carrying out alcohol protection on diethanol amine and then carrying out chlorine substitution reaction on the diethanol amine and gamma-chloropropyltrimethoxysilane. The polyurethane containing siloxane bonds is hydrolyzed when mixed with the high stability silica sol to combine with the hydroxyl groups on the surface of the silica to form chemical bonds to tightly connect the two materials.
The long-chain silane coupling agent is gamma-glycidyl ether oxyoctyl trimethoxy silane, the steric hindrance effect of the long-chain alkyl is increased, and the silicon-oxygen bond is catalyzed and hydrolyzed to further graft the high-stability silicon dioxide sol and the organosilicon polyurethane resin to form composite particles, so that the overall compatibility of the high-molecular coating liquid is improved.
Further, the solvent is an alcohol solvent, preferably ethanol, methanol or isopropanol; the auxiliary agents are defoaming agents, dispersing agents and flatting agents which are common auxiliary agents in the field of coatings and play a role in basic defoaming, dispersing and the like; the specific types and the ratios of the functional additives can be adjusted according to actual conditions, and the scheme is not limited.
The invention further provides a preparation method of the macromolecular coating liquid for the self-cleaning glass, which comprises the steps of mixing the high-stability silica sol, the organic silicon polyurethane resin and the solvent together under high-speed stirring according to the formula amount, adding the long-chain alkyl silane coupling agent and the auxiliary agent, and uniformly stirring to obtain the self-cleaning glass.
Compared with the prior art, the invention has the beneficial effects that: the macromolecular coating solution provided by the invention is a coating compounded by polyurethane resin and silica sol, wherein the silica sol is core-shell sol particles prepared by taking a fluorine-containing modifier as a core, and has uniform size, difficult agglomeration in the coating, good compatibility and high storage stability; the film is easy to form, the formed coating has strong adhesive force, and a super-hydrophobic coating is formed on the surface of a substrate which is glass, so that the glass substrate has self-cleaning performance; the silica sol particles can improve the high temperature resistance and the wear resistance of the coating, and the durability of the coating is good.
Drawings
FIG. 1 is a graph of water contact angle for example 1.
Detailed Description
The technical solutions of the present invention will be described clearly and completely with reference to the following embodiments, and it should be understood that the described embodiments are some, but not all, embodiments of the present invention. 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.
In addition, the technical features involved in the different embodiments of the present invention described below may be combined with each other as long as they do not conflict with each other.
The starting materials used in this case are commercially available without further indication, wherein the highly stable silica sol is prepared as follows:
1) adding perfluoro-n-octyl propylene oxide into a reaction bottle
With epoxy treesLipid E-03
Opening ring reaction under the catalysis of CTAB to obtain fluorine-containing epoxy resin; then adding amino-terminated polyether
(molecular weight is 600), adding ethanol as solvent, heating to 60 deg.C, stirring for 3 hr, and removing solvent to obtain modifier with hydrophilic main chain and hydrophobic side chain
Dissolving 0.25g of modifier in 60ml of absolute ethyl alcohol, adding 5ml of ammonia water, and stirring and mixing uniformly at room temperature to obtain a solution A; adding 2.2ml of ethyl orthosilicate into 5ml of absolute ethyl alcohol, and stirring and mixing uniformly at room temperature to obtain a solution B; dropwise adding the solution B into the solution A which is continuously stirred, sealing and stirring for 4 hours after the dropwise adding is finished, standing overnight, and then adding a certain amount of absolute ethyl alcohol and water to adjust the solid content of the solution B to be 1-2 wt%.
Dissolving 1.1ml of KH550 in 5ml of absolute ethyl alcohol, dropwise adding into the system in the step 2), sealing and stirring for 4h, and standing overnight to obtain the high-stability silica sol (the water contact angle is 158.5 degrees).
In the prior art, a research on modifying silica sol by adopting a fluorine-containing silane coupling agent is carried out, the hydrophobicity of the sol can be improved by adding the fluorine-containing silane coupling agent, and the silica sol has better compatibility with most of base materials with hydroxyl on the surfaces due to the existence of silicon hydroxyl, but the stability of the silica sol formed in the way is still not ideal. The fluorine-containing silane coupling agent is added after the silica sol is formed, and the compatibility is deteriorated along with the prolonging of the storage time; the formed coating is less stable in long-term environmental erosion, the hydrophobic groups on the surface are gradually lost, and finally the hydrophobicity is lost. Therefore, the fluorine-containing material is selected as the inner core to be wrapped in the silica sol, so that the stability of the sol can be effectively improved. In the selection of materials, after the epoxy resin E-03 is used as a substrate to introduce the fluorine-containing hydrophobic side chain, the epoxy groups at two ends are used to introduce the hydrophilic main chain, and the formed modifier with the hydrophilic main chain and the hydrophobic side chain can form a spherical core in the preparation process of the silica sol so as to be coated in the silica. If the coating is directly coated with a hydrophobic fluorine-containing material, spherical particles having a uniform size cannot be formed, which adversely affects the performance of the sol.
Silicone polyurethane resin:
the preparation of the organosilicon polyurethane resin is a conventional polyurethane preparation process, and can be carried out according to the following processes: adding polyol into a reaction kettle, diluting with DMF, adding half amount of isocyanate, heating to 80 ℃, stirring for reaction for 1h, then continuously adding DMF to proper viscosity, adding organic silicon diol, stirring for half an hour, then adding the rest isocyanate, reacting at 80 ℃ until the system is viscous, finally blocking with methanol, and adding DMF to adjust the solid content to 30%.
Wherein the organic silicon dihydric alcohol is prepared by alcohol protection of diethanol amine and subsequent chlorine substitution reaction of the diethanol amine and gamma-chloropropyltrimethoxysilane
At present, the silicon dioxide sol is prepared and then is usually directly sprayed on the surface of a glass substrate to form a coating, but the durability of the coating is poor, the polymer emulsion can effectively improve the performances of the sol such as durability, adhesive force and the like, but the direct mixing can cause the demulsification of a system, the sedimentation of particles in the system and the poor storage stability. However, the silicon dioxide sol with a core-shell structure and uniform size is compounded with the polyurethane resin modified by the organic silicon, so that the problems of poor toughness and easy cracking and falling caused by high coating hardness can be effectively solved, the compatibility of the composite material can be improved, and the storage time can be prolonged.
Example 1:
mixing 1 part of high-stability silica sol, 5 parts of organic silicon polyurethane resin and 3 parts of ethanol together under high-speed stirring, adding 0.1 part of gamma-glycidyl ether oxyoctyl trimethoxy silane and 2 parts of auxiliary agent, and uniformly stirring to obtain the high-stability silicon dioxide sol.
Example 2:
mixing 2 parts of high-stability silica sol, 7 parts of organic silicon polyurethane resin and 3 parts of ethanol together under high-speed stirring, adding 0.3 part of gamma-glycidyl ether oxyoctyl trimethoxy silane and 2 parts of auxiliary agent, and uniformly stirring to obtain the high-stability silicon dioxide sol.
Example 3:
mixing 3 parts of high-stability silica sol, 10 parts of organic silicon polyurethane resin and 6 parts of ethanol together under high-speed stirring, adding 0.1 part of gamma-glycidyl ether oxyoctyl trimethoxy silane and 2 parts of auxiliary agent, and uniformly stirring to obtain the high-stability silicon dioxide sol.
Comparative example 1:
the difference from example 1 is that the highly stable silica sol is prepared as follows:
dissolving 0.25g of fluorine-containing epoxy resin in 60ml of absolute ethyl alcohol, adding 5ml of ammonia water, and stirring and mixing uniformly at room temperature to obtain a solution A; adding 2.6ml of ethyl orthosilicate into 5ml of absolute ethyl alcohol, and stirring and mixing uniformly at room temperature to obtain a solution B; dropwise adding the solution B into the solution A which is continuously stirred, sealing and stirring for 4 hours after the dropwise adding is finished, standing overnight, and then adding a certain amount of absolute ethyl alcohol and water to adjust the solid content of the solution B to be 1-2 wt%.
Dissolving 2.4ml of KH550 in 5ml of absolute ethanol, dropwise adding into the system in the step 2), sealing and stirring for 4h, and standing overnight.
Comparative example 2:
adding 5ml of ammonia water into 60ml of absolute ethyl alcohol, and stirring and mixing uniformly at room temperature to obtain a solution A; adding 2.6ml of tetraethoxysilane into 5ml of absolute ethyl alcohol, and stirring and mixing uniformly at room temperature to obtain a solution B; dropwise adding the solution B into the solution A which is continuously stirred, sealing and stirring for 4 hours after the dropwise adding is finished, standing overnight, and then adding a certain amount of absolute ethyl alcohol and water to adjust the solid content of the solution B to be 1-2 wt%.
Dissolving 2.4ml of KH550 and 0.25g of modifier in 10ml of absolute ethyl alcohol, dropwise adding the mixture into the system obtained in the step 2), sealing and stirring for 4 hours, and standing overnight to obtain the silica sol.
Mixing 1 part of silica sol, 5 parts of commercially available waterborne polyurethane and 3 parts of ethanol together under high-speed stirring, adding 0.1 part of gamma-glycidyl ether oxypropyltrimethoxysilane and 2 parts of an auxiliary agent, and uniformly stirring to obtain the aqueous polyurethane adhesive.
And (3) verification:
storage stability: the resulting mixture was stored in a sealed condition for 10 days, and the presence or absence of abnormalities such as precipitation was observed.
Adhesion force: with reference to GB/T9286-1998, the adhesion between the coating and the substrate is proved to be good at the level of 0-3;
contact angle: measured at room temperature using Sci 3000F contact angle/interface system;
contamination resistance: reference GB/T9780-1988;
and (3) coating stability: the coating is acid and alkali resistant: preparing solutions with different pH values by using hydrochloric acid, sodium hydroxide and water, dripping the solutions on the surface of a finished product, and measuring a contact angle. Mechanical stability of the coating: the finished coating was peel tested using a test tape to test the contact angle of the surface after peeling. The stability of the coating is excellent if the contact angle change is not obvious, the stability of the coating is general if the contact angle changes within 10 degrees, and the stability of the coating is poor if the difference is too large.
Light transmittance: characterization was performed by uv-vis-nir spectrophotometer, with blank glass as a comparison.
TABLE 1
The data in the table show that the water contact angle of the macromolecular coating liquid prepared by compounding the high-stability silica sol and the polyurethane resin is reduced to some extent, but the reduction amplitude is smaller, the super-hydrophobicity can be still kept, and the self-cleaning function is realized. The high-molecular coating liquid has high stability and long storage time, and the formed coating has good stability, the light transmittance is about 90 percent, although the light transmittance is not as high as that of common glass, the high-molecular coating liquid can also have high light transmission effect under the condition of ensuring high adhesive force and super hydrophobicity, and can meet daily light transmission requirements.
While embodiments of the invention have been disclosed above, it is not limited to the applications listed in the description and the embodiments, which are fully applicable in all kinds of fields of application of the invention, and further modifications may readily be effected by those skilled in the art, so that the invention is not limited to the specific details without departing from the general concept defined by the claims and the scope of equivalents.
Claims (10)
1. A high-molecular coating liquid for self-cleaning glass is characterized by comprising the following raw materials in parts by weight:
1-3 parts of high-stability silica sol, 5-10 parts of organic silicon polyurethane resin, 0.1-0.5 part of long-chain alkyl silane coupling agent, 1-6 parts of solvent and 0.2-1 part of auxiliary agent;
wherein the preparation process of the high-stability silica sol is as follows:
1) adding perfluoro n-octyl epoxypropane and epoxy resin E-03 into a reaction bottle, and opening-ring reaction under the catalysis of CTAB to obtain fluorine-containing epoxy resin; then adding amino-terminated polyether, and directly heating and reacting to obtain a modifier with a hydrophilic main chain and a hydrophobic side chain;
2) preparing core-shell silica sol by using tetraethoxysilane as a precursor, a modifier as a core, absolute ethyl alcohol as a cosolvent and ammonia water as a catalyst through a sol-gel method, and then adding a certain amount of absolute ethyl alcohol and water to adjust the solid content of the core-shell silica sol to be 4-6 wt%;
3) dissolving KH550 in absolute ethyl alcohol, dropwise adding into the system in the step 2), sealing and stirring for 4h, and standing overnight to obtain high-stability silicon dioxide sol;
the main raw materials of the organic silicon polyurethane resin are isocyanate, polyalcohol and organic silicon diol.
2. The polymer coating liquid for self-cleaning glass according to claim 1, wherein the mass ratio of perfluoro-n-octyl propylene oxide to epoxy resin E-03 is 2-8: 98-92; the amino-terminated polyether is amino-terminated polyoxyethylene ether polyoxypropylene ether, and the molecular weight of the amino-terminated polyether is 600-1000.
3. The polymer coating liquid for self-cleaning glass according to claim 1, wherein the step 2) comprises the following steps: dissolving a certain amount of modifier in 60ml of absolute ethyl alcohol, adding 5ml of ammonia water, and stirring and mixing uniformly at room temperature to obtain a solution A; adding a certain amount of tetraethoxysilane into 5ml of absolute ethyl alcohol, and stirring and mixing uniformly at room temperature to obtain a solution B; dropwise adding the solution B into the solution A which is continuously stirred, sealing and stirring for 4 hours after the dropwise adding is finished, standing overnight, and then adding a certain amount of absolute ethyl alcohol and water to adjust the solid content of the solution B to be 1-2 wt%.
4. The polymer coating solution for self-cleaning glass as claimed in claim 1, wherein the amount ratio of the modifier to the tetraethoxysilane is 0.10-0.14: 1.
5. The polymer coating liquid for self-cleaning glass according to claim 1, wherein the amount of KH550 added is 30-60% by mass of tetraethoxysilane.
6. The polymer coating liquid for self-cleaning glass according to claim 1, wherein the isocyanate in the silicone polyurethane resin is isophorone isocyanate, and the polyol is a mixture of polyester polyol and polyether polyol.
7. The polymer coating liquid for self-cleaning glass according to claim 1, wherein the polyol is poly-1, 4-butanediol and poly-hexanediol adipate diol in a mass ratio of 1: 3-6.
8. The polymeric coating solution for self-cleaning glass according to claim 1, wherein the silicone diol is prepared by alcohol protection of diethanolamine and subsequent chlorine substitution reaction with gamma-chloropropyltrimethoxysilane.
9. The polymer coating solution for self-cleaning glass according to claim 1, wherein the solvent is an alcohol solvent; the auxiliary agent is a defoaming agent, a dispersing agent and a flatting agent; the long-chain silane coupling agent is gamma-glycidyl ether oxyoctyl trimethoxy silane.
10. A method for preparing a polymer coating solution for self-cleaning glass according to any one of claims 1 to 9, wherein the coating solution is prepared by mixing the high-stability silica sol, the organic silicon polyurethane resin and the solvent under high-speed stirring according to the formula amount, adding the long-chain alkyl silane coupling agent and the auxiliary agent, and uniformly stirring.
Priority Applications (1)
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| CN117025076B (en) * | 2023-09-11 | 2024-01-30 | 天津大学 | Self-cleaning anti-reflection nano film and preparation method thereof |
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