CN112521775A

CN112521775A - Preparation method of composite nano powder and coating for preparing anti-reflection and transparent heat-insulation coating

Info

Publication number: CN112521775A
Application number: CN202011598593.8A
Authority: CN
Inventors: 姚伯龙; 温焱焱; 范世龙; 王露; 曾婷; 王利魁
Original assignee: Jiangnan University
Current assignee: Jiangnan University
Priority date: 2020-12-30
Filing date: 2020-12-30
Publication date: 2021-03-19

Abstract

The invention relates to a preparation method for preparing a composite nano-powder having both anti-reflection and transparent heat insulation coatings and a coating, belonging to the preparation field of automobile glass and architectural glass. The present invention obtains the anti-reflection nano-particle@ATO composite nano-powder through the preparation of transparent and heat-insulating ATO suspension, the preparation of anti-reflection nano-particles, and the preparation of anti-reflection nano-particle@ATO composite nano-powder; and then the particles are used to prepare It has both anti-reflection and transparent thermal insulation coating. The method of the invention can prepare a coating with both anti-reflection and transparent heat insulation. The coating can be widely used in architectural glass and automotive glass where high light transmittance is required.

Description

Preparation method of composite nano powder and coating for preparing anti-reflection and transparent heat-insulation coating

Technical Field

The invention relates to a preparation method of composite nano powder and a coating for preparing a coating with antireflection and transparent heat insulation functions, belonging to the field of preparation of automobile glass and building glass.

Background

As global warming, especially in hot summer, brings extreme discomfort to people, and for this reason, people generally use air conditioners to reduce indoor/in-vehicle temperature, and the use of air conditioners causes a large amount of energy consumption. Therefore, the new concept of transparent heat insulation is provided for the students, and the students pay attention to and pay attention to the new concept.

At present, ATO (nano tin antimony oxide), ITO (nano indium tin oxide), AZO (nano zinc aluminum oxide) and the like are commonly used as transparent heat-insulating nano particles, the nano particles have certain light transmittance to visible light and have a good shielding effect on infrared, but when the content of the nano particles in a system is large, the visible light transmittance is low, so that not only indoor lighting is influenced, but also sight is influenced, and the application range of the nano particles is limited.

The antireflection film, also called an antireflection film, plays a role in reducing the loss of light energy on the surface of the glass and improving the transmittance. Therefore, the composite material has the advantages that the nano particles with the antireflection function are compounded with the transparent heat-insulation nano particles, so that the composite material has a strong barrier rate to infrared light, can realize high visible light transmittance and has excellent optical performance. Is expected to expand the application range.

Disclosure of Invention

The invention aims to overcome the defects and provides a preparation method for preparing composite nano powder with antireflection and transparent heat insulation coatings and a coating, wherein nano particles with antireflection functions are compounded with nano particles with transparent heat insulation to ensure that the nano particles have good ultraviolet shielding.

The technical scheme of the invention is a preparation method of anti-reflection nano particle @ ATO composite nano powder, which comprises the following steps:

(1) preparation of transparent insulating ATO suspension: SnCl₄·5H₂O and SbCl₂Dispersing in hydrochloric acid, and adjusting the pH value of the solution; stirring to obtain transparent heat-insulating ATO suspension;

(2) preparing the antireflection nano particles: precursor A, structure directing agent B, HCl and H₂O and C₂H₅Fully mixing OH, filtering, washing and drying after magnetic stirring to obtain the anti-reflection nano particles;

(3) preparation of anti-reflection nano particle @ ATO composite nano powder: and (3) ultrasonically dissolving the anti-reflection nano particles prepared in the step (2) in deionized water to obtain uniform and stable white suspension, then dropwise adding the ATO suspension prepared in the step (1) and ammonia water into the white suspension, magnetically stirring, filtering, washing and drying to obtain the anti-reflection nano particle @ ATO composite nano powder.

Further, the precursor A in the step (2) is one or more of tetrabutyl titanate, tetraethyl orthosilicate and tetrabutyl zirconate;

the structure directing agent B is one or more of dodecyl trimethyl ammonium chloride, polyvinylpyrrolidone and polyethylene glycol.

Further, the step (1) comprises the following specific steps: SnCl₄·5H₂O∶SbCl₂Mixing and dispersing in 10-30 mL hydrochloric acid with volume concentration of 37% according to molar ratio of 5-10: 1, and adjusting pH of the solution to 10 with concentrated ammonia water; stirring for 22-26h to obtain transparent and heat-insulating ATO suspension.

Further, the step (2) comprises the following specific steps: and (3) preparing a precursor A: structure directing agent B: HCl: h₂O：C₂H₅OH, according to a molar ratio of 1-10: 0.10-0.15: 0.10-0.20: 4.5-5.0: 20-25, magnetically stirring at 30 ℃ for 4-6h, filtering, washing, and drying at 30-70 ℃ to obtain the anti-reflection nanoparticles.

Further, the step (3) comprises the following specific steps: accurately weighing 5-10g of the anti-reflection nanoparticles prepared in the step (2), performing ultrasonic treatment for 10-30min at 30-50Hz, and dissolving in 10-20mL of deionized water to obtain uniform and stable white suspension; then 0.5-2g of ATO suspension prepared in the step (1) and 2-5mL of ammonia water are weighed and dripped into the white suspension, and the mixture is magnetically stirred for 2-5h at the temperature of 80 ℃; filtering, washing and drying for 4-6h at 50-80 ℃ to obtain the antireflection nano particle @ ATO composite nano powder.

The coating with the functions of antireflection and transparent heat insulation is prepared by adopting the composite nano powder.

Further, the steps are as follows:

(1) crushing: carrying out ultrafine grinding on the anti-reflection nano particle @ ATO composite nano powder by using a planetary ball mill to obtain ultrafine powder with uniform particle size;

(2) dispersing: weighing 5-10g of the superfine powder, dispersing in 50-100mL of deionized water, and ultrasonically dispersing for 10-30min at 30-50Hz to obtain a uniform and stable dispersion; adding 0.05-0.3% of dispersant by mass, magnetically stirring and dissolving at room temperature, then adding 5-10g of waterborne polyurethane, adding 0.2-0.5% of functional auxiliary agent by mass concentration, and uniformly stirring to obtain a dispersion liquid; and (3) coating the dispersion liquid on PET by adopting a roll coating method, and drying to obtain the composite coating with antireflection and transparent heat insulation.

Further, the dispersant is specifically a PVA-2699 type dispersant;

the functional auxiliary agent is one or more of a defoaming agent, a pH regulator and a flatting agent.

The invention has the beneficial effects that: the method can prepare the coating with both antireflection and transparent heat insulation. The coating can be widely applied to the fields of building glass and automobile glass with higher requirements on light transmittance.

Drawings

FIG. 1 is a graph showing the transmittance of an anti-reflective and transparent thermal barrier coating prepared in examples.

Detailed Description

EXAMPLE 1 preparation of composite nanopowders

(1) Preparation of transparent insulating ATO suspension: SnCl₄·5H₂O and SbCl₂Mixing at a molar ratio of 9: 1The mixture was dispersed in 10mL of hydrochloric acid (37% by volume), and the pH of the solution was adjusted to 10 with concentrated aqueous ammonia. Stirring for 24h to obtain transparent heat-insulating powder nanometer tin antimony oxide (ATO) suspension.

(2) Preparing the antireflection nano particles: mixing n-butyl titanate: polyethylene glycol: HCl: h₂O：C₂H₅OH is mixed in a molar ratio of 1: 0.10: 0.10: 4.5: and (3) stirring the 20 ingredients at 30 ℃ for 5 hours by magnetic force, filtering, washing and drying to obtain the anti-reflection nano particles.

(3) Preparation of anti-reflection nano particle @ ATO composite nano powder: accurately weighing 5g of the anti-reflection nanoparticles prepared in the step (2), ultrasonically dissolving the anti-reflection nanoparticles in 10mL of deionized water to obtain uniform and stable white suspension, then weighing 0.5g of the ATO suspension prepared in the step (1) and 2mL of ammonia water, dropwise adding the ATO suspension and the ammonia water into the white suspension, magnetically stirring the mixture for 3 hours at 80 ℃, and then filtering, washing and drying the mixture to obtain the anti-reflection nanoparticle @ ATO composite nano powder.

The preparation method of the coating with the functions of antireflection and transparent heat insulation comprises the following steps:

and carrying out ultrafine grinding on the antireflection nano particle @ ATO composite nano powder by using a planetary ball mill to obtain powder with uniform particle size. 5g of the superfine powder is weighed and dispersed in 50mL of deionized water, and the uniform and stable dispersion is obtained through ultrasonic dispersion. Adding 0.025g of PVA-2699 type dispersing agent by mass fraction, magnetically stirring and dissolving at room temperature, then adding 5g of waterborne polyurethane, adding 0.002g of defoaming agent, and uniformly stirring to obtain a dispersion liquid. The dispersion is coated on PET by a roll coating method, so that a coating with antireflection and transparent heat insulation is obtained.

Comparative example 1

The preparation method of the transparent heat-insulating powder comprises the following steps:

preparation of transparent insulating suspension: SnCl₄·5H₂O and SbCl₂The solution was mixed and dispersed in 10mL of hydrochloric acid (37% by volume) at a molar ratio of 9: 1 to adjust the pH of the solution to 10. Stirring for 24h to obtain transparent heat-insulating powder nanometer tin antimony oxide (ATO) suspension. The final solution was transferred to a hydrothermal reactor. Heating it to 200 deg.C, and reactingAnd the time is 24 hours. Filtering and drying at 100 ℃ for 10h to obtain ATO powder.

And carrying out ultrafine grinding on the ATO nano powder by utilizing a planetary ball mill to obtain powder with uniform particle size. 5g of the superfine powder is weighed and dispersed in 50mL of deionized water, and the uniform and stable dispersion is obtained through ultrasonic dispersion. Adding 0.025g of PVA-2699 type dispersing agent by mass fraction, magnetically stirring and dissolving at room temperature, then adding 5g of waterborne polyurethane, adding 0.002g of defoaming agent, and uniformly stirring to obtain a dispersion liquid. The dispersion was coated on PET by roll coating to obtain an ATO coating layer.

The graph of the transmittance of the ATO coating prepared in comparative example 1 and the antireflective nanoparticle @ ATO composite coating prepared in example 1 is shown in fig. 1, and it can be seen that with the addition of the antireflective nanoparticles, the transmittance of the coating film in visible light is obviously improved while the lower transmittance in the infrared region is ensured.

Claims

1. a preparation method of composite nano-powder is characterized in that step is:

(1) Preparation of transparent and heat-insulating ATO suspension: SnCl ₄ 5H ₂ O and SbCl ₂ were dispersed in hydrochloric acid to adjust the pH of the solution; after stirring, a transparent and heat-insulating ATO suspension was obtained;

(2) Preparation of anti-reflection nanoparticles: the precursor A, the structure-directing agent B, HCl, H ₂ O and C ₂ H ₅ OH are fully mixed, filtered, washed and dried after magnetic stirring to obtain anti-reflection nanoparticles;

(3) Preparation of anti-reflection nanoparticles@ATO composite nano-powder: take the anti-reflection nanoparticles prepared in step (2) and dissolve them in deionized water ultrasonically to obtain a uniform and stable white suspension, and then take the anti-reflection nanoparticles prepared in step (1). ATO suspension and ammonia water were added dropwise to the above white suspension under magnetic stirring, filtered, washed and dried to obtain antireflection nanoparticles@ATO composite nanopowder.

2 . The method for preparing composite nano-powder according to claim 1 , wherein the precursor A in step (2) is one of n-butyl titanate, tetraethyl orthosilicate and tetrabutyl zirconate. 3 . one or more;

The structure-directing agent B is specifically one or more of dodecyltrimethylammonium chloride, polyvinylpyrrolidone and polyethylene glycol.

3. The preparation method of composite nano-powder according to claim 1, characterized in that the specific step of step (1) is: mixing and dispersing SnCl ₄ ·5H ₂ O:SbCl ₂ in a molar ratio of 5-10:1 in 10- In 30 mL of hydrochloric acid with a volume concentration of 37%, the pH of the solution was adjusted to 10 with concentrated ammonia water; after stirring for 22-26 h, a transparent and heat-insulating ATO suspension was obtained.

4 . The method for preparing composite nano-powder according to claim 1 , wherein the specific steps of step (2) are: preparing precursor A: structure-directing agent B: HCl: H ₂ O: C ₂ H ₅ OH by moles. 5 . The ratio of 1-10: 0.10-0.15: 0.10-0.20: 4.5-5.0: 20-25 ingredients, magnetic stirring at 30 ° C for 4-6 h, filtration, washing, and drying at 30-70 ° C to obtain anti-reflection nanoparticles.

5 . The method for preparing composite nano-powder according to claim 1 , wherein the specific steps of step (3) are as follows: accurately weighing 5-10 g of the anti-reflection nanoparticles prepared in step (2), ultrasonicating at 30-50 Hz 10-30min, dissolve in 10-20mL deionized water to obtain a uniform and stable white suspension; then weigh 0.5-2g ATO suspension obtained in step (1) and 2-5mL ammonia water and add dropwise to the above white suspension magnetic stirring at 80 °C for 2-5 h; filtration, washing, and drying at 50-80 °C for 4-6 h to obtain anti-reflection nanoparticles@ATO composite nanopowder.

6. A coating with both anti-reflection and transparent heat insulation, characterized in that: it is prepared by using the composite nano-powder described in any one of claims 1-5.

7. The coating with both anti-reflection and transparent heat insulation according to claim 6, characterized in that the step is:

(1) Pulverization: Ultrafine pulverization of anti-reflection nanoparticles@ATO composite nanopowder is carried out by planetary ball mill to obtain ultrafine powder with uniform particle size;

(2) Dispersion: Weigh 5-10g of the above-mentioned ultrafine powder and disperse it in 50-100mL of deionized water, and ultrasonically disperse at 30-50Hz for 10-30min to obtain a uniform and stable dispersion; add 0.05%-0.3% of Dispersant, dissolve by magnetic stirring at room temperature, then add 5-10g water-based polyurethane, add functional additives with a mass concentration of 0.2%-0.5%, and stir to obtain a dispersion liquid; the above dispersion liquid is coated on PET by roller coating method After drying, a coating with both anti-reflection and transparent heat insulation is obtained.

8. The coating with anti-reflection and transparent heat insulation according to claim 7, characterized in that: the dispersant is specifically a PVA-2699 type dispersant;

The functional auxiliary agent is one or more of defoaming agent, pH adjusting agent and leveling agent.