Nano composite stone material protection agent and preparation method thereof

Technical field of a nano composite stone protective agent and its preparation method:

[0001] The present invention relates to a stone protective agent, in particular to a nano-composite stone protective agent and a preparation method thereof. Background technology:

[0002] Stone application occupies a large proportion in indoor decoration. For example, fluorocarbon stone protective agent is widely used in coating protection of indoor stone countertops, stone wash basins, etc., and is one of the coatings with important applications for indoor high-end stone protection. One. Stone waterproof coating is a kind of stone protection technology, and it has a wide range of applications in modern stone industry. The waterproof coating makes the synthetic resin evenly distributed on the surface of the stone or slowly penetrates into the protective film formed inside the stone, so that the stone is waterproof, anti-fouling, oil-proof, acid and alkali resistant, weathering resistant, aging resistant, freeze-thaw resistant, Anti-biological erosion and other functions, thereby improving the service life and decorative performance of the stone. Fluorocarbon resin waterproof coating belongs to a new generation of stone waterproofing agent. Compared with traditional coatings, it has many excellent characteristics, such as extremely low surface energy and strong hydrophobicity, great stain resistance, weather resistance and super long Durability (its weather resistance can reach more than 15 years), etc. However, when traditional stone protective coatings are used in the application of stone floor tiles, stone furniture, countertops, etc., they cannot meet the requirements of users for the continuous improvement of the quality of stone protective products.

Summary of the invention:

[0003] The object of the present invention overcomes the above-mentioned defects of the prior art, and provides a nano-composite stone protective agent containing carbon nanotubes-titanium dioxide-tourmaline for the surface of a stone, by adding carbon nanotubes to support Ti02/tourmaline nano The compound modifier has excellent protection effect and service life, and at the same time has excellent purification effect on indoor air pollutants, which can optimize indoor air quality.

[0004] The present invention is achieved through the following technical solutions:

[0005] A nano composite stone protective agent, the protective agent raw material includes the following components: a resin raw material composed of vinylidene fluoride resin (VDF) and acrylic resin, carbon nanotubes loaded TiO 2 / tourmaline nano composite modifier, Silane coupling agent, dibutyltin dichloride, solvent, wherein the mass ratio of resin raw material, carbon nanotube-supported Ti02/tourmaline nanocomposite modifier, silane coupling agent, and solvent is: 2~4.5:0.5~0.8: 0.02~0.04: 95~98, the addition amount of dibutyltin dichloride catalyst per liter of protective agent raw materials is 0.5~1mg, the relative mass percentages of vinylidene fluoride resin and acrylic resin in the resin raw materials are 70%~90% and 10%~30%; The solvent is a mixture of solvent oils D30, D40 and D65 with a mass ratio of 10-20: 50-65: 15-40; The carbon nanotubes supported Ti02/tourmaline nanocomposite modification The preparation method of the agent includes the following steps: 1) Add isopropanol to the deionized water while stirring, and then slowly add tetraisopropyl titanate in the same volume as the isopropanol, and then stir for 1-2h after the addition is complete. Hydrogen peroxide solution to the solution becomes clear, 60~75 °C reflux for 40-48h, you can prepare titania sol; in the prepared titania sol, add nano-SiO2 and nano-level tourmaline powder, and stir to prepare Obtain modified Ti02 sol; 2) Disperse the carbon nanotube powder in a mixed acid, sonicate for 2-3h, then wash with deionized water to neutrality, filter with a microporous membrane, and put it in a vacuum drying oven at 110°C Dry for 24h at a temperature to obtain purified carbon nanotubes; 3) Use the purified carbon nanotubes as a carrier to load the modified TiO2 sol. After the two are mixed, they are placed in an ultrasonic cleaner and ultrasonically shaken at 35-45 °C for 30 minutes. Then put it in a magnetic stirrer at 68-7 2 °C in a water bath for 1h, and then put it in a vacuum drying oven at 110 °C for 24h at a constant temperature, and dry to constant weight to obtain carbon nanotubes loaded TiO2/tourmaline nanocomposite modifier .

[0006] The purity of nano-SiO2 and nano-scale tourmaline powder is not less than 99%.

[0007] Preferably, the mass ratio of nano SiO 2, nano tourmaline powder and titanium dioxide sol in step 1) is 3~5:5~12:80~90.

[0008] The vinylidene fluoride resin is preferably a polyvinylidene fluoride homopolymer resin, which is the main waterproof functional component; the acrylic resin is preferably a methyl methacrylate resin, which increases adhesion to the substrate and a protective agent The effect of phase stability; the silane coupling agent is preferably the silane coupling agent KH550, which mainly functions to increase the bonding strength of the interface between the nano-modifier and the resin; the dibutyltin dichloride catalyst mainly functions to promote resin polymerization and improve The role of film-forming properties. The carbon nanotubes load Ti02/tourmaline nanocomposite modifier, Ti02 particles can reduce the scattering intensity of long-wave ultraviolet rays and absorb short-wave ultraviolet rays, while nano-SiO2 particles can absorb and reflect ultraviolet rays with a wavelength less than 400nm and those with a wavelength greater than 800nm. Infrared, and its absorption rate and reflectivity can reach more than 70%, which can greatly improve the anti-aging property of the protective agent. At the same time, nanoparticles have photocatalytic properties, can efficiently decompose organic matter, and are more bactericidal than hypochlorous acid, significantly increase the antibacterial corrosion resistance of the protective agent, and improve the self-cleaning performance and adhesion. At the same time, carbon nanotubes and nano-SiO2 can also enhance the hardness, scratch resistance and wear resistance of the coating.

[0009] The preparation method of the nano-composite stone protective agent, the method includes the following steps:

[0010] 1) Add isopropanol to the deionized water while stirring, and then slowly add tetraisopropyl titanate in the same volume as isopropanol dropwise, and then stir for 1-2h after the dropwise addition, and add hydrogen peroxide solution to The solution becomes clear, and it is refluxed at 60~75°C for 40-48h to obtain a titania sol; add nano-SiO2 and nanometer tourmaline powder to the prepared titania sol, and stir to prepare a modified TiO2 sol;

[0011] 2) The carbon nanotube powder is dispersed in a mixed acid, sonicated for 2-3h, then washed with deionized water to neutrality, filtered with a microporous membrane, put in a vacuum drying oven, and dried at a temperature of 110°C Obtain purified carbon nanotubes in 24 hours;

[0012] 3) The purified carbon nanotubes are used as a carrier to load the modified TiO2 sol. After the two are mixed, they are placed in an ultrasonic cleaner at 35-45°C under ultrasonic vibration for 30 minutes, and then placed in a magnetic stirrer 68 -72Ό water bath heating for 1h, and then put it in a vacuum drying oven 110°C constant temperature drying for 24h, drying to constant weight to obtain carbon nanotubes loaded TiO2 / tourmaline nano composite modifier;

[0013] 4) Vinylidene fluoride resin (VDF) and acrylic resin are used as resin raw materials, silane coupling agent is used as crosslinking agent, dibutyltin dichloride is used as catalyst, and the carbon nanotubes obtained in step 3) support Ti02/tourmaline The nano-composite modifier is a modifier. After the above-mentioned materials are dissolved in a solvent according to the above-mentioned mass ratio, the nano-composite stone protective agent is obtained by using a sand mill at room temperature to disperse for 3 to 5 minutes.

[0014] The present invention also protects the application of the nano-composite stone protective agent on the surface of the stone, and the nano-composite stone protective agent is coated on the surface of the stone to form a coating.

[0015] The beneficial effects of the present invention are as follows:

[0016] The present invention by adding carbon nanotubes loaded TiO2 / tourmaline nano composite modifier, TiO2 particles can reduce the scattering intensity of long-wave ultraviolet light, absorb short-wave ultraviolet light, and nano-SiO2 particles can absorb and reflect the ultraviolet light with a wavelength less than 400nm And infrared rays with a wavelength greater than 800nm, and its absorption and reflectivity can reach more than 70%, which can greatly improve the anti-aging property of the protective agent. At the same time, nanoparticles have photocatalytic properties, can efficiently decompose organic matter, and have more bactericidal efficacy than hypochlorous acid, significantly increase the antibacterial corrosion resistance of the protective agent, and improve the self-cleaning performance and adhesion. At the same time, carbon nanotubes and nano-SiO2 can also enhance the hardness, scratch resistance and wear resistance of the coating.

Detailed ways:

[0017] The following is a further description of the present invention, rather than a limitation of the present invention.

[0018] Embodiment 1:

[0019] Preparation of nano composite modifier: (1) Add 37.5 mL isopropanol to 1000 mL of deionized water while stirring, and then slowly add 37.5 mL of tetraisopropyl titanate dropwise, and then stir for 1 hour after the addition is complete, and add a little more Hydrogen peroxide solution until the solution becomes clear. Then transfer to a constant temperature oil tank and return to the oil bath for 48 hours to obtain titanium dioxide sol. After the sol is prepared, 15 g of nanometer SiO 2 and 25 g of nanometer tourmaline powder are added and stirred to prepare a modified TiO 2 sol. (2) Weigh 100g of carbon nanotube powder and place it in a beaker, disperse it in a mixed acid, sonicate it for 2h, then wash it with deionized water until it is neutral, filter it with a microporous membrane, and place it in a vacuum drying oven. After drying at 110°C for 24h, take it out for later use. (3) Load the modified TiO2 sol with carbon nanotubes as a carrier, mix the carbon nanotubes and the modified TiO2 sol in a beaker, place the beaker in an ultrasonic cleaner at 40 °C, ultrasonically shake for 30 minutes, and then release it. Heated in a 70°C water bath in a magnetic stirrer for 1h, and then put the beaker in a vacuum drying oven at 110°C for 24h at a constant temperature, and dried to constant weight to obtain the composite nano-modifier.

[0020] 100gD30 mineral spirits, 500gD40 mineral spirits and 400gD65 mineral spirits are mixed uniformly to obtain 1000g of solvent.

[0021] 14g of polyvinylidene fluoride homopolymer resin, 6g of methyl methacrylate resin, 5g of composite nano-modifier, 0.20g of silane coupling agent KH550, 1000g of solvent and 0.6mg of dibutyltin dichloride catalyst were placed The nano-composite stone protective agent can be obtained by using a sand mill to disperse in the dispersion kettle for 3 minutes.

[0022] Embodiment 2:

[0023] Preparation of nano-composite modifier: (1) Add 75 mL of isopropanol to 2000 mL of deionized water while stirring, and then slowly add 75 mL of tetraisopropyl titanate dropwise, and then stir for 2 hours after the dropwise addition, and add a little peroxide again Hydrogen solution until the solution becomes clear. Then transfer to a constant temperature oil tank and return to the oil bath for 48 hours to obtain titanium dioxide sol. After the sol is prepared, 50 g of nano-SiO 2 and 120 g of nano-sized tourmaline powder are added and stirred to prepare a modified TiO 2 sol. Weigh 500g of carbon nanotube powder in a beaker, disperse it in a mixed acid, sonicate it for 2h, then wash it with deionized water to neutrality, filter it with a microporous membrane, and place it in a vacuum drying oven at 110 After drying for 24 hours at °C, take it out for later use. (3) Use carbon nanotubes as a carrier to load the modified TiO2 sol, mix the carbon nanotubes and the modified TiO2 sol in a beaker, place the beaker in an ultrasonic cleaner at 40°C, ultrasonically shake for 30 minutes, and then release it. Heated in a water bath at 70°C in a magnetic stirrer for 1h, then put the beaker in a vacuum drying oven at 110°C for 24h at a constant temperature, and dried to constant weight to obtain the composite nano-modifier.

[0024] 400g of D30 mineral spirits, 1300g of D40 mineral spirits and 300g of D65 mineral spirits are mixed uniformly to obtain 2000g of solvent.

[0025] 76.50g polyvinylidene fluoride homopolymer resin, 13.50g methyl methacrylate resin, 15g composite nano-modifier, 0.80g silane coupling agent KH550, 2000g solvent and 1.9mg dichlorodibutyltin catalyst The nano-composite stone protective agent can be obtained by placing it in a dispersion kettle and dispersing for 5 minutes using a sand mill.