Penetrative film-forming stone protective agent based on modified nano titanium dioxide hydrosol, and preparation method and application of stone protective agent

Penetrating film-forming stone protective agent based on modified nano titanium dioxide hydrosol and its preparation method and application technical field

[0001] The present invention belongs to the technical field of building materials, and specifically relates to a permeable film-forming stone protective agent based on a modified nano-titanium dioxide hydrosol, and a preparation method and application thereof.

Background technique

[0002] Stone protective agent is a liquid specially used to protect stone, which is mainly composed of solute (active ingredient), solvent (thinner) and a small amount of additives. It is brushed, sprayed, coated, rolled, showered, and soaked. Make it evenly distributed on the surface of the stone or penetrate into the inside of the stone to form a kind of protection, so that the stone has the functions of waterproof, anti-fouling, acid and alkali resistance, anti-aging, anti-freezing and thawing, anti-biological erosion, etc., so as to improve the service life of the stone and The effect of decorative performance.

[0003] Nano titanium dioxide has extremely high catalytic activity and excellent semiconductor properties, and has a wide range of applications in the fields of environment, chemical industry and new energy. Compared with the nanometer titanium dioxide powder form, the nanometer titanium dioxide hydrosol has higher chemical stability, is not easy to deactivate, and is convenient for construction and application. In recent years, due to the outstanding performance of nano-titanium dioxide in photocatalysis, self-cleaning, anti-reflection, anti-bacterial, shielding, reinforcement, abrasion reduction, and waterproofing, nano-titanium dioxide hydrosol is a research hotspot in the chemical and material fields. For example, the patent application number CN201510995768.1 discloses a preparation method of an environmental purification finishing agent based on nano titanium dioxide hydrosol; for example, the patent application number CN201810018554.2 discloses a nanometer titanium dioxide used in a low-pressure gas discharge mercury lamp Preparation method of hydrosol coating; for example, the patent application number CN201611171799.6 discloses a photocatalyst air purification material using porous ceramic as a carrier, and using porous ceramic as a carrier to adsorb nano-rare earth hoe hydrosol and nano-titanium dioxide hydrosol. of.

[0004] In view of the above, the application of nano-titanium dioxide hydrosol to stone protective agent is of great significance to improve the quality and performance of the protective agent, and thereby make the stone self-cleaning, antifouling, antibacterial, impermeability, weather resistance, etc. Get a big mention.

Summary of the invention

[0005] In view of the shortcomings of the prior art, the purpose of the present invention is to provide a permeable film-forming stone protective agent based on modified nano titanium dioxide hydrosol and its preparation method and application.

[0006] The technical solution of the present invention is summarized as follows:

[0007] A permeable film-forming stone protective agent based on modified nano-titanium dioxide hydrosol, including the following components by weight percentage: modified nano-titanium dioxide hydrosol 30-55%, mercapto-modified silicone oil 16-22%, ten Heptafluorodecyltrimethoxysilane 5-10%, fluorosilicone modified acrylate emulsion 20-30%, emulsifier 0.5-2%, film forming aid 3-5%, silane coupling agent KH560 0.5-1% ;

[0008] The modified nano-titanium dioxide hydrosol is prepared by reacting the white precipitated Ti0(OH)2 produced by the hydrolysis of soluble titanium salt with nano-silica sol and metal oxide dopants under acidic conditions.

[0009] Preferably, the emulsifier is one or more of sodium dodecyl sulfonate, alkylphenol polyoxyethylene polyoxypropylene polyoxypropylene, polyvinyl alcohol, and fatty acid polyethylene glycol ester.

[0010] Preferably, the film forming aid is propylene glycol butylene, propylene glycol, propylene glycol formate acetate, dodecyl alcohol ester

One or more of.

[0011] Preferably, the preparation method of the modified nano-titanium dioxide hydrosol is as follows: the soluble titanium salt is dissolved in 18-25% aqueous ammonia solution, stirred and hydrolyzed to no longer produce Ti0 (0H)₂When the white precipitate is white, centrifuge and wash with water to remove the acid radical anion. After mixing with the metal oxide dopant, add 15-20% hydrochloric acid solution together, dissolve the gel in a water bath at 60-80 °C, and add nano silica sol dropwise. After stirring and reacting for 3 hours, neutralizing, and evaporating and concentrating to a titanium dioxide content of 8-12%, the modified nano titanium dioxide hydrosol is obtained.

[0012] Preferably, the soluble titanium salt includes one or more of titanium tetrachloride, titanium tetrabromide, titanyl chloride, titanium sulfate, and titanyl sulfate.

[0013] Preferably, the metal oxide dopant is mixed with iron trioxide and tin dioxide in a mass ratio of 4:1.

[0014] Preferably, the mass ratio of the soluble titanium salt, metal oxide dopant, and nano silica sol is 1: (0.01-0.03): (0.2-0.3) ο

[0015] A preparation method of a permeable film-forming stone protective agent based on modified nano-titanium dioxide hydrosol: mix the components in the protective agent by weight percentage.

[0016] A permeable film-forming stone protective agent based on modified nano-titanium dioxide hydrosol is applied to resin-based artificial stone, cement-based artificial stone, composite artificial stone, and sintered artificial stone.

[0017] Preferably, the application method is: sizing the stone protective agent on the artificial stone base surface and curing it naturally.

[0018] The beneficial effects of the present invention:

[0019] (1) The present invention utilizes Fe³\Sn⁴\Nano SiO2 sol modifies the Ti02 hydrosol, using SiO2 sol as a stabilizer to prevent the agglomeration of nano-TiO2 particles and avoid the gel phenomenon, Fe³\Sn⁴>Miscellaneous energy improves the photocatalytic activity of TiO2, thereby improving the performance of the protective agent for self-cleaning, antifouling, sterilization and decomposition of toxic chemical substances (such as HCH0, N0x, S0x, H2S, etc.). Among them, the introduction of the evaluation accounted for part of Ti⁴+ Is substituted to form defects in the Ti02 lattice, capture photoelectrons, reduce electron-hole recombination, and extend the life of OH radicals. In addition, metal ion doping can reduce the adsorption of Ti02 on CO2 (surface adsorption CO2 can form a stable bidentate structure with surface active urn groups and bridging oxygen), thereby preventing the deactivation of photocatalytic surface active species and enhancing the photocatalytic effect.

[0020] (2) The present invention uses modified nano-titanium dioxide hydrosol as the stone protective agent matrix, and uses the strong permeability of titanium dioxide nanoparticles to fill the pores and cracks of the stone, strengthen it, and remove the dirt and bacteria between the pores. Photolysis and removal, fluorosilicone modified acrylate emulsion has excellent film-forming properties, forming a dense protective film on the surface of the stone, improving the corrosion resistance, water resistance, and antifouling of the stone, mercapto-modified silicone oil, seventeen fluorine Decyltrimethoxysilane has excellent permeability, directly penetrates into the stone to form protection, and uses the unique low surface characteristics of organic fluorine and modified silicone oil to further improve the stone's antifouling, oil resistance and hydrophobic properties.

Detailed ways

[0021] The present invention will be further described in detail below with reference to the embodiments, so that those skilled in the art can implement it with reference to the text.

Example 1

[0023] A permeable film-forming stone protective agent based on modified nano-titanium dioxide hydrosol, including the following components by weight percentage: modified nano-titanium dioxide hydrosol 30%, mercapto-modified silicone oil 22%, heptafluorodecyl Trimethoxysilane

10%, fluorosilicone modified acrylate emulsion 30%, sodium lauryl sulfonate 2%, propylene glycol butylene 5%, silane coupling agent KH560

1%；

[0024] The preparation method of the modified nano titanium dioxide hydrosol is as follows:

[0025] S1: Mix ferric oxide and tin dioxide in a mass ratio of 4:1 to obtain a metal oxide dopant;

[0026] S2: Weigh titanium tetrachloride, metal oxide dopant, and nano-silica sol in a mass ratio of 1:0.01:0.2 for use;

[0027] S3: Dissolve titanium tetrachloride in 18% ammonia solution, stir and hydrolyze until no more Ti0(0H) is produced₂When the white precipitate is white, centrifuge and wash with water to remove the acid radical anion. After mixing with the metal oxide dopant, add it to a 15% hydrochloric acid solution, dissolve the gel in a 60°C water bath, and add nano silica sol dropwise, stirring and reacting continuously for 3 hours. After neutralization, evaporation and concentration to a titanium dioxide content of 8%, the modified nano titanium dioxide hydrosol is obtained.

Example 2

[0029] A permeable film-forming stone protective agent based on modified nano-titanium dioxide hydrosol, including the following components by weight percentage: modified nano-titanium dioxide hydrosol 42.5%, thiol modified silicone oil 19%, heptafluorodecyl Trimethoxysilane 7.5%, fluorosilicone modified acrylate emulsion 25%, alkylphenol polyoxyethylene polyoxypropylene polyoxypropylene 1.2%, propylene glycol 4%, silane coupling agent KH560 0.8%;

[0030] The preparation method of the modified nano titanium dioxide hydrosol is as follows:

[0031] S1: Mix ferric oxide and tin dioxide in a mass ratio of 4:1 to obtain a metal oxide dopant;

[0032] S2: Weigh titanium oxychloride, metal oxide dopant, and nano-silica sol in a mass ratio of 1:0.02:0.25 for use;

[0033] S3: Dissolve titanium oxychloride in a 22% aqueous ammonia solution, stir and hydrolyze until no TiO (0H) 2 white precipitate is produced, centrifuge and wash with water to remove acid radical anions, and mix with metal oxide dopants, Add 18% hydrochloric acid solution together, dissolve the gel in a 70°C water bath, and add nano silica sol dropwise, continue to stir and react for 3 hours, neutralize, and evaporate and concentrate to a titanium dioxide content of 10% to obtain the modified nano titanium dioxide Hydrosol.

Embodiment 3

[0035] A permeable film-forming stone protective agent based on modified nano-titanium dioxide hydrosol, including the following components by weight percentage: modified nano-titanium dioxide hydrosol 55%, thiol modified silicone oil 16%, heptafluorodecyl Trimethoxysilane 5%, fluorosilicone modified acrylate emulsion 20%, fatty acid polyethylene glycol ester 0.5%, dodecyl alcohol ester 3%, silane coupling agent KH560 0.5%;

[0036] The preparation method of the modified nano titanium dioxide hydrosol is as follows:

[0037] S1: Mix ferric oxide and tin dioxide in a mass ratio of 4:1 to obtain a metal oxide dopant;

[0038] S2: Weigh titanium sulfate, metal oxide dopants, and nano-silica sol in a mass ratio of 1:0.03:0.3 for use;

[0039] S3: Dissolve titanium sulfate in a 25% aqueous ammonia solution, stir and hydrolyze until no TiO(OH) is produced anymore₂When the white precipitate is white, centrifuge and wash with water to remove the acid radical anion. After mixing with the metal oxide dopant, add it to a 20% hydrochloric acid solution, dissolve the gel in a water bath at 80°C, and add nano silica sol dropwise, and continue to stir and react for 3 hours. After neutralization, evaporation and concentration to a titanium dioxide content of 12%, the modified nanometer titanium dioxide hydrosol is obtained.

[0040] After mixing the components in Examples 1-3 uniformly, they were respectively applied to the base surface of resin-based artificial stone, cement-based artificial stone, composite artificial stone, and sintered artificial stone, and cured naturally.

[0041] Table 1 lists the water resistance and anti-oil effect, acid and alkali resistance coefficient and permeability of the coatings after curing on the resin-based artificial stone base surface in Examples 1-3:

[0042] Table 1:

[0043]

<td></td><td>Water contact angle/°</td><td>Water resistance K/%</td><td>Anti-greasy effect</td><td>Acid and alkali resistance coefficient</td><td>Penetration depth/mm</td>

<td>Example 1</td><td>136</td><td>92. 5</td><td>excellent</td><td>83. 6</td><td>0. 44</td>

<td>Example 2</td><td>142</td><td>93. 8</td><td>excellent</td><td>85. 0</td><td>0.47</td>

<td>Example 3</td><td>145</td><td>94. 1</td><td>excellent</td><td>85. 7</td><td>0. 48</td>

[0044] Table 2 lists the water resistance and anti-oil effect, acid and alkali resistance coefficient and permeability of the coatings after curing on the cement-based artificial stone base surface in Examples 1-3:

[0045] Table 2:

[0046]

<td></td><td>Water contact angle/: Q;</td><td>Water resistance K/%</td><td>Anti-greasy effect</td><td>Acid and alkali resistance coefficient</td><td>Penetration depth/mm</td>

<td>Example 1</td><td>112</td><td>84. 7</td><td>excellent</td><td>81. 3</td><td>1.08</td>

<td>Example 2</td><td>116</td><td>85. 2</td><td>excellent</td><td>82. 4</td><td>1. 17</td>

<td>Example 3</td><td>1.18</td><td>85. 8</td><td>excellent</td><td>82. 9</td><td>1. 32</td>

[0047] Table 3 lists the water resistance and anti-oil effect, acid and alkali resistance coefficient and permeability performance of the coating in Examples 1-3 after curing on the composite artificial stone base surface:

[0048] Table 3:

[0049]

<td></td><td>Water contact angle/°</td><td>Water resistance K/%</td><td>Anti-greasy effect</td><td>Acid and alkali resistance coefficient/%</td><td>Penetration depth/mm</td>

<td>Example 1</td><td>131</td><td>89. 4</td><td>excellent</td><td>83.8</td><td>0. 87</td>

<td>Example 2</td><td>136</td><td>91.6</td><td>excellent</td><td>84.6</td><td>0. 91</td>

<td>Example 3</td><td>140</td><td>93. 1</td><td>excellent</td><td>85. 2</td><td>0. 94</td>

[0050] Table 4 lists the water resistance and anti-oil effect, acid and alkali resistance coefficient and permeability of the coating in Examples 1-3 after curing on the base surface of the sintered artificial stone:

[0051] Table 4:

[0052]

<td></td><td>Water contact angle/°:</td><td>Water resistance K/%</td><td>Anti-greasy effect</td><td>Acid and alkali resistance coefficient/%</td><td>Penetration depth/ mm</td>

<td>Example 1</td><td>138</td><td>94.6</td><td>excellent</td><td>7&amp; 8</td><td>0.65</td>

<td>Example 2</td><td>145</td><td>95. 3</td><td>excellent</td><td>80. 5</td><td>0, 72</td>

<td>Example 3</td><td>148</td><td>96. 1</td><td>excellent</td><td>82. 1</td><td>0. 74</td>

[0053] It can be seen from Table 1 to Table 4 that the present invention significantly improves the water resistance, antifouling performance, acid and alkali resistance of artificial stone, and has excellent permeability and film-forming properties, forming protection on the surface and inside of the stone. Floor.

[0054] Although the embodiments of the present invention have been disclosed as above, they are not limited to the applications listed in the embodiments. It can be applied to various fields suitable for the present invention. For those skilled in the art, Other modifications can be easily implemented, so the present invention is not limited without departing from the general concept defined by the claims and equivalent scope

In specific details.