CN108047938B - High-antifouling-performance silicon-fluorine emulsion and preparation method thereof - Google Patents
High-antifouling-performance silicon-fluorine emulsion and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a high antifouling silicon-fluorine emulsion, which comprises the following components: 30-50 wt% of micromolecule silane, 5-15 wt% of fluororesin emulsion, 0.5-3 wt% of fluorosilane modified titanium dioxide, 1-3 wt% of composite emulsifier, 0.5-2 wt% of light stabilizer, 1-3 wt% of silane coupling agent, 3-5 wt% of silica sol and the balance of deionized water. In addition, a preparation method of the high antifouling silicon-fluorine emulsion is also disclosed. The invention not only ensures that the product has good and lasting hydrophobic, oleophobic and antifouling functions, but also ensures that the product has better permeability and excellent weather resistance, and simultaneously does not change the appearance and the air permeability of the surface of the base material; and the preparation process is simple, safe, environment-friendly and free of peculiar smell, and can be widely used for water resistance and stain resistance of substrates such as concrete, stone, GRC and the like.
Description
Technical Field
The invention relates to the technical field of surface protection of base materials, in particular to a high antifouling silicon-fluorine emulsion and a preparation method thereof.
Background
Concrete, stone, GRC and the like are all porous materials, various capillaries, pores and the like exist in the concrete, the stone, the GRC and the like, particularly, the surfaces of the concrete, the stone, the GRC and the like are rough, and dust, pollutants, automobile exhaust and the like in the atmosphere are deposited on the surfaces of substrates. With the help of water, contaminants can follow capillaries, pores, etc. into the substrate and leave stains on the surface. This not only affects the appearance, but also makes removal difficult, especially for decorative fair-faced concrete or GRC elements where surface soil resistance is of particular importance.
The most effective method of surface protection is to prevent the substrate from contacting water and other harmful substances, and specifically, to form a durable protective layer on the surface of the substrate and at a certain depth. In recent years, silicone materials have been widely used for surface protection of substrates because of their excellent hydrophobicity and high-temperature aging resistance. However, the formed protective layer still cannot realize a durable surface antifouling effect, because the molecular chain segment of the surface protective layer is still damaged by ultraviolet rays under long-term outdoor sunlight irradiation, so that the surface hydrophobic property is reduced, and the surface antifouling capacity is reduced; in addition, in the surface protection system in the prior art, organic solvents are mostly used, so that the defects and hazards of odor, toxicity, volatility, flammability and explosiveness are caused.
Disclosure of Invention
The invention aims to overcome the defects of the prior art, and provides the high antifouling silicon-fluorine emulsion suitable for the surface of the porous base material, which does not change the surface color of the base material after being coated or sprayed on the surface of the base material, has lasting hydrophobic and oleophobic properties, has excellent antifouling effect, is safe to use, environment-friendly and free from peculiar smell. Another object of the present invention is to provide a method for preparing the above-mentioned silicone-fluorine emulsion having high antifouling property.
The purpose of the invention is realized by the following technical scheme:
the invention provides a high antifouling silicon-fluorine emulsion, which comprises the following components: 30-50 wt% of micromolecular silane, 5-15 wt% of fluororesin emulsion, 0.5-3 wt% of fluorosilane modified titanium dioxide, 1-3 wt% of composite emulsifier, 0.5-2 wt% of light stabilizer, 1-3 wt% of silane coupling agent, 3-5 wt% of silica sol and the balance of deionized water; wherein,
the structural formula of the micromolecular silane is CnH2n+1-Si(OR1)m-R3-mWherein R is1Is methyl or ethyl, n is more than or equal to 4 and less than or equal to 8, m is more than or equal to 1 and less than or equal to 3, and n and m are integers; r is C1-6 saturated alkane.
Furthermore, the particle size of the fluorosilane modified titanium dioxide is 10-100 nm.
Further, the composite emulsifier is formed by compounding at least two of alkylphenol ethoxylates OP series, sodium dodecyl sulfate, sorbitan fatty acid ester span series, fatty alcohol polyoxyethylene ether peregal series, AEO series, nonylphenol polyoxyethylene ether NP series and sorbitan fatty acid ester polyoxyethylene ether Tween series.
In the scheme, the light stabilizer is o-hydroxybenzophenone, benzotriazole, salicylate, triazine, substituted acrylonitrile, piperidine derivative and imidazolone derivativeThe silane coupling agent is one or a combination of gamma-aminopropyl triethoxysilane, vinyl triethoxysilane, gamma-methacryloxypropyl trimethoxysilane, N- β (aminoethyl) -gamma-aminopropyl trimethoxysilane, gamma-methacryloxypropyl trimethoxysilane and gamma- (2, 3-epoxypropoxy) propyl trimethoxysilane, and the silica sol is nano SiO with the particle size of 10-100 nm and the concentration of 30 percent2An aqueous dispersion.
The other purpose of the invention is realized by the following technical scheme:
the preparation method of the high antifouling silicon-fluorine emulsion provided by the invention comprises the following steps:
(1) preparation of silane emulsions
Uniformly mixing the micromolecule silane with a silane coupling agent, a composite emulsifier and part of deionized water to obtain a silane emulsion;
(2) and uniformly mixing the silane emulsion and the fluororesin emulsion, and uniformly mixing the mixture with silica sol, fluorosilane modified titanium dioxide, a light stabilizer and the residual deionized water to obtain the high antifouling performance silicofluoride emulsion.
Further, in the step (1) of the preparation method of the present invention, the compound emulsifier is added in two times, that is:
stirring the micromolecular silane, the silane coupling agent and 50-80 wt% of composite emulsifier at 25-60 ℃ for 30-90 min, and uniformly mixing to obtain solution A;
adding the rest of the composite emulsifier into 50-75 wt% of deionized water, and stirring for 30-90 min at 25-60 ℃ to prepare a solution B;
and then, dropwise adding the solution A into the solution B under a stirring state, adjusting the pH value of a solution system to 5-7 after dropwise adding is completed, and stirring for 30-90 min at the temperature of 25-60 ℃ and the stirring speed of 1000-3000 r/min to prepare the silane emulsion.
Further, in the step (2), after the silane emulsion and the fluororesin emulsion are stirred for 30-90 min at 25-60 ℃, the stirring condition is maintained, and the silica sol, the fluorosilane modified titanium dioxide, the light stabilizer and the residual deionized water are sequentially added and uniformly mixed.
The invention has the following beneficial effects:
(1) the high antifouling silicofluoride emulsion has excellent high and low temperature resistance, aging resistance and hydrophobicity of the organosilicon material; meanwhile, due to the introduction of the organic fluorine material, the coating has excellent performances of oil resistance, solvent resistance, chemical stability, lower surface energy and the like, and pollutants such as water, oil and the like are difficult to adhere to the surface or permeate into the substrate (the water contact angle is 106-112 degrees, and the penetration depth is 3.4-4.4 mm), so that the coating has good pollution resistance.
(2) The fluorosilane modified titanium dioxide has better dispersibility and compatibility in the formula system, and the introduction of the fluorosilane modified titanium dioxide endows the coating with excellent ultraviolet resistance, further improves the aging resistance of the coating, and is beneficial to improving the hydrophobic and oleophobic properties of the coating. In addition, the introduction of the fluorosilane modified titanium dioxide ensures that the coating has photocatalytic activity, can degrade organic pollutants in a photocatalytic manner, has a certain sterilization function, and can effectively inhibit the growth of microorganisms, moss and the like.
(3) The silica sol and the fluororesin emulsion are mixed and dissolved, so that the fluororesin emulsion is uniformly distributed in gaps of the silicon-oxygen-silicon inorganic coating, residual hydrophilic groups in the inorganic coating are shielded, the coating has certain elasticity, and the formed coating has the characteristics of both inorganic coating and organic coating and makes up for the defects of the inorganic coating and the organic coating. After the silica sol is solidified, a silica-shaped network structure is formed, and the coating is acid-base resistant, so that the coating performance is improved.
(4) The high antifouling silicon-fluorine emulsion has the advantages of low price and wide applicability; the performances of oil resistance, low surface energy, aging resistance and the like of the organic fluorine function are finally embodied by the fluororesin emulsion, so the unit cost of the system is lower, and the system can be suitable for most of the engineering cost requirements.
(5) The high antifouling silicon-fluorine emulsion has stable performance and good storage stability, and does not have obvious precipitation or agglomeration after being placed at room temperature for 12 months.
(6) The invention has simple production process and convenient use; and the product system is emulsion type, and does not need organic solvent, thereby avoiding the problems of odor, toxicity, volatility, flammability, explosive hazard and the like caused by using organic solvent, being safe, environment-friendly and free from peculiar smell, and being widely applied to surface protection of concrete, stone, GRC and the like.
The present invention will be described in further detail with reference to examples.
Detailed Description
The invention provides a high antifouling silicon-fluorine emulsion, which is a composite system mainly formed by micromolecular silane, fluorine resin emulsion, fluorine silane modified titanium dioxide, a composite emulsifier, a light stabilizer, a silane coupling agent and silica sol. Wherein,
fluororesin emulsion, can be prepared by fluoroolefin, vinyl compound and vinyl siloxane monomer through emulsion polymerization; or taking the fluorine-containing polymer emulsion as a seed, and carrying out emulsion copolymerization on the vinyl siloxane monomer and other monomers to obtain the product; or the side chain fluorine-containing acrylic emulsion.
The fluorosilane modified titanium dioxide is prepared by the method disclosed in patent No. 201410669702.9, namely, titanium dioxide sol solution is prepared by hydrolysis titanium alkoxide synthesis; then grafting fluorine modified alkyl silane on the surface of the titanium dioxide to obtain the fluorosilane modified titanium dioxide nano material. In the embodiment of the invention, the fluorosilane modified titanium dioxide is ground to a particle size of 10-100 nm.
The silica sol is nano SiO with the particle size of 10-100 nm and the concentration of 30 percent2An aqueous dispersion.
The first embodiment is as follows:
the preparation method of the high antifouling silicon-fluorine emulsion comprises the following steps:
(1) preparation of silane emulsions
Weighing 30g of isobutyl triethoxysilane, 1g of gamma-methacryloxypropyl trimethoxysilane and 0.6g of composite emulsifier (OP10 and NP10 are 0.3g respectively), pouring into a container, heating in water bath to 25 ℃, and stirring at 1000r/min for 30min to obtain solution A;
weighing 0.4g of composite emulsifier (OP10 and NP10 are 0.2g respectively) and adding into 30g of deionized water, and stirring at 25 ℃ at the speed of 1000r/min for 30min to prepare solution B;
then, slowly dripping the solution A into the solution B at the speed of 0.1-0.3 mL/s under the stirring state of 1000 r/min; after the dropwise addition is finished, adjusting the pH value of a solution system to be 5-7 by using phosphoric acid, and then stirring for 30min at the temperature of 25 ℃ and the stirring speed of 1000r/min to prepare a silane emulsion;
(2) mixing the silane emulsion with 5g of fluororesin emulsion, and stirring at 25 ℃ and 1000r/min for 30 min; keeping the stirring condition, sequentially adding 3g of silica sol, 0.5g of fluorosilane modified titanium dioxide, 0.5g of light stabilizer (0.25 g of UV-9 and UV-P respectively) and 29g of deionized water, and uniformly mixing to obtain the high antifouling silicofluoride emulsion.
Example two:
the preparation method of the high antifouling silicon-fluorine emulsion comprises the following steps:
(1) preparation of silane emulsions
Weighing 35g of octyl triethoxysilane, 2g of gamma-aminopropyl triethoxysilane and 1g of composite emulsifier (0.5 g of sodium dodecyl sulfate and 0.5g of span20 respectively), pouring into a container, heating in water bath to 35 ℃, and stirring at 1500r/min for 40min to obtain solution A;
weighing 0.5g of composite emulsifier (0.25 g of each of sodium dodecyl sulfate and span 20) and adding into 28g of deionized water, and stirring at 35 ℃ at 1500r/min for 35min to obtain solution B;
then, slowly dripping the solution A into the solution B at the speed of 0.1-0.3 mL/s under the stirring state of 1500 r/min; after the dropwise addition is finished, adjusting the pH value of a solution system to be 5-7 by using phosphoric acid, and then stirring for 30min at the temperature of 35 ℃ and the stirring speed of 1500r/min to prepare a silane emulsion;
(2) mixing the silane emulsion with 7g of fluororesin emulsion, and stirring at 30 ℃ and 1300r/min for 35 min; keeping the stirring condition, and sequentially adding 4g of silica sol, 1.5g of fluorosilane modified titanium dioxide, 1g of light stabilizer (0.5 g of each of UV-531 and UV-327) and 20g of deionized water to uniformly mix to obtain the high antifouling silicofluoride emulsion.
Example three:
the preparation method of the high antifouling silicon-fluorine emulsion comprises the following steps:
(1) preparation of silane emulsions
Weighing 40g of isobutyl trimethoxy silane, 3g of vinyl triethoxy silane and 1g of composite emulsifier (0.5 g of peregal 15 and AEO9 respectively), pouring into a container, heating in water bath to 60 ℃, and stirring at the speed of 2000r/min for 40min to obtain solution A;
weighing 1g of composite emulsifier (0.5 g of peregal 15 and AEO9 respectively) and adding into 25g of deionized water, and stirring at 40 ℃ at 2200r/min for 30min to obtain solution B;
then, slowly dripping the solution A into the solution B at the speed of 0.1-0.3 mL/s under the stirring state of 1200 r/min; after the dropwise addition is finished, adjusting the pH value of a solution system to be 5-7 by using phosphoric acid, and then stirring for 40min at the temperature of 35 ℃ and the stirring speed of 1300r/min to prepare a silane emulsion;
(2) mixing the silane emulsion with 6.5g of fluororesin emulsion, and stirring at 45 ℃ and 1800r/min for 90 min; keeping the stirring condition, sequentially adding 5g of silica sol, 2g of fluorosilane modified titanium dioxide, 1.5g of light stabilizer (0.75 g of each of UV-317 and UV-326) and 15g of deionized water, and uniformly mixing to obtain the high antifouling silicofluoride emulsion.
Example four:
the preparation method of the high antifouling silicon-fluorine emulsion comprises the following steps:
(1) preparation of silane emulsions
Weighing 45g of octyl trimethoxy silane, 2.5g of N- β (aminoethyl) -gamma-aminopropyl trimethoxy silane and 2g of composite emulsifier (1 g of Tween40 and NP20 respectively), pouring into a container, heating in a water bath to 60 ℃, and stirring at the speed of 3000r/min for 90min to obtain solution A;
weighing 0.5g of composite emulsifier (Tween40 and NP20, 0.25g of each) and adding into 17.5g of deionized water, and stirring at the speed of 2500r/min for 60min at the temperature of 60 ℃ to prepare solution B;
then, slowly dripping the solution A into the solution B at the speed of 0.1-0.3 mL/s under the stirring state of 3000 r/min; after the dropwise addition is finished, adjusting the pH value of a solution system to be 5-7 by using phosphoric acid, and then stirring for 70min at the temperature of 50 ℃ and the stirring speed of 1500r/min to prepare a silane emulsion;
(2) mixing the silane emulsion with 13g of fluororesin emulsion, and stirring at 60 ℃ and 3000r/min for 80 min; keeping the stirring condition, and sequentially adding 4.5g of silica sol, 3g of fluorosilane modified titanium dioxide, 2g of light stabilizer TBS salicylic acid p-tert-butyl phenyl ester and 10g of deionized water to be uniformly mixed to obtain the high antifouling silicofluoride emulsion.
Example five:
the preparation method of the high antifouling silicon-fluorine emulsion comprises the following steps:
(1) preparation of silane emulsions
Weighing 50g of isobutyl triethoxysilane, 2g of gamma- (2, 3-epoxypropoxy) propyl trimethoxysilane and 2g of composite emulsifier (1 g of Tween20 and OP10 respectively), pouring into a container, heating in water bath to 45 ℃, and stirring at the speed of 2200r/min for 70min to obtain solution A;
weighing 1g of composite emulsifier (0.5 g of Tween20 and OP10 respectively) and adding into 11.5g of deionized water, and stirring at the temperature of 60 ℃ at the speed of 1800r/min for 60min to prepare solution B;
then, slowly dripping the solution A into the solution B at a speed of 0.1-0.3 mL/s under the stirring state of 2000 r/min; after the dropwise addition is finished, adjusting the pH value of a solution system to be 5-7 by using phosphoric acid, and then stirring for 45min at 40 ℃ and at a stirring speed of 3000r/min to prepare a silane emulsion;
(2) mixing the silane emulsion with 15g of fluororesin emulsion, and stirring at 40 ℃ and 1500r/min for 50 min; keeping the stirring condition, and sequentially adding 4g of silica sol, 2.5g of fluorosilane modified titanium dioxide, 2g of light stabilizer OPS p-octyl phenyl salicylate and 10g of deionized water to uniformly mix to obtain the high antifouling silicofluoride emulsion.
Example six:
the preparation method of the high antifouling silicon-fluorine emulsion comprises the following steps:
(1) preparation of silane emulsions
Weighing 38g of isobutyl triethoxysilane, 3g of gamma- (2, 3-epoxypropoxy) propyl trimethoxysilane and 2g of a composite emulsifier (OP10 and 1g of sodium dodecyl sulfate respectively), pouring into a container, heating in a water bath to 45 ℃, and stirring at the speed of 2500r/min for 40min to obtain solution A;
weighing 0.5g of composite emulsifier (OP10 and 0.25g of sodium dodecyl sulfate respectively) and adding into 27g of deionized water, and stirring at 45 ℃ at the speed of 1000r/min for 30min to obtain solution B;
then, slowly dripping the solution A into the solution B at the speed of 0.1-0.3 mL/s under the stirring state of 1000 r/min; after the dropwise addition is finished, adjusting the pH value of a solution system to be 5-7 by using phosphoric acid, and then stirring for 55min at the temperature of 40 ℃ and the stirring speed of 2500r/min to prepare a silane emulsion;
(2) mixing the silane emulsion with 12g of fluororesin emulsion, and stirring at 40 ℃ and 2000r/min for 90 min; keeping the stirring condition, sequentially adding 3g of silica sol, 3g of fluorosilane modified titanium dioxide, 1.5g of light stabilizer OPS p-octylphenyl salicylate and 10g of deionized water, and uniformly mixing to obtain the high antifouling silicofluoride emulsion.
The results of the measurements of the protective performance of the high anti-fouling silicone-fluorine emulsion prepared by the embodiments of the present invention are shown in table 1.
TABLE 1 protective Properties of highly soil resistant fluorosilicone emulsions prepared in accordance with the examples of the present invention
Claims (6)
1. The high antifouling silicon-fluorine emulsion is characterized by comprising the following components: 30-50 wt% of micromolecular silane, 5-15 wt% of fluororesin emulsion, 0.5-3 wt% of fluorosilane modified titanium dioxide with the particle size of 10-100 nm, 1-3 wt% of composite emulsifier, 0.5-2 wt% of light stabilizer, 1-3 wt% of silane coupling agent, 3-5 wt% of silica sol and the balance of deionized water; wherein,
the structural formula of the micromolecular silane is CnH2n+1-Si(OR1)m-R3-mWherein R is1Is methyl or ethyl, n is more than or equal to 4 and less than or equal to 8, m is more than or equal to 1 and less than or equal to 3, and n and m are integers; r is C1-6 saturated alkane;
the light stabilizer is one or the combination of o-hydroxybenzophenone, benzotriazole, salicylate, triazine, substituted acrylonitrile, piperidine derivative, imidazolone derivative and azacycloalkanone derivative;
the silica sol is nano SiO with the particle size of 10-100 nm and the concentration of 30 percent2An aqueous dispersion;
the water contact angle of the silicon-fluorine emulsion on the surface of the base material is 106-112 DEG, and the penetration depth is 3.4-4.4 mm.
2. The high stain resistant silicone-fluorine emulsion according to claim 1, wherein: the composite emulsifier is formed by compounding at least two of alkylphenol ethoxylates OP series, sodium dodecyl sulfate, sorbitan fatty acid ester span series, fatty alcohol polyoxyethylene ether peregal series, AEO series, nonylphenol polyoxyethylene ether NP series and sorbitan fatty acid ester polyoxyethylene ether Tween series.
3. The highly antifouling silicofluoride emulsion according to claim 1, wherein said silane coupling agent is one or a combination of γ -aminopropyltriethoxysilane, vinyltriethoxysilane, γ -methacryloxypropyltrimethoxysilane, N- β (aminoethyl) - γ -aminopropyltrimethoxysilane, γ -methacryloxypropyltrimethoxysilane, γ - (2, 3-epoxypropoxy) propyltrimethoxysilane.
4. A method for preparing the silicone-fluorine emulsion with high antifouling property according to any one of claims 1 to 3, characterized by comprising the steps of:
(1) preparation of silane emulsions
Uniformly mixing the micromolecule silane with a silane coupling agent, a composite emulsifier and part of deionized water to obtain a silane emulsion;
(2) and uniformly mixing the silane emulsion and the fluororesin emulsion, and uniformly mixing the mixture with silica sol, fluorosilane modified titanium dioxide, a light stabilizer and the residual deionized water to obtain the high antifouling performance silicofluoride emulsion.
5. The method for preparing a silicone-fluorine emulsion with high antifouling property according to claim 4, wherein: in the step (1), the compound emulsifier is added twice, namely:
stirring the micromolecular silane, the silane coupling agent and 50-80 wt% of composite emulsifier at 25-60 ℃ for 30-90 min, and uniformly mixing to obtain solution A;
adding the rest of the composite emulsifier into 50-75 wt% of deionized water, and stirring for 30-90 min at 25-60 ℃ to prepare a solution B;
and then, dropwise adding the solution A into the solution B under a stirring state, adjusting the pH value of a solution system to 5-7 after dropwise adding is completed, and stirring for 30-90 min at the temperature of 25-60 ℃ and the stirring speed of 1000-3000 r/min to prepare the silane emulsion.
6. The method for preparing a silicone-fluorine emulsion with high stain resistance according to claim 4 or 5, wherein: in the step (2), after the silane emulsion and the fluororesin emulsion are stirred for 30-90 min at 25-60 ℃, keeping the stirring condition, and sequentially adding silica sol, fluorosilane modified titanium dioxide, a light stabilizer and the rest deionized water to uniformly mix.
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| CN109593392B (en) * | 2018-12-14 | 2021-07-30 | 郑州大学 | A kind of preparation method and application of water-soluble amphiphobic modified material |
| CN109970977B (en) * | 2019-04-11 | 2021-09-07 | 山东省科学院新材料研究所 | A kind of titanium dioxide doped silicone resin micropowder and its preparation method and application |
| CN116159728B (en) * | 2022-12-29 | 2024-03-15 | 北京卫星制造厂有限公司 | Transparent wear-resistant antifouling barrier layer for artificial stone surface and preparation method thereof |
| CN116640505B (en) * | 2023-06-12 | 2024-06-21 | 中轻检验认证有限公司 | Functional photo-curable leather finishing agent system and preparation method and application thereof |
| CN118146717B (en) * | 2024-05-11 | 2024-07-09 | 成都阿多尼斯环保技术服务有限公司 | Stone curing agent and preparation method thereof |
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