CN108047940B - High-permeability high-weather-resistance environment-friendly type silicon-fluorine emulsion and preparation method thereof - Google Patents
High-permeability high-weather-resistance environment-friendly type silicon-fluorine emulsion and preparation method thereof Download PDFInfo
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- CN108047940B CN108047940B CN201711419999.3A CN201711419999A CN108047940B CN 108047940 B CN108047940 B CN 108047940B CN 201711419999 A CN201711419999 A CN 201711419999A CN 108047940 B CN108047940 B CN 108047940B
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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D183/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Coating compositions based on derivatives of such polymers
- C09D183/04—Polysiloxanes
- C09D183/08—Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen, and oxygen
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- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
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- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/16—Antifouling paints; Underwater paints
- C09D5/1656—Antifouling paints; Underwater paints characterised by the film-forming substance
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
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- C08K2003/2241—Titanium dioxide
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
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- C08K9/00—Use of pretreated ingredients
- C08K9/04—Ingredients treated with organic substances
- C08K9/06—Ingredients treated with organic substances with silicon-containing compounds
Abstract
The invention discloses a high-permeability high-weather-resistance environment-friendly silicon-fluorine emulsion which comprises 30-50 wt% of micromolecule silane, 10-20 wt% of fluoroalkyl siloxane, 0.5-3 wt% of fluorosilane modified titanium dioxide, 1-3 wt% of composite organic silicon emulsifier, 0.5-1.5 wt% of fluorine-containing surfactant, 3-5 wt% of silica sol and the balance of deionized water. In addition, the preparation method of the high-permeability, high-weather-resistance and environment-friendly type 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 excellent permeability and 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 high-permeability high-weather-resistance environment-friendly type 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 environment-friendly type silicon-fluorine emulsion which is suitable for the surface of the porous base material and has high permeability and high weather resistance. The invention also aims to provide a preparation method of the high-permeability, high-weather-resistance and environment-friendly type silicon-fluorine emulsion.
The purpose of the invention is realized by the following technical scheme:
the invention provides a high-permeability high-weather-resistance environment-friendly type silicon-fluorine emulsion, which comprises the following components: 30-50 wt% of micromolecular silane, 10-20 wt% of fluoroalkyl siloxane, 0.5-3 wt% of fluorosilane modified titanium dioxide, 1-3 wt% of composite organic silicon emulsifier, 0.5-1.5 wt% of fluorine-containing surfactant, 3-5 wt% of silica sol and the balance of deionized water; wherein the content of the first and second substances,
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, n and m are integers, and R is saturated alkane with 1-6 carbon atoms;
the structural formula of the fluoroalkyl siloxane is as follows: rf-(CH2)n-Si(OR1)3Wherein R is1Is methyl or ethyl, RfIs CmF2m+1Or C6F5N is more than or equal to 0 and less than or equal to 3, m is more than or equal to 1 and less than or equal to 13, and n and m are integers.
Furthermore, the particle size of the fluorosilane modified titanium dioxide is 10-100 nm.
Further, the composite organic silicon 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 above scheme, the fluorine-containing surfactant of the present invention is one or a combination of an anionic fluorocarbon surfactant, a cationic fluorocarbon surfactant, a zwitterionic fluorocarbon surfactant, a nonionic fluorocarbon surfactant, and a silicon-containing fluorocarbon surfactant. 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-permeability high-weather-resistance environment-friendly type silicon-fluorine emulsion provided by the invention comprises the following steps:
(1) preparation of silane emulsions
Uniformly mixing the micromolecular silane, a composite organic silicon emulsifier and part of deionized water to obtain a silane emulsion;
(2) preparation of fluoroalkyl siloxane emulsions
Uniformly mixing the fluoroalkyl siloxane with a fluorine-containing surfactant and the rest of deionized water to obtain fluoroalkyl siloxane emulsion;
(3) and uniformly mixing the silane emulsion and the fluoroalkyl siloxane emulsion, and uniformly mixing the mixture with silica sol and fluoroalkyl silane modified titanium dioxide to obtain the high-permeability, high-weather-resistance and environment-friendly type silicon-fluorine emulsion.
Further, in the step (1) of the preparation method of the present invention, the composite silicone emulsifier is added in two times, that is:
uniformly mixing the micromolecular silane and 50-70 wt% of composite organic silicon emulsifier by stirring for 30-90 min at 25-60 ℃ to prepare solution A;
adding the rest of the composite organic silicon emulsifier into 30-70 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) of the preparation method of the present invention, the fluorosurfactant is added in two times, that is:
uniformly mixing the fluoroalkyl siloxane with 50-70 wt% of fluorine-containing surfactant at 25-60 ℃ for 30-90 min to obtain a liquid C;
adding the rest fluorine-containing surfactant into the rest deionized water, and stirring for 30-90 min at 25-60 ℃ to prepare solution D;
and then, dripping the solution C into the solution D under the stirring state, adjusting the pH value of a solution system to 5-7 after finishing dripping, and stirring for 30-90 min under the conditions of 25-60 ℃ and the stirring speed of 1000-3000 r/min to prepare the fluoroalkyl siloxane emulsion.
Further, in the step (3), the silane emulsion and the fluoroalkyl siloxane emulsion are stirred for 30-90 min at 25-60 ℃, the stirring condition is maintained, and the silica sol and the fluoroalkyl silane modified titanium dioxide are sequentially added and uniformly mixed.
The invention has the following beneficial effects:
(1) the high-permeability high-weather-resistance environment-friendly type silicon-fluorine emulsion has excellent high and low temperature resistance, aging resistance and hydrophobicity (the contact angle of water is 137-146 degrees) of an 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, so that the coating has good pollution resistance.
(2) The high-permeability high-weather-resistance environment-friendly type silicon-fluorine emulsion disclosed by the invention is composed of micromolecular compounds, has good permeability even in high-grade concrete products (C50 concrete, the penetration depth reaches 4.5-5.4 mm), can effectively penetrate into the base material and is combined with the base material by chemical bonds, and a net-shaped three-dimensional waterproof oil-proof antifouling layer taking an organosilicon material and a fluorocarbon chain as main materials is formed on the surface of the base material and at a certain depth, so that water can be prevented from entering the interior for a long time and effectively, and pollution is avoided; meanwhile, a closed film cannot be generated on the surface, so that the appearance color and the air permeability of the base material are not influenced.
(3) The fluorosilane modified titanium dioxide has better dispersibility and compatibility in the 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.
(4) The silica sol is doped in the system and forms a silica-shaped network structure after curing, so that the coating is acid-base resistant and the coating performance is improved.
(5) The high-permeability, high-weather-resistance and environment-friendly type silicon-fluorine emulsion disclosed by the invention 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 embodiment of the invention provides a high-permeability, high-weather-resistance and environment-friendly type silicon-fluorine emulsion, which is a composite system mainly formed by micromolecular silane, fluoroalkyl siloxane, fluorosilane modified titanium dioxide, a composite organic silicon emulsifier, a fluorine-containing surfactant and silica sol. Wherein the content of the first and second substances,
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 embodiment of the invention relates to a high-permeability, high-weather-resistant and environment-friendly type silicon-fluorine emulsion, which comprises the following steps:
(1) preparation of silane emulsions
Weighing 30g of isobutyl trimethoxy silane and 0.6g of composite organic silicon emulsifier (OP10 and NP10 are 0.3g respectively), pouring into a container, heating in a water bath to 25 ℃, and stirring at the speed of 1000r/min for 30min to prepare solution A;
weighing 0.4g of composite organic silicon emulsifier (OP10 and NP10 are 0.2g respectively) and adding into 19g 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) preparation of fluoroalkyl siloxane emulsions
Weighing 10g of tridecafluorooctyl trimethoxysilane and 0.25g of perfluoroalkyl polyether, pouring into a container, heating in water bath to 25 ℃, and stirring at the speed of 1000r/min for 30min to obtain solution C;
weighing 0.25g of perfluoroalkyl polyether, adding into 36g of deionized water, and stirring at 25 ℃ at the speed of 1000r/min for 30min to obtain solution D;
then, slowly dripping the solution C into the solution D 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 fluoroalkyl siloxane emulsion;
(3) mixing the silane emulsion with the fluoroalkyl siloxane emulsion, and stirring at 25 ℃ and 1000r/min for 30 min; keeping the stirring condition, sequentially adding 3g of silica sol and 0.5g of fluorosilane modified titanium dioxide, and uniformly mixing to obtain the high-permeability high-weather-resistance environment-friendly silicon-fluorine emulsion.
Example two:
the embodiment of the invention relates to a high-permeability, high-weather-resistant and environment-friendly type silicon-fluorine emulsion, which comprises the following steps:
(1) preparation of silane emulsions
Weighing 40g of isobutyl triethoxysilane and 2g of composite organic silicon emulsifier (1 g of each of sodium dodecyl sulfate and span 20), pouring into a container, heating in water bath to 35 ℃, and stirring at 1500r/min for 40min to obtain solution A;
weighing 1g of composite organic silicon emulsifier (0.5 g of each of sodium dodecyl sulfate and span 20) and adding into 22g of deionized water, and stirring at the temperature of 30 ℃ at the speed of 2000r/min for 35min 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 60min at 35 ℃ and the stirring speed of 1000r/min to prepare a silane emulsion;
(2) preparation of fluoroalkyl siloxane emulsions
Weighing 13g of tridecafluorooctyltriethoxysilane and 0.5g of perfluoroalkyl betaine, pouring into a container, heating in water bath to 40 ℃, and stirring at the speed of 2000r/min for 60min to obtain solution C;
weighing 0.5g of perfluoroalkyl betaine, adding into 15g of deionized water, and stirring at 45 ℃ at a speed of 1500r/min for 30min to obtain solution D;
then, slowly dripping the solution C into the solution D at the 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 40min at the temperature of 35 ℃ and the stirring speed of 1500r/min to prepare fluoroalkyl siloxane emulsion;
(3) mixing the silane emulsion with the fluoroalkyl siloxane emulsion, and stirring at 35 ℃ and 1500r/min for 70 min; keeping the stirring condition, sequentially adding 4g of silica sol and 2g of fluorosilane modified titanium dioxide, and uniformly mixing to obtain the high-permeability high-weather-resistance environment-friendly silicofluoride emulsion.
Example three:
the embodiment of the invention relates to a high-permeability, high-weather-resistant and environment-friendly type silicon-fluorine emulsion, which comprises the following steps:
(1) preparation of silane emulsions
Weighing 50g of octyl triethoxysilane and 1g of composite organic silicon emulsifier (0.5 g of peregal 15 and AEO9 respectively), pouring into a container, heating in water bath to 45 ℃, and stirring at 1500r/min for 90min to obtain solution A;
weighing 0.5g of composite organic silicon emulsifier (0.25 g of peregal 15 and AEO9 respectively) and adding into 14g of deionized water, and stirring at 35 ℃ at 2000r/min for 70min 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 60min at the temperature of 60 ℃ and the stirring speed of 1500r/min to prepare a silane emulsion;
(2) preparation of fluoroalkyl siloxane emulsions
Weighing 15g of pentadecafluorononyl trimethoxy silane and 1g of perfluorooctyl sulfonyl fluoride, pouring into a container, heating in a water bath to 25 ℃, and stirring at the speed of 2000r/min for 80min to obtain solution C;
weighing 0.5g of perfluorooctyl sulfonyl fluoride, adding into 10.5g of deionized water, and stirring at the temperature of 45 ℃ at the speed of 1500r/min for 40min to prepare solution D;
then, slowly dripping the solution C into the solution D 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 40min at the temperature of 25 ℃ and the stirring speed of 3000r/min to prepare fluoroalkyl siloxane emulsion;
(3) mixing the silane emulsion with the fluoroalkyl siloxane emulsion, and stirring at 30 ℃ and 1500r/min for 30 min; keeping the stirring condition, sequentially adding 5g of silica sol and 2.5g of fluorosilane modified titanium dioxide, and uniformly mixing to obtain the high-permeability high-weather-resistance environment-friendly silicon-fluorine emulsion.
Example four:
the embodiment of the invention relates to a high-permeability, high-weather-resistant and environment-friendly type silicon-fluorine emulsion, which comprises the following steps:
(1) preparation of silane emulsions
Weighing 50g of octyl trimethoxy silane and 1g of composite organic silicon emulsifier (0.5 g of Tween40 and OP13 respectively), pouring into a container, heating in water bath to 45 ℃, and stirring at the speed of 1500r/min for 70min to obtain solution A;
weighing 1g of composite organic silicon emulsifier (0.5 g of Tween40 and OP13 respectively) and adding into 13g of deionized water, and stirring at the temperature of 35 ℃ at the speed of 1800r/min for 70min to prepare liquid 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 80min at the temperature of 35 ℃ and the stirring speed of 1500r/min to prepare a silane emulsion;
(2) preparation of fluoroalkyl siloxane emulsions
Weighing 17g of pentadecafluorononyl triethoxysilane and 1g of perfluoroalkyl polyether phosphate, pouring into a container, heating in water bath to 40 ℃, and stirring at the speed of 1000r/min for 40min to obtain solution C;
weighing 0.5g of perfluoroalkyl polyether phosphate, adding into 10g of deionized water, and stirring at the temperature of 50 ℃ at the speed of 2000r/min for 30min to obtain solution D;
then, slowly dripping the solution C into the solution D at the 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 30min at the temperature of 45 ℃ and the stirring speed of 2000r/min to prepare fluoroalkyl siloxane emulsion;
(3) mixing the silane emulsion with the fluoroalkyl siloxane emulsion, and stirring at 50 ℃ and 2500r/min for 60 min; keeping the stirring condition, sequentially adding 3.5g of silica sol and 3g of fluorosilane modified titanium dioxide, and uniformly mixing to obtain the high-permeability high-weather-resistance environment-friendly silicofluoride emulsion.
Example five:
the embodiment of the invention relates to a high-permeability, high-weather-resistant and environment-friendly type silicon-fluorine emulsion, which comprises the following steps:
(1) preparation of silane emulsions
Weighing 40g of isobutyl triethoxysilane and 1.5g of composite organic silicon emulsifier (1 g of sodium dodecyl sulfate and 0.5g of NP10 emulsifier), pouring into a container, heating in water bath to 45 ℃, and stirring at 2000r/min for 40min to obtain solution A;
weighing 1.5g of composite organic silicon emulsifier (1 g of sodium dodecyl sulfate and 0.5g of NP10 emulsifier), adding into 20g of deionized water, and stirring at 35 deg.C at 1500r/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 1500 r/min; after the dropwise addition is finished, phosphoric acid is adopted to adjust the pH value of a solution system to be 5-7, and then stirring is carried out for 90min at the temperature of 60 ℃ and the stirring speed of 2200r/min, so as to prepare silane emulsion;
(2) preparation of fluoroalkyl siloxane emulsions
Weighing 20g of heptadecafluorodecyltrimethoxysilane and 1g of perfluoroalkyl acrylate, pouring into a container, heating in a water bath to 60 ℃, and stirring at the speed of 1500r/min for 80min to obtain solution C;
weighing 0.5g of perfluoroalkyl acrylate, adding into 11.5g of deionized water, and stirring at 45 ℃ at a speed of 1500r/min for 30min to obtain solution D;
then, slowly dripping the solution C into the solution D 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 50min at the temperature of 55 ℃ and the stirring speed of 1500r/min to prepare fluoroalkyl siloxane emulsion;
(3) mixing the silane emulsion with the fluoroalkyl siloxane emulsion, and stirring at 45 ℃ and 1500r/min for 40 min; keeping the stirring condition, sequentially adding 2.5g of silica sol and 1.5g of fluorosilane modified titanium dioxide, and uniformly mixing to obtain the high-permeability high-weather-resistance environment-friendly silicofluoride emulsion.
Example six:
the embodiment of the invention relates to a high-permeability, high-weather-resistant and environment-friendly type silicon-fluorine emulsion, which comprises the following steps:
(1) preparation of silane emulsions
Weighing 35g of octyl triethoxysilane and 1.5g of composite organic silicon emulsifier (1 g of OP10 emulsifier and 0.5g of peregal 15 emulsifier), pouring into a container, heating in water bath to 55 ℃, and stirring at 2500r/min for 60min to obtain solution A;
weighing 1g of composite organic silicon emulsifier (1 g of OP10 emulsifier and 0.5g of peregal 15 emulsifier), adding into 20g of deionized water, and stirring at 45 deg.C at 2500r/min for 40min 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 70min at the temperature of 50 ℃ and the stirring speed of 1200r/min to prepare a silane emulsion;
(2) preparation of fluoroalkyl siloxane emulsions
Weighing 20g of heptadecafluorodecyltriethoxysilane and 1g of fluorinated polyether siloxane, pouring into a container, heating in water bath to 45 ℃, and stirring at the speed of 1500r/min for 70min to obtain solution C;
weighing 0.5g of fluorinated polyether siloxane, adding into 16g of deionized water, and stirring at the temperature of 45 ℃ at the speed of 1500r/min for 30min to prepare a solution D;
then, slowly dripping the solution C into the solution D 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 45min at the temperature of 55 ℃ and the stirring speed of 1500r/min to prepare fluoroalkyl siloxane emulsion;
(3) mixing the silane emulsion with the fluoroalkyl siloxane emulsion, and stirring at 45 ℃ and 1500r/min for 40 min; keeping the stirring condition, sequentially adding 3g of silica sol and 2g of fluorosilane modified titanium dioxide, and uniformly mixing to obtain the high-permeability high-weather-resistance environment-friendly silicofluoride emulsion.
The test results of the protective performance of the high-permeability, high-weather-resistance and environment-friendly type silicon-fluorine emulsion prepared by the embodiments of the invention are shown in table 1.
TABLE 1 protective Properties of high-permeability, high-weatherability and environment-friendly type silicon fluorine emulsion prepared by the embodiments of the present invention
Claims (6)
1. A high-permeability high-weather-resistance environment-friendly type silicon-fluorine emulsion is characterized by comprising the following components: 30-50 wt% of micromolecular silane, 10-20 wt% of fluoroalkyl siloxane, 0.5-3 wt% of fluorosilane modified titanium dioxide with the particle size of 10-100 nm, 1-3 wt% of composite organic silicon emulsifier, 0.5-1.5 wt% of fluorine-containing surfactant, 3-5 wt% of silica sol and the balance of deionized water; wherein the content of the first and second substances,
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, n and m are integers, and R is saturated alkane with 1-6 carbon atoms;
the structural formula of the fluoroalkyl siloxane is as follows: rf-(CH2)n-Si(OR1)3Wherein R is1Is methyl or ethyl, RfIs CmF2m+1Or C6F5N is more than or equal to 0 and less than or equal to 3, m is more than or equal to 1 and less than or equal to 13, and n and m are integers;
the fluorine-containing surfactant is one or the combination of an anionic fluorocarbon surfactant, a cationic fluorocarbon surfactant, a zwitterionic fluorocarbon surfactant, a non-ionic fluorocarbon surfactant and a silicon-containing fluorocarbon surfactant;
the silica sol is nano SiO with the particle size of 10-100 nm and the concentration of 30 percent2An aqueous dispersion;
the penetration depth of the silicon-fluorine emulsion in C50 concrete is 4.9-5.4 mm.
2. The high-permeability, high-weatherability and environment-friendly type silicon-fluorine emulsion according to claim 1, wherein: the composite organic silicon 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 preparation method of the high-permeability, high-weatherability and environment-friendly type silicon-fluorine emulsion as claimed in claim 1 or 2, which is characterized by comprising the following steps:
(1) preparation of silane emulsions
Uniformly mixing the micromolecular silane, a composite organic silicon emulsifier and part of deionized water to obtain a silane emulsion;
(2) preparation of fluoroalkyl siloxane emulsions
Uniformly mixing the fluoroalkyl siloxane with a fluorine-containing surfactant and the rest of deionized water to obtain fluoroalkyl siloxane emulsion;
(3) and uniformly mixing the silane emulsion and the fluoroalkyl siloxane emulsion, and uniformly mixing the mixture with silica sol and fluoroalkyl silane modified titanium dioxide to obtain the high-permeability, high-weather-resistance and environment-friendly type silicon-fluorine emulsion.
4. The preparation method of the high-permeability, high-weatherability and environment-friendly type silicon-fluorine emulsion according to claim 3, which is characterized in that: in the step (1), the compound organic silicon emulsifier is added twice, namely:
uniformly mixing the micromolecular silane and 50-70 wt% of composite organic silicon emulsifier by stirring for 30-90 min at 25-60 ℃ to prepare solution A;
adding the rest of the composite organic silicon emulsifier into 30-70 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.
5. The preparation method of the high-permeability, high-weatherability and environment-friendly type silicon-fluorine emulsion according to claim 3 or 4, characterized in that: in the step (2), the fluorine-containing surfactant is added twice, namely:
uniformly mixing the fluoroalkyl siloxane with 50-70 wt% of fluorine-containing surfactant at 25-60 ℃ for 30-90 min to obtain a liquid C;
adding the rest fluorine-containing surfactant into the rest deionized water, and stirring for 30-90 min at 25-60 ℃ to prepare solution D;
and then, dripping the solution C into the solution D under the stirring state, adjusting the pH value of a solution system to 5-7 after finishing dripping, and stirring for 30-90 min under the conditions of 25-60 ℃ and the stirring speed of 1000-3000 r/min to prepare the fluoroalkyl siloxane emulsion.
6. The preparation method of the high-permeability, high-weatherability and environment-friendly type silicon-fluorine emulsion according to claim 3, which is characterized in that: in the step (3), after the silane emulsion and the fluoroalkyl siloxane emulsion are stirred for 30-90 min at 25-60 ℃, keeping the stirring condition, and sequentially adding silica sol and fluoroalkyl silane modified titanium dioxide to be uniformly mixed.
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| CN108841324B (en) * | 2018-06-26 | 2020-06-05 | 王春林 | Halogen-free flame-retardant silane water-based paint and preparation and application thereof |
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