CN111117328A - Preparation method of anti-fouling composition with photocatalytic performance - Google Patents
Preparation method of anti-fouling composition with photocatalytic performance Download PDFInfo
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- CN111117328A CN111117328A CN201811283721.2A CN201811283721A CN111117328A CN 111117328 A CN111117328 A CN 111117328A CN 201811283721 A CN201811283721 A CN 201811283721A CN 111117328 A CN111117328 A CN 111117328A
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- 239000000203 mixture Substances 0.000 title claims abstract description 42
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- 238000002360 preparation method Methods 0.000 title claims abstract description 23
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 115
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- 239000000377 silicon dioxide Substances 0.000 claims abstract description 60
- 239000004408 titanium dioxide Substances 0.000 claims abstract description 35
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 28
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- 238000002156 mixing Methods 0.000 claims abstract description 14
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical class C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000012153 distilled water Substances 0.000 claims abstract description 12
- 238000001914 filtration Methods 0.000 claims abstract description 9
- 239000008367 deionised water Substances 0.000 claims abstract description 7
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 7
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 claims abstract description 6
- 229910000077 silane Inorganic materials 0.000 claims abstract description 6
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- 238000000576 coating method Methods 0.000 claims description 60
- 239000011248 coating agent Substances 0.000 claims description 53
- 239000002105 nanoparticle Substances 0.000 claims description 19
- 239000000758 substrate Substances 0.000 claims description 16
- 238000004519 manufacturing process Methods 0.000 claims description 15
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 12
- 239000011521 glass Substances 0.000 claims description 10
- 238000010992 reflux Methods 0.000 claims description 9
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 8
- QUSNBJAOOMFDIB-UHFFFAOYSA-N Ethylamine Chemical compound CCN QUSNBJAOOMFDIB-UHFFFAOYSA-N 0.000 claims description 8
- 150000001875 compounds Chemical class 0.000 claims description 7
- 238000004042 decolorization Methods 0.000 claims description 7
- 239000003456 ion exchange resin Substances 0.000 claims description 7
- 229920003303 ion-exchange polymer Polymers 0.000 claims description 7
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 5
- 125000002843 carboxylic acid group Chemical group 0.000 claims description 5
- 125000003700 epoxy group Chemical group 0.000 claims description 5
- 125000000524 functional group Chemical group 0.000 claims description 5
- 229910052739 hydrogen Inorganic materials 0.000 claims description 5
- 239000001257 hydrogen Substances 0.000 claims description 5
- 239000011347 resin Substances 0.000 claims description 5
- 229920005989 resin Polymers 0.000 claims description 5
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 4
- 229910021529 ammonia Inorganic materials 0.000 claims description 4
- 238000001035 drying Methods 0.000 claims description 4
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- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 claims description 2
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 abstract description 5
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- STZCRXQWRGQSJD-GEEYTBSJSA-M methyl orange Chemical compound [Na+].C1=CC(N(C)C)=CC=C1\N=N\C1=CC=C(S([O-])(=O)=O)C=C1 STZCRXQWRGQSJD-GEEYTBSJSA-M 0.000 description 3
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
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- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- 229910010298 TiOSO4 Inorganic materials 0.000 description 1
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- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
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- KADRTWZQWGIUGO-UHFFFAOYSA-L oxotitanium(2+);sulfate Chemical compound [Ti+2]=O.[O-]S([O-])(=O)=O KADRTWZQWGIUGO-UHFFFAOYSA-L 0.000 description 1
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Images
Classifications
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- C—CHEMISTRY; METALLURGY
- 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
- 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
- C09D5/1606—Antifouling paints; Underwater paints characterised by the anti-fouling agent
- C09D5/1612—Non-macromolecular compounds
- C09D5/1618—Non-macromolecular compounds inorganic
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
- B01J21/08—Silica
-
- B01J35/39—
Abstract
The invention provides a preparation method of an anti-fouling composition with photocatalytic performance, which comprises the following steps: 1) the preparation method of the anatase phase titanium dioxide hydrosol comprises the following specific steps: i) dissolving titanyl sulfate in deionized water, ii) adding a proper amount of organic base, adjusting the pH value to 6-10, iii) filtering out the precipitate and washing with a large amount of distilled water to obtain a filter cake, iv) adding the filter cake into distilled water, and slowly dropwise adding a proper amount of H while stirring2O2Until the filter cake is completely dissolved; 2) treating hydrosol obtained by mixing two kinds of spherical silicon dioxide with different particle sizes by using hydrogenated ion exchange resin, and modifying by using epoxy silane to obtain silicon dioxide mixed hydrosol, and 3) mixing the anatase titanium dioxide hydrosol and the silicon dioxide mixed hydrosol according to a certain proportion. The anti-fouling composition with photocatalytic performance prepared by the method of the invention introduces TiO with photocatalytic performance2Component (b) ofAnd (4) antifouling performance.
Description
Technical Field
The invention relates to the field of anti-fouling, in particular to a preparation method of an anti-fouling composition with photocatalytic performance.
Background
At present, a plurality of anti-fouling coatings for organic pollutants or inorganic pollutants are available, for example, CN106398522 (silver dragon, etc.) discloses a SiO2 anti-fouling coating which has better anti-fouling performance, but because the coating utilizes electrostatic interaction to realize anti-fouling performance, the anti-fouling capability for organic pollutants is slightly poor, and US2008280103(UETSUKA, etc.) discloses a coating with high hardness and high adhesion, which is composed of titanium dioxide particles with different shapes, has good photocatalytic performance, can have better anti-fouling capability for organic pollutants, but has limited anti-fouling capability for inorganic pollutants.
CN103804966 (li jian sheng, etc.) discloses an antireflection coating with photocatalytic performance, which is composed of two parts, one part is titanium dioxide sol, and the other part is silicon dioxide sol formed by hydrolysis and condensation of silane, and the coating has high hydrophilicity, high photocatalytic activity and high light transmittance, but because the silicon dioxide particle sol is only single particle accumulation, the particle size is single and no surface treatment is performed, the anti-fouling capability to inorganic pollutants is limited.
In some fields, such as solar cells, architectural glass and the like, an anti-fouling coating is needed, which has better anti-fouling performance on organic pollutants and inorganic pollutants. CN101088606 (gold, etc.) discloses a self-cleaning coating with photocatalytic performance, which is composed of two parts, one part is titanium dioxide sol, and the other part is silica particle sol, and the coating is a transparent coating with high hydrophilicity and high photocatalytic activity, but the silica particle sol is only pure particle accumulation and is not subjected to surface treatment, so that the anti-fouling capability to inorganic pollutants is relatively limited.
Disclosure of Invention
The invention aims to provide a preparation method of an anti-fouling composition with photocatalytic performance, so as to meet the requirement of higher anti-fouling performance.
According to one aspect of the present invention, there is provided a process for the preparation of an anti-fouling composition having photocatalytic properties, comprising the steps of:
1) the preparation method of the anatase phase titanium dioxide hydrosol comprises the following specific steps:
i) the titanyl sulfate is dissolved in the deionized water,
ii) adding a proper amount of organic base, adjusting the pH value to 6-10,
iii) filtering off the precipitate to obtain a filter cake,
iv) adding the filter cake into distilled water, and slowly dropwise adding a proper amount of H while stirring2O2Stopping stirring after the filter cake is completely dissolved;
2) treating hydrosol obtained by mixing two kinds of spherical silicon dioxide with different particle sizes by using hydrogenated ion exchange resin, and modifying by using epoxy silane to obtain silicon dioxide mixed hydrosol, wherein the method comprises the following specific steps:
i) mixing a first group of spherical silica nanoparticles with an average diameter of less than 20nm and a second group of spherical silica nanoparticles with an average diameter of 20nm to 120nm in a certain proportion, wherein the weight ratio of the first group of silica nanoparticles to the second group of spherical silica nanoparticles is at least 1.5 to 1,
ii) adding a proper amount of hydrogen type ion exchange resin, stirring to adjust the pH value to be less than 4,
iii) filtering off the exchange resin,
iv) dropping 0.1 to 5 wt.% of an alkoxysilane compound containing a single terminal alkoxysilane group and a single terminal functional group selected from a carboxylic acid group or an epoxy group, based on 100 wt.% of the total weight of the silica hydrosol, and stirring at room temperature for at least 1h,
3) and mixing the anatase titanium dioxide hydrosol and the silicon dioxide mixed hydrosol according to a certain proportion to obtain the anti-fouling composition with photocatalytic performance.
According to some embodiments of the present invention, the titanium dioxide hydrosol of the anatase phase is prepared by adding a suitable amount of organic base to adjust the pH to 7-9.
According to certain embodiments of the invention, the organic base is selected from one or more of the following organic bases: ammonia, ethylamine and triethylamine.
According to some embodiments of the present invention, the precipitate is filtered and washed with distilled water to remove sulfate and organic base from the surface of the precipitate.
According to certain embodiments of the present invention, the titanium dioxide hydrosol obtained by the preparation is heated and refluxed for not more than 48 hours to obtain the titanium dioxide sol.
According to certain embodiments of the present invention, the titanium dioxide hydrosol obtained by the preparation method is heated and refluxed for 3h to 12h to obtain the titanium dioxide sol.
According to certain embodiments of the present invention, the titanium dioxide hydrosol obtained by the preparation method is heated and refluxed for 5h to 7h to obtain the titanium dioxide sol.
According to another aspect of the present invention, there is provided an anti-fouling composition prepared according to any of the preparation methods described herein.
According to another aspect of the present invention, there is provided an anti-fouling coating applied on a substrate and dried according to the anti-fouling composition.
According to certain embodiments of the invention, the substrate is glass.
According to certain embodiments of the invention, the substrate is white glass.
According to certain embodiments of the invention, the coating method is selected from one or more of the following: knife coating, wiping, brushing, dipping, spraying, and rolling.
According to some embodiments of the invention, the anti-fouling coating has a good inorganic anti-fouling performance, as indicated by Δ H less than or equal to 5% after ash shaking experiments;
according to some embodiments of the present invention, the anti-fouling coating has good organic anti-fouling performance, which is characterized by a decolorization rate of greater than or equal to 60% after a decolorization test,
according to certain embodiments of the present invention, the anti-smudge coating is applied to glass with good optical clarity, as indicated by a refractive index between 1.40 and 1.70.
The above summary is not intended to describe each disclosed embodiment of every implementation of the present invention. The features and advantages of the above and further embodiments of the present invention will become more apparent by describing in detail exemplary embodiments thereof with reference to the attached drawings.
Drawings
FIG. 1 shows TiO before and after heat treatment2XRD profile of the sol.
Detailed Description
It is to be understood that other various embodiments can be devised and modified by those skilled in the art in light of the teachings herein without departing from the scope or spirit of the invention. The following detailed description is, therefore, not to be taken in a limiting sense.
Unless otherwise indicated, all numbers expressing feature sizes, quantities, and physical characteristics used in the specification and claims are to be understood as being modified in all instances by the term "about". Accordingly, unless indicated to the contrary, the numerical parameters set forth in the foregoing specification and attached claims are approximations that can be suitably varied by those skilled in the art in seeking to obtain the desired properties utilizing the teachings disclosed herein. The use of numerical ranges by endpoints includes all numbers within that range and any range within that range, for example, 1, 2, 3, 4, and 5 includes 1, 1.1, 1.3, 1.5, 2, 2.75, 3, 3.80, 4, and 5, and the like.
The invention provides a preparation method of an anti-fouling composition with photocatalytic performance, which comprises the following steps:
1) the preparation method of the anatase phase titanium dioxide hydrosol comprises the following specific steps:
i) the titanyl sulfate is dissolved in the deionized water,
ii) adding organic alkali, adjusting the pH value to 6-10,
iii) filtering off the precipitate to obtain a filter cake,
iv) the filter cake is poured into distilled water, and H is added in an amount of 30 wt.%2O2Stirring the aqueous solution, and stopping stirring until the filter cake is completely dissolved, e.g. H2O2Insufficient, the filter cake is not completely dissolved, and the dissolved part is removed to carry out the next step;
2) treating hydrosol obtained by mixing two kinds of spherical silicon dioxide with different particle sizes by using hydrogenated ion exchange resin, and modifying by using epoxy silane to obtain silicon dioxide mixed hydrosol, wherein the method comprises the following specific steps:
i) mixing a first set of spherical silica nanoparticles having an average diameter of less than or equal to 20nm and a second set of spherical silica nanoparticles having an average diameter of 20nm to 120nm, the first and second sets of spherical silica nanoparticles being present in a weight ratio of at least 1.5 to 1,
ii) adding hydrogen type ion exchange resin, stirring to adjust the pH value to be less than or equal to 4,
iii) filtering off the exchange resin,
iv) dropping 0.1 to 5 wt.% of an alkoxysilane compound containing a single terminal alkoxysilane group and a single terminal functional group selected from a carboxylic acid group or an epoxy group, based on 100 wt.% of the total weight of the silica hydrosol, and stirring at room temperature for at least 1h,
3) and mixing the anatase titanium dioxide hydrosol and the silicon dioxide mixed hydrosol according to a certain proportion to obtain the anti-fouling composition with photocatalytic performance.
The organic base is a conventional organic base, preferably selected from one or more of the following: ammonia, ethylamine and triethylamine. The organic alkali is used for adjusting the pH value of the titanyl sulfate hydrosol so as to precipitate the titanium dioxide powder. Adding the organic base, adjusting pH to 6-10, preferably 7-9, when pH is less than 6, the subsequent treatment can only generate yellow precipitate, and sol can not be obtained, when pH is more than 10, the subsequent treatment can obtain sol, but H is consumed2O2Too much is not suitable for use.
Optionally, the precipitate is filtered off and washed with distilled water, preferably to remove all sulfate ions and excess organic base.
Adding said H2O2The resulting titania cake is dissolved and reacted with a complex, and stirring is carried out at room temperature or under heating without any particular limitation as long as the stirring time is not particularly limited, and the resulting titania cake is not subjected to any particular stirring procedure, and is allowed to react with the resulting titania cake to obtain a complexThe cake was dissolved until all of it was dissolved.
When the diameter of the first group of silicon dioxide nano particles is more than 20nm, the anti-fouling performance of the obtained anti-fouling composition to inorganic pollutants is poor, and when the diameter of the second group of spherical silicon dioxide nano particles is less than 20, the anti-fouling performance of the obtained anti-fouling composition to inorganic pollutants is also poor. The weight ratio of the first group of silica nanoparticles to the second group of spherical silica nanoparticles is at least 1.5 to 1, and when the weight ratio is less than 1.5 to 1, the antifouling performance is poor.
The hydrogen-type ion exchange resin is not particularly limited, and may be IR120H manufactured by dow chemical company. The hydrogen-type ion exchange resin reduces the pH value of the silica hydrosol and simultaneously removes cations in the silica hydrosol so as to be stably mixed with the titanium dioxide hydrosol, and when the pH value of the silica hydrosol is more than 4, the added titanium dioxide hydrosol is unstable and can generate precipitation.
The alkoxysilane compound has a single terminal alkoxysilane group and a single terminal functional group (e.g., GPTMS) selected from a carboxylic acid group or an epoxy group, and is present in an amount of 0.1 to 5 wt.%, based on 100 wt.% of the total weight of the silica hydrosol, and when the alkoxysilane compound is present in an amount of less than 0.1 wt.%, the resulting antisoiling composition has poor antisoiling properties against inorganic contaminants, and when the alkoxysilane compound is present in an amount of more than 5 wt.%, the silica sol is unstable and precipitates more.
The titanium dioxide hydrosol has the function of providing a good organic anti-fouling effect and simultaneously influences the light transmittance of the anti-fouling composition, the silicon dioxide mixed hydrosol has the function of providing a good inorganic anti-fouling effect, the proportion of the anatase titanium dioxide hydrosol to the silicon dioxide mixed hydrosol is different when the anatase titanium dioxide hydrosol and the silicon dioxide mixed hydrosol are mixed, the obtained anti-fouling composition is different, when the content of the anatase titanium dioxide hydrosol is less than 50 wt.%, the total weight of the anti-fouling composition is 100 wt.%, the inorganic anti-fouling effect of the anti-fouling composition is good, and when the content of the anatase titanium dioxide hydrosol is more than 30 wt.%, the total weight of the anti-fouling composition is 100 wt.%, the organic anti-fouling effect of the anti-fouling composition. When the titanium dioxide hydrosol content of the anatase is 40-50 wt.%, the antifouling composition is colorless and transparent and has good light transmission based on 100 wt.% of the total weight of the antifouling composition.
The preparation method of the anti-fouling composition with photocatalytic performance can further carry out heating reflux treatment on the prepared titanium dioxide hydrosol for no more than 48 hours to obtain the titanium dioxide sol, wherein the reflux time is preferably 3-12 hours, more preferably 5-7 hours, when the reflux time is less than 3 hours, the anti-fouling performance of the obtained anti-fouling composition on organic pollutants is poor, and when the reflux time is more than 12 hours, the haze of the obtained anti-fouling composition is very high, so that the colorless and transparent anti-fouling composition cannot be obtained.
The invention provides a method for preparing an anti-fouling coating, which comprises the following steps: the antifouling composition is applied to the surface of the substrate, a wet antifouling composition coating is formed on the surface of the substrate, and the wet antifouling composition coating is dried to obtain an antifouling coating which is attached to the surface of the substrate.
The anti-fouling composition may be applied to the surface of the substrate by methods known in the art, which may preferably be one or more of the following: knife coating, wipe coating, brush coating, dip coating, spray coating, and roll coating. The anti-fouling composition may be dried using suitable drying methods known in the art and the drying process may be carried out at ambient or elevated temperature, for example the temperature may be 20-180 ℃, alternatively 20-150 ℃, alternatively 20-120 ℃.
The present invention provides a number of preferred embodiments relating to a process for the preparation of anti-fouling compositions having photocatalytic properties.
Preferred embodiment 1 is a method of preparing an anti-fouling composition having photocatalytic properties comprising the steps of:
1) the preparation method of the anatase phase titanium dioxide hydrosol comprises the following specific steps:
i) the titanyl sulfate is dissolved in the deionized water,
ii) adding a proper amount of organic base, adjusting the pH value to 6-10,
iii) filtering off the precipitate to obtain a filter cake,
iv) adding the filter cake into distilled water, and slowly dropwise adding a proper amount of H while stirring2O2Stopping stirring after the filter cake is completely dissolved;
2) treating hydrosol obtained by mixing two kinds of spherical silicon dioxide with different particle sizes by using hydrogenated ion exchange resin, and modifying by using epoxy silane to obtain silicon dioxide mixed hydrosol, wherein the method comprises the following specific steps:
i) mixing a first group of spherical silica nanoparticles with an average diameter of less than 20nm and a second group of spherical silica nanoparticles with an average diameter of 20nm to 120nm in a certain proportion, wherein the weight ratio of the first group of silica nanoparticles to the second group of spherical silica nanoparticles is at least 1.5 to 1,
ii) adding a proper amount of hydrogen type ion exchange resin, stirring to adjust the pH value to be less than 4,
iii) filtering off the exchange resin,
iv) dropping 0.1 to 5 wt.% of an alkoxysilane compound containing a single terminal alkoxysilane group and a single terminal functional group selected from a carboxylic acid group or an epoxy group, based on 100 wt.% of the total weight of the silica hydrosol, and stirring at room temperature for at least 1h,
3) and mixing the anatase titanium dioxide hydrosol and the silicon dioxide mixed hydrosol according to a certain proportion.
Preferred embodiment 2 is the production method according to preferred embodiment 1, wherein, in producing the titanium dioxide hydrosol in the anatase phase, a suitable amount of an organic base is added to adjust the pH to 7 to 9.
Preferred embodiment 3 is the production method according to preferred embodiment 1 or 2, wherein the organic base is selected from one or more of the following organic bases: ammonia, ethylamine and triethylamine.
Preferred embodiment 4 is the production method according to preferred embodiment 1, wherein the precipitate is filtered off and washed with distilled water, and sulfate groups and organic bases on the surface of the precipitate are washed clean.
Preferred embodiment 5 is the production method according to preferred embodiment 1, wherein the titania sol obtained by the production is heated under reflux for not more than 48 hours to obtain a titania sol.
Preferred embodiment 6 is the production method according to preferred embodiment 1, wherein the titania sol obtained by the production is heated and refluxed for 3 to 12 hours to obtain a titania sol.
Preferred embodiment 7 is the production method according to preferred embodiment 1, wherein the titania sol obtained by the production is heated and refluxed for 5 to 7 hours to obtain a titania sol.
Preferred embodiment 8 is an anti-fouling composition prepared according to the method of any one of preferred embodiments 1-7.
Preferred embodiment 9 is an antifouling coating layer obtained by applying the antifouling composition of preferred embodiment 8 to a substrate and drying the composition.
Preferred embodiment 10 is the anti-smudge coating of preferred embodiment 9, wherein the substrate is glass.
Preferred embodiment 11 is the anti-smudge coating of preferred embodiment 10, wherein the substrate is ultra-white glass.
Preferred embodiment 12 is an anti-smudge coating as described in preferred embodiment 9 applied to the substrate using one or more coating methods selected from the group consisting of: knife coating, wiping, brushing, dipping, spraying, and rolling.
Preferred embodiment 13 is an anti-smudge coating, as described in preferred embodiments 9-12, having a Δ H of less than or equal to 5%.
Preferred embodiment 14 is an anti-smudge coating of preferred embodiments 9-12 having a discoloration rate of greater than or equal to 60%.
Preferred embodiment 15 is an anti-smudge coating as described in preferred embodiments 9-12, the anti-smudge coating having a refractive index of 1.40 to 1.70.
Examples
The following examples and comparative examples are provided to aid in the understanding of the present invention and should not be construed as limiting the scope of the invention. All parts and percentages are by weight unless otherwise indicated.
The raw materials used in the examples of the present invention and the comparative examples are shown in table 1 below.
Table 1 raw materials used in examples and comparative examples
The antifouling properties of the antifouling coatings or antifouling members provided in the examples and comparative examples were evaluated mainly by a water contact angle test. The antifouling coatings or antifouling members provided in examples and comparative examples were evaluated for their antifouling properties against inorganic contaminants by a surface resistance property test, a dry dust shaking test, a transmittance and a haze measurement, and for their antifouling properties against organic contaminants by a discoloration rate test.
Water contact Angle test
The water contact angle tester is an optical contact angle tester
DSA100), water drop size 5 μ L, and the average of five measurements was recorded, the lower the contact angle the better the hydrophilicity. Generally speaking, the better the hydrophilicity of the coating, the better the corresponding self-cleaning performance, i.e. the better the anti-fouling performance to inorganic substances, and the contact angle is less than 5 degrees, so the contact angle is less than 5 degrees, and the test results are all recorded. Contact angles less than 10 ° are considered to have better anti-fouling properties against inorganic substances.
And (3) surface resistance testing:
according to ASTM D257-Surface resistivity (s.r.) measurements were made using a resistivity meter (ACL-385, available from ACL Staticide corporation) at 23C, RH ═ 50%. The side of the sample to be tested is placed on the table soil horizontally and upwards. The surface resistivity was measured by placing two parallel electrodes of the meter against the test surface. The average of four measurements was recorded. Resistivity of 106-1011It is considered to have better antifouling performance to inorganic matters.
Dry dust shaking test
Samples (uncoated, half-coated or fully coated glass panels) were exposed to Arizona Test Dust (0 to 70um, available from Powder Technology corporation) maintained at 10% relative humidity. The side of the sample to be tested was placed in a horizontal position into a top snap-on polypropylene container (Ul tra-seal (tm), length 23.2cmn, width 16.8cm, height 6.4cm, 1.4 liter capacity, available from steralite corporation) into which 1000g of fresh arizona test dust had been previously placed. The container was buckled and then gently shaken back and forth at a fixed frequency of 1 time per second for 1 minute to allow the dust to move across the surface of the sample. The cap was then removed and the sample removed from the dust and shaken gently-times.
Transmittance and haze measurements
The anti-fouling performance of the dried coatings was evaluated by measuring the transmission and haze of the samples before and after the dry dust test. The transmittance and HAZE measurements were made according to ASTM D1003-13 using a transparence meter (BYK HAZE-GARD PLUS, available from BYK-Gardner). Five measurements were taken for different areas of each sample surface and the average of these five measurements was recorded.
Δ T initial transmittance-transmittance after exposure
Δ H-haze after Exposure-initial haze
The smaller the Δ T and Δ H, the better the inorganic anti-fouling ability. Better inorganic anti-fouling performance is considered to be achieved when the delta T is less than or equal to 1 percent and the delta H is less than or equal to 5 percent.
Anti-fouling coating thickness and refractive index measurements
The anti-fouling coating thickness and refractive index measuring instrument is an ellipsometer (M-2000, purchased from J.A. Woollam Co.), the sample to be measured is horizontally placed on a test bench, the surface to be measured is upward for measurement, and the adopted fitting result MSE is required to be lower than 10.0. When the substrate is glass with a refractive index of 1.50, the anti-fouling coating is colorless as the refractive index of the anti-fouling coating is closer to 1.50, and the anti-fouling coating provided by the invention is desirably colorless and transparent, so the visual effect is better when the refractive index of the anti-fouling coating is between 1.40 and 1.70.
Decolorization ratio test
Heating a sample to be tested in an oven at 120 ℃ for 10min, then placing the sample into 60mL of 6mg/L methyl orange aqueous solution, placing the sample and the methyl orange aqueous solution together in an ultraviolet test box, wherein the distance between the sample and a light source is 10cm, after irradiating the sample for 19 hours under 7W of 254nm ultraviolet light, taking out 5-10mL of the methyl orange aqueous solution, testing the absorbance under the wavelength of 500nm by using an ultraviolet-visible spectrophotometer (Genesys 10uv, available from Thermo Fisher Scientific Inc), and calculating the decolorization rate according to the following formula:
percent destaining ═ 100% Abs onset-Abs final/Abs onset
The larger the decoloration rate is, the better the antifouling performance of the antifouling coating to organic matters is, therefore, the antifouling coating provided by the invention is considered to have better antifouling performance to organic matters when the decoloration rate is more than or equal to 60%.
Preparation of titanium dioxide hydrosol
Comparative example 1:
8.5g of TiOSO4·xH2Adding O into 76.50g of deionized water, stirring at room temperature for 2h, and adding 16.25g of NH after completely dissolving3·H2O adjust pH to 8.5, filter precipitate and wash 3 times with large amount of distilled water to remove water soluble ions. The washed filter cake is put into 170g of distilled water and stirred, and 13.8mL of H is slowly added dropwise2O2And after stirring for 1 hour, stopping stirring, standing for 24 hours, and performing reflux treatment for 6 hours to obtain the titanium dioxide hydrosol.
Preparation of silica hydrosols
Comparative example 2:
146.84g of deionized water, 45.16g of Nalco8699 and 6.00g of Nalco1050 were mixed and stirred at room temperature for 30min, an appropriate amount of IR120H hydrogen type ion exchange resin was added and stirred for 1h to adjust the pH to 2-3, after the exchange resin was filtered off, 2.00g of GPTMS was added dropwise and stirred at room temperature for 2h to obtain a silica hydrosol.
Preparation of anti-fouling compositions with photocatalytic properties
Example 1-example 5:
the titanium dioxide hydrosol and the silicon dioxide hydrosol are mixed and stirred for 10min respectively according to the proportion of 9: 1, 7: 3, 5: 5, 4: 6 and 3: 7.
1. Phase state of titanium dioxide sol
FIG. 1 shows TiO before and after heat treatment2XRD profile of the sol. As can be seen from FIG. 1, after heat treatment, perhaps due to TiO2The particle size of the sol becomes larger, the peak of the XRD curve becomes obvious, but the peak position keeps the same, and the particle size is well consistent with the standard peak position of anatase type, which indicates that TiO is subjected to heat treatment or not2The sol is anatase type. However, if the sol is not subjected to heat treatment, more H exists in the sol2O2The subsequent experiment can be influenced, and the transparency of the anti-fouling coating can be influenced by overlarge sol particles obtained after the heat treatment time is too long, so that the subsequent experiment is carried out for 6 hours.
TABLE 2 different proportions of TiO2/SiO2Water contact angle, resistance and refractive index of mixed anti-fouling coating
As can be seen from Table 2, following SiO2The content is increased, the surface resistance is increased, but the content is 106-1011Within the range of (1), the antistatic performance is better. Meanwhile, the water contact angle is gradually reduced, which shows that the hydrophilicity of the anti-fouling coating is gradually increased, and the anti-fouling performance of inorganic substances is also gradually improved when SiO2When the weight percentage of the inorganic substance is more than 50 w.t.%, the water contact angle is less than 10 degrees, and the inorganic substance has better self-cleaning performance, so that the inorganic substance has certain help on the anti-fouling capability of inorganic substances. Simultaneously with SiO2The content is increased, and the refractive index of the anti-fouling coating is reduced when SiO is used2Weight ofWhen the content of the anti-fouling coating is 30-70%, the refractive index of the anti-fouling coating is in the range of 1.40-1.70, the color of the coating is lighter, and when SiO is used2When the weight percentage of the coating is 40-50%, the refractive index of the coating is 1.48-1.56, which is close to 1.50, and the coating is almost colorless and has better visual effect.
TABLE 3 different proportions of TiO2/SiO2Shaking ash anti-fouling experimental result of anti-fouling coating
As can be seen from Table 3, after the ash shaking test, TiO2The coating does not have the anti-pollution effect on inorganic substances but has the SiO effect2The content is increased, the anti-pollution effect on inorganic matters is gradually improved, and when SiO is used2When the weight percentage of the inorganic substance is increased to be more than or equal to 30 wt%, the delta T is less than 1 percent and the delta H is less than 5 percent after the ash shaking test, and the inorganic substance has better anti-fouling effect on inorganic substances.
TABLE 4 TiO in different proportions2/SiO2Methyl orange decoloration experimental result of anti-fouling coating
As can be seen from Table 4, pure TiO2The coating has better photocatalytic performance, is far better than that of a white glass substrate and is SiO-coated2The content is increased, the photocatalytic performance is not rapidly reduced, and SiO2The weight percentage of the active carbon is increased from 0 percent to 70 percent, and the decolorization ratio after the decolorization experiment is reduced from 70 percent to 61 percent and is not reduced too much.
In summary, when SiO is used2When the weight percentage of the anti-fouling coating is more than or equal to 30 percent, the anti-fouling coating has good hydrophilicity and the resistivity is 106-1011Within the range of Q/sq, the inorganic substance has better antistatic capability, so the inorganic substance has better anti-fouling capability. When SiO is present2When the weight percentage of the anti-fouling coating is less than or equal to 70 percent, the anti-fouling capability of the anti-fouling coating to organic matters is better. When SiO is present2Between 30% and 70% by weight, the refraction of the anti-fouling coatingThe ratio is in the range of 1.40-1.70. Thus when SiO is present2From 30% to 70%, preferably from 50% to 60%, by weight, a colorless transparent antifouling coating having good antifouling properties both towards organic and inorganic materials is obtained.
Although the foregoing detailed description contains many specific details for the purpose of illustration, it will be appreciated by those of ordinary skill in the art that numerous variations, alterations, substitutions and alterations to these details are within the scope of the invention as claimed. Therefore, the disclosure described in the detailed description does not impose any limitation on the invention as claimed. The proper scope of the invention should be determined by the appended claims and their proper legal equivalents. All cited references are incorporated herein by reference in their entirety.
Claims (15)
1. A process for the preparation of an anti-fouling composition having photocatalytic properties comprising the steps of:
1) the preparation method of the anatase phase titanium dioxide hydrosol comprises the following specific steps:
i) the titanyl sulfate is dissolved in the deionized water,
ii) adding a proper amount of organic base, adjusting the pH value to 6-10,
iii) filtering off the precipitate to obtain a filter cake,
iv) adding the filter cake into distilled water, and slowly dropwise adding a proper amount of H while stirring2O2Stopping stirring after the filter cake is completely dissolved;
2) treating hydrosol obtained by mixing two kinds of spherical silicon dioxide with different particle sizes by using hydrogenated ion exchange resin, and modifying by using epoxy silane to obtain silicon dioxide mixed hydrosol, wherein the method comprises the following specific steps:
i) mixing a first group of spherical silica nanoparticles with an average diameter of less than 20nm and a second group of spherical silica nanoparticles with an average diameter of 20nm to 120nm in a certain proportion, wherein the weight ratio of the first group of silica nanoparticles to the second group of spherical silica nanoparticles is at least 1.5 to 1,
ii) adding a proper amount of hydrogen type ion exchange resin, stirring to adjust the pH value to be less than 4,
iii) filtering off the exchange resin,
iv) dropping 0.1 to 5 wt.%, based on 100 wt.% of the total weight of the aqueous silica sol, of an alkoxysilane compound comprising a single terminal alkoxysilane group and a single terminal functional group selected from carboxylic acid groups or epoxy groups and stirring for at least 1h,
3) mixing the anatase titanium dioxide hydrosol and the silicon dioxide mixed hydrosol, wherein the pure weight ratio of titanium dioxide to silicon dioxide is 7: 3-3: 7, and obtaining the anti-fouling composition with photocatalytic performance.
2. The process according to claim 1, wherein the aqueous titanium dioxide sol in anatase phase is prepared by adding an appropriate amount of an organic base to adjust the pH to 7 to 9.
3. The process according to claim 1 or 2, wherein the organic base is selected from one or more of the following organic bases: ammonia, ethylamine and triethylamine.
4. The method according to claim 1, wherein the precipitate is filtered and washed with distilled water to remove sulfate and organic base from the surface of the precipitate.
5. The production method according to claim 1, wherein the titanium dioxide hydrosol obtained by the production is heated under reflux for not more than 48 hours to obtain a titanium dioxide sol.
6. The production method according to any one of claims 1 to 3, wherein the titanium dioxide hydrosol obtained by the production is subjected to a heat reflux treatment for 3 to 12 hours to obtain a titanium dioxide sol.
7. The production method according to any one of claims 1 to 3, wherein the titanium dioxide hydrosol obtained by the production is subjected to a heat reflux treatment for 5 to 7 hours to obtain a titanium dioxide sol.
8. An anti-fouling composition prepared according to the preparation method of any one of claims 1 to 7.
9. An antifouling coating layer obtained by applying the antifouling composition according to claim 8 to a substrate and drying the coating layer.
10. An anti-fouling coating according to claim 9, said substrate being glass.
11. An anti-fouling coating according to claim 10, said substrate being ultra-white glass.
12. An antifouling coating as claimed in claim 9, said coating method being selected from one or more of: knife coating, wiping, brushing, dipping, spraying, and rolling.
13. An antifouling coating as claimed in claims 9 to 12, having a Δ H of less than or equal to 5%.
14. An antifouling coating as claimed in claims 9 to 12, having a decolourisation rate of greater than or equal to 60%.
15. An antifouling coating as claimed in claims 9 to 12, having a refractive index of from 1.40 to 1.70.
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