CN109355012B - Preparation method and application of fluorine-containing organosilicon hydrophobic agent containing nano-diamond - Google Patents
Preparation method and application of fluorine-containing organosilicon hydrophobic agent containing nano-diamond Download PDFInfo
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- CN109355012B CN109355012B CN201811287684.2A CN201811287684A CN109355012B CN 109355012 B CN109355012 B CN 109355012B CN 201811287684 A CN201811287684 A CN 201811287684A CN 109355012 B CN109355012 B CN 109355012B
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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
- 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
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- C09D4/00—Coating compositions, e.g. paints, varnishes or lacquers, based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; Coating compositions, based on monomers of macromolecular compounds of groups C09D183/00 - C09D183/16
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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
- C09D5/18—Fireproof paints including high temperature resistant paints
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- C—CHEMISTRY; METALLURGY
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- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/04—Polysiloxanes
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Abstract
The invention discloses a preparation method and application of a fluorine-containing organosilicon hydrophobic agent containing nano-diamond. The invention discloses a fluorine-containing organosilicon hydrophobic agent containing nano-diamond, which is prepared by the following steps: adding long-chain carbon alkyl siloxane, long-chain fluorine-containing alkyl siloxane hydrolysate, nano diamond or derivatives thereof and fluorine-containing polyether into trifluorotrichloroethane (CFC113a) under stirring to obtain the fluorine-containing organosilicon hydrophobic agent containing nano diamond. The invention adopts the long-carbon chain alkyl siloxane, the fluorine-containing alkyl siloxane, the nano diamond and the derivative thereof and the fluorine-containing polyether to be used together, thereby not only ensuring that the product has good hydrophobic property and transparency, but also improving the wear resistance and having certain oleophobic property, and being mainly used for the smooth surface of materials such as glass, ceramics, metal and the like.
Description
Technical Field
The invention belongs to the field of hydrophobing agents, and discloses a preparation method and application of a nano-diamond-containing organosilicon hydrophobing agent.
Background
The lower the surface free energy of the material, the more hydrophobic it is. However, even a smooth surface with the lowest surface energy has a contact angle with water of only 119 °. The siloxane containing long-chain fluorine-containing groups is a substance with very low surface free energy, and the contact angle of a single-layer film of long-chain fluorocarbon to water is 118 degrees as disclosed in US 6395331. The patent discloses that the long-chain fluorocarbon is hydrolyzed by hydrochloric acid, acetic acid or hydrochloric acid, and the prepared hydrophobic agent has hydrochloric acid content of about 5 per mill and is strongly acidic; isopropyl ether and ethylene glycol are used as solvents, so that the film is flammable, has a high boiling point and cannot be directly formed at room temperature.
Disclosure of Invention
The invention aims to overcome the defects of the background technology and provide a preparation method and application of fluorine-containing organosilicon containing nano-diamond, so as to improve the wear resistance of a hydrophobic agent after a hydrophobic film is formed on a smooth surface.
In order to improve the wear resistance of the hydrophobing agent after a hydrophobic film is formed on a smooth surface, the technical scheme of the invention comprises the following processes: adding long-chain alkyl siloxane, long-chain fluorine-containing alkyl siloxane hydrolysate, nano diamond or derivatives thereof and fluorine-containing polyether into a solvent CFC113a under stirring at room temperature to obtain the fluorine-containing organosilicon hydrophobing agent containing the nano diamond. The main raw materials comprise the following components in percentage by mass: 0.4-5 per mill of long-carbon chain alkyl siloxane; 0.2-4 per mill of fluorine-containing alkyl siloxane hydrolysate; 0.05-0.8 per mill of nano diamond or derivatives thereof; 0-2.0 per mill of fluorine-containing polyether; the remainder being solvent CFC113 a.
The fluorine-containing organosilicon hydrophobing agent containing the nanodiamond is prepared by the following method: adding long-chain alkyl siloxane, long-chain fluorine-containing alkyl siloxane hydrolysate, nano diamond or derivatives thereof and fluorine-containing polyether into a solvent CFC113a under stirring to obtain the fluorine-containing organosilicon hydrophobic agent containing nano diamond.
The long-chain fluorine-containing group-containing siloxane includes a structure represented by formula (I):
wherein n is 8-11; r1、R2、R3Each independently being methoxy, ethoxy, methyl, ethyl, perfluoroalkyl, R1、R2、R3At least one group in the above-mentioned groups is methoxy group or ethoxy group.
Representative examples of long chain fluoro group containing siloxane hydrolysates include, but are not limited to: (tridecafluoro-1, 1,2, 2-tetrahydrooctyl) trimethoxysilane, (tridecafluoro-1, 1,2, 2-tetrahydrooctyl) methyldimethoxysilane, (heptadecafluoro-1, 1,2, 2-tetrahydrodecyl) trimethyoxysilane, (heptadecafluoro-1, 1,2, 2-tetrahydrodecyl) triethoxysilane, (heptadecafluoro-1, 1,2, 2-tetrahydrodecyl) methyldimethoxysilane, perfluorotetradecyl-1, 1,2, 2-tetrahydrotriethoxysilane, perfluorododecyl-1, 1,2, 2-tetrahydrotriethoxysilane, perfluorotetradecyl-1, 1,2, 2-tetrahydrotrifluoromethyldiethoxysilane, and other hydrolysis products of fluorine-containing silanes.
The long carbon chain alkyl siloxane includes one or two of n-dodecyl trimethyl (ethoxy) silicane, n-tetradecyl trimethyl (ethoxy) silicane, n-hexadecyl trimethyl (ethoxy) silicane and n-octadecyl trimethyl (ethoxy) silicane.
The nano-diamond or the derivative thereof comprises one of nano-diamond, nano-diamond modified by n-dodecyl trimethyl (ethoxy) silicane, nano-diamond modified by n-hexadecyl trimethyl (ethoxy) silicane, nano-diamond modified by n-heptadecafluorodecyl trimethyl (ethoxy) silicane and fluorinated nano-diamond.
The fluorine-containing polyether is an oligomer with the molecular weight of 2000-6000.
The fluorine-containing organosilicon hydrophobic agent containing the nano-diamond can be applied to surface hydrophobic treatment of glass, ceramics, metal, plastics and paint.
Compared with the prior art, the invention has the beneficial effects that: hydrolyzing the long-chain fluorine-containing alkyl siloxane by using solid acid, wherein the prepared hydrophobic agent is close to neutrality; the solvent uses CFC113a, which has no environmental pollution, is not flammable and has improved safety. In addition, the wear resistance of the nano-diamond or the derivative thereof is obviously improved due to the addition of the nano-diamond or the derivative thereof, and the contact angle is reduced by less than 5 degrees in a wear resistance test experiment.
Detailed Description
The present invention will be described in further detail with reference to specific examples, but the scope of the present invention is not limited thereto.
Preparation method of fluoroalkyl siloxane hydrolysate (taking (heptadecafluoro-1, 1,2, 2-tetrahydrodecyl) methyldimethoxysilane as an example): adding 20.0g of mesoporous sulfonic acid, 5g of (heptadecafluoro-1, 1,2, 2-tetrahydrodecyl) methyldimethoxysilane, 925g of ethanol and 50g of water into a three-necked bottle with a thermometer, reacting for 13h under stirring at the reaction temperature of 40-45 ℃, cooling to room temperature, filtering to remove the catalyst to obtain a hydrolysis reaction solution, and distilling under reduced pressure to obtain the fluorine-containing alkyl siloxane hydrolysate.
The preparation method of the silane modified nano-diamond takes the n-hexadecyl trimethyl (ethyl) oxysilane modified nano-diamond as an example: 0.8g of dried nano-diamond, 10g of toluene and n-hexadecyl trimethyl (ethyl) oxysilane are added into a reaction bottle and refluxed for 18 hours.
The preparation method of the fluorinated nanodiamond comprises the following steps: filling the dried nano-diamond into a tubular reactor, slowly introducing anhydrous hydrogen fluoride, and reacting for 4 hours at 400 ℃.
Contact angle test: the contact angle was measured using a contact angle measuring instrument, model JC2000D, from Shanghai morning digital technical Equipment Ltd, using 5. mu.L of deionized water per measurement, and the average of the 5 measurements was taken.
And (3) wear resistance test: the contact angle is measured before and after the test by a linear abrasion meter, flannel, a load of 9.8N/cm2, 40 round-trip/min, a round-trip distance of 12 +/-2 cm and a round-trip time of 10000.
Example 1
Under the stirring at room temperature, adding 99.9g of solvent CFC113a into a reaction bottle, adding 0.04g of n-hexadecyl trimethoxy silane, 0.02g of perfluorododecyl-1, 1,2, 2-tetrahydrotriethoxysilane hydrolysate and 0.0050g of nano-diamond, continuing to stir for 0.5h after the addition is finished, wherein the initial contact angle is 109.1 degrees, and the contact angle is 107.8 degrees after the abrasion resistance test.
Comparative example 1
Under the condition of stirring at room temperature, 99.9g of solvent CFC113a99.9 is added into a reaction bottle, 0.04g of n-hexadecyl trimethoxy silane and 0.02g of hydrolysis product of perfluorododecyl-1, 1,2, 2-tetrahydrotriethoxy silane are added, the stirring is continued for 0.5h after the addition is finished, the initial contact angle is 106.9 degrees, and the contact angle is 90.5 degrees after the abrasion resistance test.
Example 2
Under the stirring at room temperature, adding 0.06g of n-dodecyl triethoxysilane, 0.02g of perfluorododecyl-1, 1,2, 2-tetrahydrotriethoxysilane hydrolysate and 0.0050g of nano diamond into a reaction bottle of solvent CFC113a 99.9.9 g, continuing to stir for 0.5h after the addition, wherein the initial contact angle is 101.1 degrees, and the contact angle is 98.9 degrees after the wear resistance test.
Example 3
Stirring at room temperature, adding 99.8g of solvent CFC113a 99.8 into a reaction bottle, adding 0.08g of n-octadecyl triethoxy silane, (0.10 g of heptadecafluoro-1, 1,2, 2-tetrahydrodecyl) methyldimethoxy silane hydrolysate, 0.06g of n-hexadecyl triethoxy silane modified nano diamond and 0.01g of fluorine-containing polyether (molecular weight 2000-2800), continuing stirring for 0.5h after the addition is finished, wherein the initial contact angle is 119.0 degrees, and the contact angle after the abrasion resistance test is 116.6 degrees.
Example 4
Stirring at room temperature, adding 99.4g of solvent CFC113a 99.4 to a reaction bottle, adding 0.1g of n-hexadecyl trimethoxy silane, 0.3g of perfluorotetradecyl-1, 1,2, 2-tetrahydrotrifluoromethyl diethoxy silane hydrolysate, 0.08g of n-heptadecafluorodecyl triethoxy silane modified nano diamond and 0.05g of fluorine-containing polyether (molecular weight is 3200-4000), continuing stirring for 0.5h after the addition is finished, wherein the initial contact angle is 107.8 degrees, and the contact angle after the wear resistance test is 106.0 degrees.
Example 5
Under the stirring at room temperature, adding solvent CFC113a 98.8.8 g into a reaction bottle, adding n-tetradecyl triethoxy silane 0.3g, trimethoxy silane hydrolysate (tridecafluoro-1, 1,2, 2-tetrahydrooctyl) 0.4g, n-dodecyl trimethoxy silane modified nano diamond 0.06g and fluorine-containing polyether (molecular weight 3200-4000) 0.5g, continuing to stir for 0.5h after the addition, wherein the initial contact angle is 100.8 degrees, and the contact angle is 96.2 degrees after the wear resistance test.
Example 6
Stirring at room temperature, adding 99.4g of solvent CFC113a 99.4 into a reaction bottle, adding 0.5g of n-octadecyl trimethoxy silane, 0.1g of n-heptadecafluorodecyl triethoxy silane hydrolysate, 0.01g of fluorinated nano diamond and 0.2g of fluorine-containing polyether (with the molecular weight of 3200-4000) (with the molecular weight of 4800-5200), stirring for 0.5h after adding, wherein the initial contact angle is 116.1 degrees, and the contact angle after the wear resistance test is 111.8 degrees.
Example 7
Under the condition of stirring at room temperature, adding 113 g of solvent CFC113a 100g into a reaction bottle, adding 0.06g of n-hexadecyl trimethoxy silane, 0.06g of heptadecafluorodecyl trimethoxy silane hydrolysate, 0.001g of nano diamond and 0.01g of fluorine-containing polyether (with the molecular weight of 3200-4000), continuing stirring for 0.5h after the addition is finished, wherein the initial contact angle is 117.4 degrees, and the contact angle is 115.2 degrees after the wear resistance test.
Example 8
The clean glass slide was immersed for 2min in example 7, left at room temperature with a humidity of less than 50% for 24h, and wiped with a nonwoven fabric at a contact angle of 115.2 °.
The clean glazed ceramic was dipped in example 7 for 2min, left at room temperature with a humidity of less than 50% for 24h, and wiped with a non-woven cloth with a contact angle of 113.7 °.
Claims (3)
1. A preparation method of a fluorine-containing organosilicon hydrophobic agent containing nano-diamond comprises the following steps: adding long-chain alkyl siloxane, long-chain fluorine-containing alkyl siloxane hydrolysate, nano diamond or derivatives thereof and fluorine-containing polyether into a solvent CFC113a under stirring at room temperature to obtain a fluorine-containing organosilicon hydrophobizing agent containing the nano diamond; wherein the mass percentage composition is as follows: 0.4-5 per mill of long-chain C-alkyl siloxane and 0.2-4 per mill of long-chain fluorine-containing alkyl siloxane hydrolysate; 0.05-0.8 per mill of nano-diamond or derivatives thereof, 0-2.0 per mill of fluorine-containing polyether, and the balance of solvent CFC113 a; the long chain fluoroalkyl containing siloxane comprises a structure represented by formula (I):
wherein n is 8-11; r1、R2、R3Each independently being methoxy, ethoxy, methyl, ethyl, perfluoroalkyl, R1、R2、R3At least one group in the above-mentioned groups is methoxyl group and ethoxyl group;
the long-carbon chain alkyl siloxane is one or two of n-dodecyl trimethoxy silane, n-dodecyl triethoxy silane, n-tetradecyl trimethoxy silane, n-tetradecyl triethoxy silane, n-octadecyl trimethoxy silane and n-octadecyl triethoxy silane.
2. The method for preparing the nanodiamond-containing fluorine-containing organosilicon hydrophobizing agent according to claim 1, wherein the nanodiamond or the derivative thereof is: the nano-diamond is one of nano-diamond modified by n-dodecyl trimethoxy silane or n-dodecyl triethoxy silane, nano-diamond modified by n-hexadecyl trimethoxy silane or n-hexadecyl triethoxy silane, nano-diamond modified by n-heptadecafluorodecyl trimethoxy silane or n-heptadecafluorodecyl triethoxy silane and fluorinated nano-diamond.
3. The preparation method of the nano-diamond-containing fluorine-containing organosilicon hydrophobic agent according to claim 1, wherein the fluorine-containing polyether is an oligomer with a molecular weight of 2000-6000.
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| JP2022542909A (en) * | 2019-07-25 | 2022-10-07 | ヴァルフレ ディ ボンゾ，ロベルト | Coating composition with polysiloxane-modified carbon nanoparticles |
| JP7255692B2 (en) * | 2019-08-20 | 2023-04-11 | 信越化学工業株式会社 | Water- and oil-repellent member and method for manufacturing water- and oil-repellent member |
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| CA2175849C (en) * | 1995-06-01 | 2003-07-15 | George B. Goodwin | Autophobic water repellent surface treatment |
| US9694388B2 (en) * | 2013-05-14 | 2017-07-04 | University Of Houston System | Waterproof coating with nanoscopic/microscopic features and methods of making same |
| CN103992043B (en) * | 2014-05-15 | 2016-08-24 | 奇瑞汽车股份有限公司 | A kind of preparation method of water-repelling agent |
| CN104445218A (en) * | 2014-11-20 | 2015-03-25 | 广州汇纳新材料科技有限公司 | Fluoroalkylsilane modified silicon dioxide nano material as well as preparation method and application thereof |
| US11292920B2 (en) * | 2015-06-10 | 2022-04-05 | Ppg Industries Ohio, Inc. | Water repellant surface treatment for aircraft transparencies and methods of treating aircraft transparencies |
| CN105776887B (en) * | 2016-03-11 | 2018-02-16 | 奇瑞汽车股份有限公司 | A kind of hydrophober, hydrophobic glass and preparation method thereof |
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