CN108977030B - Preparation method of fluorinated halloysite nanotube/waterborne polyurethane composite hydrophobic coating - Google Patents
Preparation method of fluorinated halloysite nanotube/waterborne polyurethane composite hydrophobic coating Download PDFInfo
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- CN108977030B CN108977030B CN201810831984.6A CN201810831984A CN108977030B CN 108977030 B CN108977030 B CN 108977030B CN 201810831984 A CN201810831984 A CN 201810831984A CN 108977030 B CN108977030 B CN 108977030B
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- Prior art keywords
- nanotube
- waterborne polyurethane
- coating
- polyurethane composite
- halloysite
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- HPTYUNKZVDYXLP-UHFFFAOYSA-N aluminum;trihydroxy(trihydroxysilyloxy)silane;hydrate Chemical class O.[Al].[Al].O[Si](O)(O)O[Si](O)(O)O HPTYUNKZVDYXLP-UHFFFAOYSA-N 0.000 title claims abstract description 54
- 239000002131 composite material Substances 0.000 title claims abstract description 48
- 230000002209 hydrophobic effect Effects 0.000 title claims abstract description 27
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- 229910052621 halloysite Inorganic materials 0.000 claims abstract description 29
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- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 27
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- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 claims description 9
- 239000012975 dibutyltin dilaurate Substances 0.000 claims description 9
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- SJECZPVISLOESU-UHFFFAOYSA-N 3-trimethoxysilylpropan-1-amine Chemical compound CO[Si](OC)(OC)CCCN SJECZPVISLOESU-UHFFFAOYSA-N 0.000 claims description 6
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 6
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- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 claims description 6
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- UPMLOUAZCHDJJD-UHFFFAOYSA-N 4,4'-Diphenylmethane Diisocyanate Chemical compound C1=CC(N=C=O)=CC=C1CC1=CC=C(N=C=O)C=C1 UPMLOUAZCHDJJD-UHFFFAOYSA-N 0.000 claims description 5
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- KKYDYRWEUFJLER-UHFFFAOYSA-N 1,1,2,2,3,3,4,4,5,5,6,6,7,7,10,10,10-heptadecafluorodecyl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)CCC(F)(F)F KKYDYRWEUFJLER-UHFFFAOYSA-N 0.000 claims description 3
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- PMQIWLWDLURJOE-UHFFFAOYSA-N triethoxy(1,1,2,2,3,3,4,4,5,5,6,6,7,7,10,10,10-heptadecafluorodecyl)silane Chemical compound CCO[Si](OCC)(OCC)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)CCC(F)(F)F PMQIWLWDLURJOE-UHFFFAOYSA-N 0.000 claims description 3
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- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 description 2
- 229910000838 Al alloy Inorganic materials 0.000 description 2
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- -1 perfluorooctane copper Chemical compound 0.000 description 2
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- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 1
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- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
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- 235000021355 Stearic acid Nutrition 0.000 description 1
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 1
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- OPQARKPSCNTWTJ-UHFFFAOYSA-L copper(ii) acetate Chemical compound [Cu+2].CC([O-])=O.CC([O-])=O OPQARKPSCNTWTJ-UHFFFAOYSA-L 0.000 description 1
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- SNGREZUHAYWORS-UHFFFAOYSA-N perfluorooctanoic acid Chemical compound OC(=O)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)F SNGREZUHAYWORS-UHFFFAOYSA-N 0.000 description 1
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Abstract
The invention provides a preparation method of a fluorinated halloysite nanotube/waterborne polyurethane composite hydrophobic coating. According to the method, silane-modified halloysite nanotubes are introduced into aqueous polyurethane emulsion, a composite coating with a micro-nano coarse structure is formed by spraying, and then the composite coating is subjected to surface modification by fluorosilane, so that the fluorinated halloysite nanotube/aqueous polyurethane hydrophobic coating is obtained. The trachelospermi nanotube adopted by the invention is a natural nanoparticle with a tubular shape, has the advantages of easily obtained raw materials, low cost, unique surface characteristics, high dispersion capability, good biocompatibility and the like. The halloysite nanotube/waterborne polyurethane composite coating is sprayed on the surface of a matrix by adopting a spraying method to form a micro-nano coarse structure, the operation is easy, the preparation method is suitable for preparing large-area coatings, and the thickness of the formed coatings is relatively uniform. The surface modification method is adopted, the coating is modified by utilizing the fluorosilane, the using amount of a solvent is saved, and the operation is simple and rapid.
Description
Technical Field
The invention relates to the technical field of water-based paint preparation, in particular to a preparation method of a fluorinated halloysite nanotube/water-based polyurethane composite hydrophobic coating.
Background
Polyurethanes are multifunctional polymers containing urethane structures in the molecular chain, and are generally prepared by stepwise polymerization of di-or polyisocyanates with compounds containing two or more active hydrogens. A binary colloidal system formed by dissolving or dispersing a polyurethane resin in water is Waterborne Polyurethane (WPU).
The structure and the proportion of the hard section and the soft section of the waterborne polyurethane can be flexibly adjusted, and the waterborne polyurethane has the advantages of non-inflammability, small smell, no pollution, energy conservation, convenient operation and processing and the like, so that the waterborne polyurethane is more and more widely applied to the fields of environment-friendly coatings, printing ink, adhesives and the like. But at the same time, because hydrophilic groups are introduced into the polyurethane molecular chain, the hydrophobicity and solvent resistance of the waterborne polyurethane film are deteriorated, and the application of the waterborne polyurethane film in the waterproof and antifouling fields is limited.
The method mainly comprises two methods on the premise of high water-based polyurethane hydrophobicity, namely, a rough surface with a micro-nano structure is constructed, so that air is retained in a lower layer of water; secondly, surface modification is carried out by using a low surface energy reagent, thereby reducing the surface energy. The preparation method of the hydrophobic coating mainly comprises an etching method, a plasma treatment method, a sol-gel method and a spraying method.
The etching method is a method for preparing the surface of the super-hydrophobic material by etching a micro or nano rough structure on the surface of the material. Huangzi Fang et al (proceedings of Hunan university of Industrial science 2011,25(4): 5-8.) adopts a chemical etching method to prepare a super-hydrophobic surface on an aluminum alloy substrate, and the specific scheme is that the surface of the aluminum alloy is etched by using a mixed solution of hydrochloric acid and oxalic acid, and is modified by using stearic acid after being soaked and oxidized by using a potassium permanganate solution. The etching method has the advantages of high precision, batch production and mature technology. The disadvantages are slow processing speed, high cost and high requirement on processing environment.
Plasma treatment is a new type of surface treatment that chemically modifies the surface of a substrate to impart specific properties thereto. Yung et al [ Carbon,2018,127, 195-.]Using vapor deposition method to obtain regularly arranged carbon nanotube array, changing the structure of the top surface by two plasma treatments, making the surface treated by oxygen plasma possess super-hydrophilicity, and using CF4The plasma treated surface material has superhydrophobicity. The method has the defects that the selectable matrix materials are limited, and the quality of batch processing is difficult to ensure.
The sol-gel method is to carry out hydrolysis-condensation reaction on a chemical precursor under certain conditions to generate sol, and then volatilize or thermally decompose the solvent to form gel with a three-dimensional network structure. Zhai et al [ Journal of Applied Polymer science,2013,128(3): 1715-.]Firstly, APTES (gamma-aminopropyltriethoxysilane) is used as an end-capping agent to cap the PU prepolymer, and then tetraethoxysilane with different contents is added to carry out hydrolytic condensation to obtain a series of SiO2A PU emulsion; and as the silicon content increases, the water contact angle of the coating film surface increases, and the water resistance improves. The sol-gel method has good controllability and high preparation efficiency, and the synthesis method does not need heating and the like. Disadvantages are that the precursors are expensive, the co-solvents are toxic and pollute the environment, and the reaction takes up to several days.
The spray coating method is a coating method in which a coating material is dispersed into uniform and fine droplets by pressure with a spray gun and applied to the surface of an object. And can be classified into air spraying, airless spraying, electrostatic spraying, and the like. The spraying method has high operation efficiency, and can be used in both manual operation and industrial automatic production, so the application range is very wide. Yang et al [ New Journal of chemistry,2011,35(3):576-580 ] utilizes perfluorooctanoic acid and copper acetate to react to obtain perfluorooctane copper, and the reaction product is dispersed in ethanol and sprayed on the surface of a substrate to obtain the super-amphiphobic coating, and the contact angles of the coating to hexadecane and dodecane are both larger than 150 degrees.
A common method of reducing the surface energy of materials is to introduce low surface energy substances such as silicones, organofluorine, and the like. The organosilicon modified polyurethane is mainly characterized in that polysiloxane with reactive groups is reacted with terminal isocyanate to introduce organosilicon chain segments with low surface energy into polyurethane chain segments. Most of fluorinated polyurethane is synthesized by taking bifunctional fluorinated polyether as a raw material, the main chain of the molecular structure of the product contains fluorine atoms, but the product is difficult to migrate to the surface under the action of the main chain of the molecule, so that excellent hydrophobic performance is difficult to obtain, and the price of the fluorinated polyether is generally higher.
The construction of the micro-nano structure is mainly realized by forming or adding nano particles. Halloysite nanotubes (HAL) are pure natural mineral silicate materials, and have the advantages of abundant reserves, low price, wide raw material sources and simple purification process. And the halloysite nanotube has a perfect one-dimensional hollow tubular structure as Carbon Nanotubes (CNTs), has fewer defect structures, has higher theoretical strength and heat resistance of inorganic nanoparticles, and can greatly improve the strength, heat resistance and water resistance of the material when applied to a polymer material. The preparation process of the carbon nano tube with high strength is complex and expensive, and the extensive research and application of the carbon nano tube are limited.
Disclosure of Invention
The invention mainly aims to provide a preparation method of a fluorinated halloysite nanotube/waterborne polyurethane composite hydrophobic coating with good hydrophobic property, which overcomes the defects of the prior art and has the characteristics of simple process and the like.
The invention also aims to provide application of the fluorinated halloysite nanotube/waterborne polyurethane composite emulsion as a hydrophobic coating, in the method, silane-modified halloysite nanotubes are introduced into waterborne polyurethane, sprayed on the surface of a matrix to form a micro-nano-scale rough structure, and then fluorinated silane is used for surface modification, so that the fluorinated halloysite nanotube/waterborne polyurethane hydrophobic coating is prepared by a simple and rapid method, and the process is simple and easy to operate.
The invention discloses a preparation method of a fluorinated halloysite nanotube/waterborne polyurethane composite hydrophobic coating, which comprises the following steps:
s1, modifying halloysite nanotubes,
weighing a certain mass of the trachelospermi nanotube, dissolving the trachelospermi nanotube in an ethanol water solution, ultrasonically vibrating for 30-45min, adding a certain mass of ammonia water and 3-aminopropyltrimethoxysilane, stirring at normal temperature for 24-36 h, then centrifugally separating, washing with absolute ethanol and water for 2-3 times respectively, centrifugally separating, and drying to obtain the modified trachelospermi nanotube;
s2, preparing halloysite nanotube/waterborne polyurethane composite emulsion,
mixing the modified halloysite nanotube, isocyanate and polyalcohol, reacting at 75-90 ℃ until the NCO content reaches a stable state, adding a certain mass of 2, 2-dimethylolbutyric acid, 1, 4-butanediol, dibutyltin dilaurate and acetone, reacting for 3-4h, reducing the temperature to 40-50 ℃, adding a certain mass of triethylamine for neutralization for 25-30min, then adding a certain mass of deionized water, stirring and emulsifying at the revolution of 1000 plus materials of 1200r/min for 45-60min, and removing the acetone by reduced pressure distillation to obtain a halloysite nanotube/waterborne polyurethane composite emulsion;
s3, preparing the halloysite nanotube/waterborne polyurethane composite coating,
spraying the fluoridized halloysite nanotube/waterborne polyurethane composite emulsion prepared in the step S2 on the surface of a cleaned matrix by using a spray gun, and drying at room temperature to obtain a halloysite nanotube/waterborne polyurethane composite coating;
s4, preparing a fluorinated halloysite nanotube/waterborne polyurethane hydrophobic coating,
and spraying a fluorosilane ethanol solution on the surface of the coating by using a spray gun, and drying at room temperature to obtain the fluorinated halloysite nanotube/waterborne polyurethane composite hydrophobic coating.
Further, the mass ratio of the ethanol aqueous solution, the 3-aminopropyltrimethoxysilane, the ammonia water and the trachelol nanotubes in the step S1 is 100: 10-20: 5-10: 0.5 to 2.
Further, the mass ratio of the modified trachelospermine nanotube, the isocyanate, the polyol, the dibutyltin dilaurate, the acetone, the 2, 2-dimethylolbutyric acid, the 1, 4-butanediol, the triethylamine and the deionized water in the step S2 is 0.1-0.5: 5-10: 20-40: 0.1-0.5: 20-40: 0.7-1.5: 0.6-1.5: 0.4-0.8: 30-60.
Further, the isocyanate in the step S2 may be Toluene Diisocyanate (TDI), or isophorone diisocyanate (IPDI), or diphenylmethane diisocyanate (MDI); the polyol may be a polyether polyol, or a polycarbonate diol, or a polypropylene glycol.
Further, the fluorosilane in the step S3 may be heptadecafluorodecyltrimethoxysilane or heptadecafluorodecyltriethoxysilane.
The invention also provides a fluorinated halloysite nanotube/waterborne polyurethane composite hydrophobic coating prepared by any one of the methods.
Compared with the prior art, the invention has the following advantages:
1. the trachelospermi nanotube for constructing the micro-nano coarse structure is a natural nanoparticle with a tubular shape, has the advantages of easily obtained raw materials, low cost, unique surface characteristics, high dispersing capacity, good biocompatibility and the like.
2. The halloysite nanotube/waterborne polyurethane composite coating is sprayed on the surface of a matrix by adopting a spraying method to form a micro-nano coarse structure, the method is easy to operate, is suitable for preparing large-area coatings, and the formed coatings are relatively uniform in thickness.
3. The surface modification method is adopted, the coating is modified by utilizing fluorosilane, the use amount of a solvent is saved, and the operation is simple and quick.
Based on the reasons, the invention can be widely popularized in the technical field of water-based paint preparation.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings needed to be used in the description of the embodiments or the prior art will be briefly introduced below, and it is obvious that the drawings in the following description are some embodiments of the present invention, and for those skilled in the art, other drawings can be obtained according to these drawings without creative efforts.
FIG. 1 is a scanning electron micrograph of the present invention's Trachelospermum nanotubes.
FIG. 2 is an IR spectrum of an Angorostone nanotube before and after silane modification in accordance with example 1 of the present invention.
FIG. 3 is an IR spectrum of a fluorinated annealed Epstein nanotube/waterborne polyurethane composite coating in example 2 of the present invention.
FIG. 4 is an IR spectrum of an aqueous polyurethane coating of comparative example 1 of the present invention.
FIG. 5 shows the results of the static contact angle test of examples of the present invention and comparative examples.
Detailed Description
It should be noted that the embodiments and features of the embodiments may be combined with each other without conflict. The present invention will be described in detail below with reference to the embodiments with reference to the attached drawings.
In order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. The following description of at least one exemplary embodiment is merely illustrative in nature and is in no way intended to limit the invention, its application, or uses. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
FIG. 1 is a scanning electron micrograph of an Trachelospermum nanotube, which shows that it has a hollow tubular structure with a smooth surface and two open ends. The length and the diameter of each nanotube are different, the length of each nanotube is 200-1000 nm, the inner diameter of each nanotube is 10-35 nm, the outer diameter of each nanotube is about 40-100 nm, and the nanotubes are natural nanotubes with cavity structures.
The invention provides a preparation method of a fluorinated halloysite nanotube/waterborne polyurethane composite hydrophobic coating, which comprises the following steps:
s1, modifying halloysite nanotubes,
weighing a certain mass of the trachelospermi nanotube, dissolving the trachelospermi nanotube in a 75% ethanol water solution, ultrasonically vibrating for 30-45min, adding a certain mass of ammonia water and 3-aminopropyltrimethoxysilane, stirring at normal temperature for 24-36 h, then centrifugally separating, washing with absolute ethanol and water for 2-3 times respectively, centrifugally separating, and drying to obtain the modified trachelospermi nanotube.
S2, preparing halloysite nanotube/waterborne polyurethane composite emulsion,
mixing the modified halloysite nanotube, isocyanate and polyol, and reacting at 75-90 ℃ until the NCO content reaches a stable state. Adding a certain mass of 2, 2-dimethylolbutyric acid, 1, 4-butanediol, dibutyltin dilaurate and acetone, reacting for 3-4h, reducing the temperature to 40-50 ℃, adding a certain mass of triethylamine for neutralization for 25-30min, then adding deionized water, stirring and emulsifying for 45-60min at the speed of 1000-1200r/min, and removing the acetone by reduced pressure distillation to obtain the halloysite nanotube/waterborne polyurethane composite emulsion.
S3, preparing the halloysite nanotube/waterborne polyurethane composite coating,
spraying the fluoridized halloysite nanotube/waterborne polyurethane composite emulsion prepared in the step S2 on the surface of a cleaned matrix by using a spray gun, and drying at room temperature to obtain a halloysite nanotube/waterborne polyurethane composite coating;
s4, preparing the fluoridized halloysite nanotube/waterborne polyurethane composite hydrophobic coating,
and spraying a fluorosilane ethanol solution on the surface of the composite coating by using a spray gun, and drying at room temperature to obtain the fluorinated halloysite nanotube/waterborne polyurethane hydrophobic coating.
The mass ratio of the ethanol aqueous solution, the 3-aminopropyltrimethoxysilane, the ammonia water and the trachelol nanotube in the step S1 is 100: 10-20: 5-10: 0.5 to 2.
The mass ratio of the modified trachelospermine nanotube, the isocyanate, the polyol, the dibutyltin dilaurate, the acetone, the 2, 2-dimethylolbutyric acid, the 1, 4-butanediol, the triethylamine and the deionized water in the step S2 is 0.1-0.5: 5-10: 20-40: 0.1-0.5: 20-40: 0.7-1.5: 0.6-1.5: 0.4-0.8: 30-60.
The isocyanate in the step S2 may be Toluene Diisocyanate (TDI), isophorone diisocyanate (IPDI), or diphenylmethane diisocyanate (MDI); the polyol may be a polyether polyol, or a polycarbonate diol, or a polypropylene glycol.
The fluorosilane is heptadecafluorodecyltrimethoxysilane or heptadecafluorodecyltriethoxysilane.
The invention also provides a fluorinated halloysite nanotube/waterborne polyurethane hydrophobic coating prepared by any one of the methods.
FIG. 2 is an infrared spectrum of (APTMS-HAL) Trachelospermic nanotubes before (HAL) and after (APTMS-HAL) modification with a silane coupling agent. The halloysite nanotubes before and after modification can be found to be 3698cm-1And 3617cm-1The strong absorption peaks exist at the positions and respectively correspond to O-H stretching vibration of the hydroxyl on the inner surface of the halloysite nanotube and the hydroxyl in the halloysite nanotube; other characteristic peaks, e.g. Si-O bonds at 1095m-1And 1030cm-1Is subjected to stretching vibration, and the Si-O-Al bond is 540cm-1Bending vibration, Si-O-Si bond at 458cm-1The bending vibration can be seen in both curves. But the modified halloysite nanotube is 2843cm-1And 2917cm-1New vibration peaks appear at the positions corresponding to the symmetric and antisymmetric stretching vibration peaks of the C-H bond respectively, and are also found at 1473cm-1Has N-H characteristic peak, and the appearance of the characteristic peak in the curve indicates that the halloysite nanotube is successfully modified.
Example 1
Adding 12.8g of polycarbonate diol (PCDL2000) and 400mg of modified trachelospermi nanotubes into a three-neck flask provided with a condenser tube and a stirrer, raising the temperature to 85 ℃, adding 5g of isophorone diisocyanate into the flask after the PCDL is completely dissolved and is uniformly mixed with the trachelospermi nanotubes, and continuously stirring and reacting until the NCO content reaches a stable value. Adding 0.7g of 2, 2-dimethylolbutyric acid (DMBA) hydrophilic chain extender, 0.54g of 1, 4-butanediol micromolecule chain extender and two drops of dibutyltin dilaurate catalyst, simultaneously adding acetone, reacting until the NCO content reaches a stable value, reducing the reaction temperature to 50 ℃, adding 0.47g of triethylamine for neutralization for 30min, then adding deionized water, stirring and emulsifying for 1h at the revolution of 1200r/min, and removing the acetone by reduced pressure distillation to obtain the waterborne polyurethane composite emulsion. Spraying the composite coating on the surface of a cleaned substrate, and drying at room temperature to obtain the fluoridated halloysite nanotube/waterborne polyurethane composite coating. And uniformly spraying a fluorosilane ethanol solution with the mass fraction of 1% on the surface of the composite coating by using a spray gun, and drying at room temperature to obtain the fluorinated halloysite nanotube/waterborne polyurethane composite hydrophobic coating.
And (3) characterizing the prepared fluorinated tourmalinite nanotube/waterborne polyurethane composite hydrophobic coating. FIG. 3 shows the infrared spectrum of the fluorinated annealed nanotube/waterborne polyurethane composite hydrophobic coating, and the test result of the water contact angle is shown in FIG. 5. The infrared spectrum can be seen at 2270cm-1No characteristic peak of-NCO was observed, indicating that all of-NCO had participated in the reaction and that the concentration was 3350cm-1、1730cm-1、1530cm-1、1245cm-1All the parts have strong absorption peaks which respectively represent an N-H stretching vibration peak, a C ═ O stretching vibration peak, an N-H deformation vibration peak and a-NHCOO-middle-C-O stretching vibration peak of carbamate, and the absorption peak is 2943cm-1Wherein represents CH in the molecular chain of polyurethane3And CH2Peak of stretching vibration at 1045cm-1Has a distinct absorption peak, which is attributed to the stretching vibration of Si-O, 898cm-1The peak is the C-F telescopic vibration absorption peak, and the coupling of hydroxyl on the surface of the WPU film and the low-surface-energy fluorine silane is shown through a covalent bond, so that fluorine atoms are introduced to the surface of the coating.
Example 2
Different from the embodiment 1, the modified trachelospermi nanotube 400mg is changed to 300mg, and other components and processes are the same.
Comparative example 1
12.8g of polycarbonate diol (PCDL2000) is added into a three-neck flask provided with a condenser tube and a stirrer, the temperature is raised to 85 ℃, after the PCDL is completely dissolved, 5g of isophorone diisocyanate is added into the flask, and the stirring is continued until the NCO content reaches a stable value. Adding 0.7g of 2, 2-dimethylolbutyric acid (DMBA) hydrophilic chain extender, 0.54g of 1, 4-butanediol micromolecule chain extender, two drops of dibutyltin dilaurate catalyst and acetone, reacting until the NCO content reaches a stable value, reducing the reaction temperature to 50 ℃, adding 0.47g of triethylamine for neutralization for 30min, then adding deionized water, stirring and emulsifying for 1h at the revolution of 1200r/min, and removing the acetone by reduced pressure distillation to obtain the waterborne polyurethane emulsion. And uniformly spraying the prepared emulsion on the surface of a cleaned substrate, and drying at room temperature to obtain the waterborne polyurethane coating.
Comparative example 2
Adding 12.8g of polycarbonate diol (PCDL2000) and 400mg of modified trachelospermi nanotubes into a three-neck flask provided with a condenser tube and a stirrer, raising the temperature to 85 ℃, adding 5g of isophorone diisocyanate into the flask after the PCDL is completely dissolved and is uniformly mixed with the trachelospermi nanotubes, and continuously stirring to react until the NCO content reaches a stable value. Adding 0.7g of 2, 2-dimethylolbutyric acid (DMBA) hydrophilic chain extender, 0.54g of 1, 4-butanediol micromolecule chain extender, two drops of dibutyltin dilaurate catalyst and acetone, reacting until the NCO content reaches a stable value, reducing the temperature to 50 ℃, adding 0.47g of triethylamine for neutralization for 30min, then adding deionized water, stirring and emulsifying for 1h at the revolution of 1200r/min, and removing the acetone by reduced pressure distillation to obtain the complex emulsion of the angstromite nanotube/waterborne polyurethane. Spraying the composite coating on the surface of a cleaned substrate, and drying at room temperature to obtain the tourmalinite nanotube/waterborne polyurethane composite coating.
And (3) characterizing the prepared waterborne polyurethane coating. FIG. 4 shows the IR spectrum of the aqueous polyurethane coating and the test results of water contact angle are shown in FIG. 5. It can be seen from the infrared spectrum at 2270cm-1No characteristic peak of-NCO was observed, indicating that all of-NCO had participated in the reaction and that the concentration was 3350cm-1、1730cm-1、1530cm-1、1245cm-1All the parts have strong absorption peaks which respectively represent an N-H stretching vibration peak, a C ═ O stretching vibration peak, an N-H deformation vibration peak and a-NHCOO-middle-C-O stretching vibration peak of carbamate, and the absorption peak is 2943cm-1Wherein represents CH in the molecular chain of polyurethane3And CH2And (4) stretching vibration peaks, which prove that the waterborne polyurethane coating is formed.
The wettability of the surface of the aqueous polyurethane coating was characterized in the above examples by the static Contact Angle (CA) using the following water contact angle test method: a contact angle tester PT-705B manufactured by Pocet corporation, Dongguan, was used to perform the test by dropping a drop of water onto the coating surface with 2. mu.l of deionized water, 5 points were measured for each sample, and the average value was taken.
As can be seen from fig. 5, the water contact angle of the aqueous polyurethane coating in comparative example 1 was 75 °, showing significant hydrophilicity; the water contact angle of the aqueous polyurethane composite coating modified by the trachelospermine nanotube in the comparative example 2 is 98 degrees, mainly because the trachelospermine nanotube forms a micro-nano structure on the surface of the coating, the contact angle is increased; the water contact angle of the composite coating modified by the fluorosilane in the example 1 is 118 degrees, the water contact angle of the composite coating in the example 2 is 113 degrees, and the coating has obvious hydrophobicity, on one hand, because the nano particles form a micro-nano structure layer capable of capturing air on the surface of the coating, liquid drops can not permeate into the coating, so that the water contact angle of the surface of the coating is improved; on the other hand, because the hydroxyl on the surface of the water-based polyurethane coating is coupled with the fluorinated silane coupling agent with low surface energy, fluorine atoms with low surface energy are introduced to the surface of the coating, and the hydrophobic effect is obviously enhanced.
Finally, it should be noted that: the above embodiments are only used to illustrate the technical solution of the present invention, and not to limit the same; while the invention has been described in detail and with reference to the foregoing embodiments, it will be understood by those skilled in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some or all of the technical features may be equivalently replaced; and the modifications or the substitutions do not make the essence of the corresponding technical solutions depart from the scope of the technical solutions of the embodiments of the present invention.
Claims (5)
1. A preparation method of a fluorinated halloysite nanotube/waterborne polyurethane composite hydrophobic coating is characterized by comprising the following steps:
s1, modifying halloysite nanotubes,
weighing a certain mass of the trachelospermi nanotube, dissolving the trachelospermi nanotube in an ethanol water solution, ultrasonically vibrating for 30-45min, adding a certain mass of ammonia water and 3-aminopropyltrimethoxysilane, stirring at normal temperature for 24-36 h, then centrifugally separating, washing with absolute ethanol and water for 2-3 times respectively, centrifugally separating, and drying to obtain the modified trachelospermi nanotube, wherein the mass ratio of the ethanol water solution to the 3-aminopropyltrimethoxysilane to the ammonia water to the trachelospermi nanotube is 100: 10-20: 5-10: 0.5 to 2;
s2, preparing halloysite nanotube/waterborne polyurethane composite emulsion,
mixing the modified halloysite nanotube, isocyanate and polyalcohol, reacting at 75-90 ℃ until the NCO content reaches a stable state, adding a certain mass of 2, 2-dimethylolbutyric acid, 1, 4-butanediol, dibutyltin dilaurate and acetone, reacting for 3-4h, reducing the temperature to 40-50 ℃, adding a certain mass of triethylamine for neutralization for 25-30min, then adding a certain mass of deionized water, stirring and emulsifying at the revolution of 1000 plus materials of 1200r/min for 45-60min, and removing the acetone by reduced pressure distillation to obtain a halloysite nanotube/waterborne polyurethane composite emulsion;
s3, preparing the halloysite nanotube/waterborne polyurethane composite coating,
spraying the fluoridized halloysite nanotube/waterborne polyurethane composite emulsion prepared in the step S2 on the surface of a cleaned matrix by using a spray gun, and drying at room temperature to obtain a halloysite nanotube/waterborne polyurethane composite coating;
s4, preparing the fluoridized halloysite nanotube/waterborne polyurethane composite hydrophobic coating,
and spraying a fluorosilane ethanol solution on the surface of the coating by using a spray gun, and drying at room temperature to obtain the fluorinated halloysite nanotube/waterborne polyurethane composite hydrophobic coating.
2. The preparation method according to claim 1, wherein the mass ratio of the modified trachelospermine nanotube, the isocyanate, the polyol, the dibutyltin dilaurate, the acetone, the 2, 2-dimethylolbutyric acid, the 1, 4-butanediol, the triethylamine and the deionized water in step S2 is 0.1-0.5: 5-10: 20-40: 0.1-0.5: 20-40: 0.7-1.5: 0.6-1.5: 0.4-0.8: 30-60.
3. The method according to claim 2, wherein the isocyanate in step S2 is toluene diisocyanate, isophorone diisocyanate, or diphenylmethane diisocyanate; the polyol may be a polyether polyol or a polycarbonate diol or a polypropylene glycol.
4. The method of claim 1, wherein the fluorosilane of step S4 is heptadecafluorodecyltrimethoxysilane or heptadecafluorodecyltriethoxysilane.
5. A fluorinated halloysite nanotube/aqueous polyurethane composite hydrophobic coating prepared by the method of any one of claims 1-4.
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| CN111909418B (en) * | 2020-08-17 | 2021-09-03 | 吉林大学 | Modified polyimide aerogel and preparation method and application thereof |
| CN112480774B (en) * | 2020-11-27 | 2023-09-19 | 天津日津科技股份有限公司 | Halloysite modified fluororesin coating agent and preparation method thereof |
| CN113533139B (en) * | 2021-06-28 | 2022-05-24 | 福建农林大学 | Long-term stable method for modifying surface by polymer |
| CN114957909B (en) * | 2022-07-26 | 2023-08-29 | 河北大学 | Ablation-resistant halloysite nanotube/phenolic resin composite material and preparation method thereof |
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| CN117304866B (en) * | 2023-11-24 | 2024-03-19 | 山东永安胶业有限公司 | Indoor anti-pollution decorative adhesive for wallhanging stone |
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