CN114276680B - Super-hydrophobic composite material and preparation method and application thereof - Google Patents
Super-hydrophobic composite material and preparation method and application thereof Download PDFInfo
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- 239000002131 composite material Substances 0.000 title claims abstract description 81
- 230000003075 superhydrophobic effect Effects 0.000 title claims abstract description 53
- 238000002360 preparation method Methods 0.000 title claims abstract description 22
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 71
- SCPWMSBAGXEGPW-UHFFFAOYSA-N dodecyl(trimethoxy)silane Chemical compound CCCCCCCCCCCC[Si](OC)(OC)OC SCPWMSBAGXEGPW-UHFFFAOYSA-N 0.000 claims abstract description 49
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 48
- 238000003756 stirring Methods 0.000 claims abstract description 47
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims abstract description 38
- 238000006243 chemical reaction Methods 0.000 claims abstract description 30
- 238000000576 coating method Methods 0.000 claims abstract description 25
- 229910004298 SiO 2 Inorganic materials 0.000 claims abstract description 24
- CTENFNNZBMHDDG-UHFFFAOYSA-N Dopamine hydrochloride Chemical compound Cl.NCCC1=CC=C(O)C(O)=C1 CTENFNNZBMHDDG-UHFFFAOYSA-N 0.000 claims abstract description 22
- 239000011248 coating agent Substances 0.000 claims abstract description 22
- 229960001149 dopamine hydrochloride Drugs 0.000 claims abstract description 22
- 239000007822 coupling agent Substances 0.000 claims abstract description 16
- 239000003960 organic solvent Substances 0.000 claims abstract description 11
- 238000002156 mixing Methods 0.000 claims abstract description 10
- 239000002105 nanoparticle Substances 0.000 claims abstract description 8
- 239000012670 alkaline solution Substances 0.000 claims abstract description 5
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 32
- 238000000034 method Methods 0.000 claims description 31
- 239000008367 deionised water Substances 0.000 claims description 26
- 229910021641 deionized water Inorganic materials 0.000 claims description 26
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 22
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 22
- 230000035484 reaction time Effects 0.000 claims description 15
- 239000000243 solution Substances 0.000 claims description 11
- YYLGKUPAFFKGRQ-UHFFFAOYSA-N dimethyldiethoxysilane Chemical compound CCO[Si](C)(C)OCC YYLGKUPAFFKGRQ-UHFFFAOYSA-N 0.000 claims description 10
- CPUDPFPXCZDNGI-UHFFFAOYSA-N triethoxy(methyl)silane Chemical compound CCO[Si](C)(OCC)OCC CPUDPFPXCZDNGI-UHFFFAOYSA-N 0.000 claims description 10
- 238000001035 drying Methods 0.000 claims description 9
- 238000005406 washing Methods 0.000 claims description 9
- 239000002184 metal Substances 0.000 claims description 6
- 229910052751 metal Inorganic materials 0.000 claims description 6
- 238000001816 cooling Methods 0.000 claims description 5
- XTUSEBKMEQERQV-UHFFFAOYSA-N propan-2-ol;hydrate Chemical compound O.CC(C)O XTUSEBKMEQERQV-UHFFFAOYSA-N 0.000 claims description 5
- 238000001132 ultrasonic dispersion Methods 0.000 claims description 5
- 239000003973 paint Substances 0.000 claims description 3
- 238000001291 vacuum drying Methods 0.000 claims description 3
- 239000010963 304 stainless steel Substances 0.000 claims description 2
- 229910001209 Low-carbon steel Inorganic materials 0.000 claims description 2
- 229910000589 SAE 304 stainless steel Inorganic materials 0.000 claims description 2
- 238000005119 centrifugation Methods 0.000 claims description 2
- 238000005536 corrosion prevention Methods 0.000 claims description 2
- 239000005028 tinplate Substances 0.000 claims description 2
- 238000005260 corrosion Methods 0.000 abstract description 8
- 230000007797 corrosion Effects 0.000 abstract description 7
- 239000000758 substrate Substances 0.000 abstract description 7
- 229920001690 polydopamine Polymers 0.000 description 27
- 230000000052 comparative effect Effects 0.000 description 15
- 230000002209 hydrophobic effect Effects 0.000 description 14
- 239000000463 material Substances 0.000 description 14
- 238000010438 heat treatment Methods 0.000 description 13
- 230000000694 effects Effects 0.000 description 11
- 238000002474 experimental method Methods 0.000 description 11
- 235000019441 ethanol Nutrition 0.000 description 9
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 7
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 6
- 239000010935 stainless steel Substances 0.000 description 6
- 229910001220 stainless steel Inorganic materials 0.000 description 6
- AFCARXCZXQIEQB-UHFFFAOYSA-N N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical class O=C(CCNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 AFCARXCZXQIEQB-UHFFFAOYSA-N 0.000 description 5
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 4
- 238000004364 calculation method Methods 0.000 description 4
- 230000008878 coupling Effects 0.000 description 4
- 238000010168 coupling process Methods 0.000 description 4
- 238000005859 coupling reaction Methods 0.000 description 4
- RSKGMYDENCAJEN-UHFFFAOYSA-N hexadecyl(trimethoxy)silane Chemical compound CCCCCCCCCCCCCCCC[Si](OC)(OC)OC RSKGMYDENCAJEN-UHFFFAOYSA-N 0.000 description 4
- 238000002329 infrared spectrum Methods 0.000 description 4
- 239000011259 mixed solution Substances 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 239000012798 spherical particle Substances 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- HQYALQRYBUJWDH-UHFFFAOYSA-N trimethoxy(propyl)silane Chemical compound CCC[Si](OC)(OC)OC HQYALQRYBUJWDH-UHFFFAOYSA-N 0.000 description 4
- TUQLLQQWSNWKCF-UHFFFAOYSA-N trimethoxymethylsilane Chemical compound COC([SiH3])(OC)OC TUQLLQQWSNWKCF-UHFFFAOYSA-N 0.000 description 4
- 238000005299 abrasion Methods 0.000 description 3
- 238000010521 absorption reaction Methods 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- YGUFXEJWPRRAEK-UHFFFAOYSA-N dodecyl(triethoxy)silane Chemical compound CCCCCCCCCCCC[Si](OCC)(OCC)OCC YGUFXEJWPRRAEK-UHFFFAOYSA-N 0.000 description 3
- 239000011780 sodium chloride Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 230000003746 surface roughness Effects 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- 230000002194 synthesizing effect Effects 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- 229910021529 ammonia Inorganic materials 0.000 description 2
- 229910052736 halogen Inorganic materials 0.000 description 2
- 150000002367 halogens Chemical class 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 231100000331 toxic Toxicity 0.000 description 2
- 230000002588 toxic effect Effects 0.000 description 2
- 240000002853 Nelumbo nucifera Species 0.000 description 1
- 235000006508 Nelumbo nucifera Nutrition 0.000 description 1
- 235000006510 Nelumbo pentapetala Nutrition 0.000 description 1
- 244000137852 Petrea volubilis Species 0.000 description 1
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 1
- -1 alkyl DTES Chemical compound 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 230000003373 anti-fouling effect Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000005234 chemical deposition Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000003618 dip coating Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 238000000707 layer-by-layer assembly Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 238000000643 oven drying Methods 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 238000007747 plating Methods 0.000 description 1
- 238000005498 polishing Methods 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
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- 238000009210 therapy by ultrasound Methods 0.000 description 1
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Abstract
The invention discloses a super-hydrophobic composite material, a preparation method and application thereof. The preparation method of the super-hydrophobic composite material comprises the following steps: (1) Mixing absolute ethyl alcohol, water and alkaline solution, adding tetraethoxysilane, reacting to obtain SiO 2 A nanoparticle; (2) Dopamine hydrochloride and SiO 2 Mixing the nano particles, reacting, adding dodecyl trimethoxy silane, and reacting again to obtain a composite material; (3) And (3) dissolving the coupling agent in an organic solvent, adding the composite material, and stirring for reaction to obtain the super-hydrophobic composite material. The super-hydrophobic composite material obtained by the preparation method is coated on the surface of the substrate, has good bonding performance with the substrate, is not easy to peel off, and reduces the average corrosion rate of the formed coating by more than 50 percent.
Description
Technical Field
The invention relates to the field of high polymer materials, in particular to a super-hydrophobic composite material, a preparation method and application thereof.
Background
In recent years, inspired by the lotus leaf effect, the superhydrophobic surface has attracted extensive scientific attention due to its unique wettability. Researchers have found that by varying the chemical composition of the solid surface as well as the surface morphology, regulation of the wetting properties of the solid surface can be achieved. The literature indicates that the existing methods for preparing the super-hydrophobic composite material comprise an etching method, a chemical deposition method, an optical plating method, a layer-by-layer assembly method, a plasma technology method and the like, the operation process of the methods is complex, equipment is expensive, the durability, the mechanical stability and the like of the prepared coating are poor, the application of the prepared coating is limited in industry, the halogen-containing hydrophobic material is widely applied to the preparation research of the hydrophobic material due to the excellent physical and chemical properties of the halogen-containing hydrophobic material, but the problems of environmental friendliness, manufacturing cost and the like are also limited in industry. Therefore, an environment-friendly, low-cost, abrasion-resistant and simple-process superhydrophobic coating is to be developed.
Disclosure of Invention
The invention aims at overcoming the defects and shortcomings of the prior art and providing a preparation method of a super-hydrophobic composite material.
The invention also aims to provide the super-hydrophobic composite material prepared by the preparation method.
It is a further object of the present invention to provide the use of the above superhydrophobic composite.
The aim of the invention is achieved by the following technical scheme: a preparation method of a super-hydrophobic composite material comprises the following steps:
(1) Preparation of SiO 2 Nanoparticles
Mixing absolute ethyl alcohol, water and alkaline solution, adding tetraethoxysilane, reacting to obtain SiO 2 A nanoparticle;
(2) Preparation of composite materials
Combining dopamine hydrochloride with SiO of the step (1) 2 Mixing the nano particles, reacting, adding dodecyl trimethoxy silane, reacting again, cooling, centrifuging, washing and drying to obtain a composite material;
(3) And (3) dissolving a coupling agent in an organic solvent, adding the composite material in the step (2), and stirring for reaction to obtain the super-hydrophobic composite material.
The dosage of the absolute ethyl alcohol in the step (1) is 50-100 according to the volume ratio of the absolute ethyl alcohol to the tetraethoxysilane: 4-12 proportion calculation; preferably, the volume ratio of the tetraethoxysilane to the tetraethoxysilane is 90: and (5) calculating the ratio of 10.
The water consumption in the step (1) is 1-50 according to the volume ratio of the water to the tetraethoxysilane: 4-12 proportion calculation; preferably, the volume ratio of the tetraethoxysilane to the tetraethoxysilane is 10: and (5) calculating the ratio of 10.
The water in the step (1) is deionized water.
The alkaline solution in the step (1) is one or more than two of ammonia water, naOH solution and KOH solution; preferably ammonia.
The concentration of the ammonia water is 25-30% by mass; preferably 28% by mass.
The volume ratio of the ammonia water to the tetraethoxysilane is 1-5: 4-12 proportion calculation; preferably, the volume ratio of the tetraethoxysilane to the tetraethoxysilane is 4: and (5) calculating the ratio of 10.
The mixing condition in the step (1) is that stirring is carried out for 10-40 min at 300-700 rpm under the temperature of 35-45 ℃; preferably 600rpm at 40 ℃.
The reaction condition in the step (1) is 20-50 ℃ for 5-9 h; preferably at 40℃for 5h.
The reaction described in step (1) was carried out at a stirring speed of 600rpm.
The reaction time in the step (2) is 16-24 hours; preferably 24h.
The time of the re-reaction in the step (2) is 5-9 h; preferably 5h.
The re-reaction described in step (2) was carried out at a stirring speed of 600rpm.
The cooling in step (2) is cooling to room temperature.
The speed of centrifugation described in step (2) was 6000r/min.
The washing in the step (2) is to wash to neutrality by adopting deionized water and absolute ethyl alcohol.
The drying in the step (2) is vacuum drying to constant weight.
The temperature of the vacuum drying is 25-70 ℃; preferably 60 ℃.
The ratio of the consumption of the dopamine hydrochloride, the dodecyl trimethoxysilane and the ethyl orthosilicate in the step (2) is 0.1-0.8 g: 2-10 mL: 4-12 mL of the mixture ratio is calculated; preferably the ratio of the amount of dopamine hydrochloride, dodecyl trimethoxysilane and ethyl orthosilicate in step (1) is 0.6g:2mL:10mL of the mixture ratio is calculated.
The coupling agent in the step (3) is one or more than two of KH-550, KH-560, methyltriethoxysilane and dimethyldiethoxysilane; methyltriethoxysilane and dimethyldiethoxysilane are preferred.
The concentration of the coupling agent in the step (3) in the organic solvent is 2-50% by volume; preferably 15-45% by volume; more preferably 23.8% by volume.
The coupling agent in the step (3) and the composite material obtained in the step (2) are mixed according to the proportion of 1.25-3.75: 0.2 to 1.0 proportion calculation; preferably, the coupling agent and the composite material obtained in the step (2) are mixed according to 3.75mL:0.6g of the mixture ratio is calculated.
The organic solvent in the step (3) is aqueous solution of isopropanol which is an organic solvent.
The aqueous solution of the isopropyl alcohol is prepared from the isopropyl alcohol and water according to the volume ratio of 1-3: 3-1 proportion; preferably, the ratio of the isopropanol to the water is 3:1 by volume.
The mode of dissolving the coupling agent in the organic solvent in the step (3) is ultrasonic dispersion.
The ultrasonic dispersion time is 3-30 min; preferably 10min.
The stirring reaction in the step (3) is 300-700 rpm stirring reaction for 0.1-0.5 h.
The super-hydrophobic composite material is prepared by the preparation method.
The application of the super-hydrophobic composite material in metal corrosion prevention.
The metal is preferably one of 304 stainless steel, low carbon steel and tinplate.
The application method comprises the following steps: adding the super-hydrophobic composite material into a coating, stirring and mixing uniformly at 20-70 ℃, and coating the coating on the metal surface to form a coating.
The pH value of the paint is 2-11; preferably 4.
The stirring speed is 300-700 rpm; preferably 600rpm.
The stirring time is 5-360 min.
Compared with the prior art, the invention has the following advantages and effects:
(1) The super-hydrophobic composite material is directly coated on the surface of a substrate, has good bonding performance with the substrate, is not easy to peel off, and reduces the average corrosion rate of the formed coating by more than 50 percent.
(2) The preparation method of the super-hydrophobic composite material is simple, has no harsh reaction conditions, is environment-friendly, does not need toxic organic solvents, and has the advantages of readily available raw materials, wide sources and no toxic byproducts.
(3) According to the invention, by changing parameter conditions such as the reactant dosage, the reaction temperature, the alkaline matter dosage, the reaction time, the rotating speed and the like, the obtained super-hydrophobic composite material has higher hydrophobic performance, and the existence of the super-hydrophobic composite material means that the composite coating achieves better self-cleaning, antifouling and deicing effects in natural environment, and finally, the composite coating can be widely applied in the anti-corrosion field.
Drawings
FIG. 1 is an infrared spectrum (IR) diagram of the superhydrophobic composite prepared in example 1.
Fig. 2 is a field emission Scanning Electron Microscope (SEM) image of the superhydrophobic composite prepared in example 1.
FIG. 3 is a graph showing the results of the water contact angle test after the abrasion resistance test of the superhydrophobic composite prepared in example 1.
Fig. 4 is a graph of the results of contact angle measurements for the different hydrophobic materials of comparative example 13.
Detailed Description
The present invention will be described in further detail with reference to examples and drawings, but embodiments of the present invention are not limited thereto. The specific conditions are not specified, and the process is carried out according to conventional conditions or conditions suggested by manufacturers. The reagents or apparatus used were conventional products commercially available without the manufacturer's attention.
DTMS: dodecyl trimethoxy silane; DTES: dodecyl triethoxy silane; HTMS: hexadecyltrimethoxysilane; APTES: 3-aminopropyl triethoxysilane; TMMS: trimethoxymethylsilane; TMPS: trimethoxypropylsilane.
Example 1
(1) Polydopamine/DTMS/SiO 2 Synthesis of composite materials: adding 90mL of absolute ethyl alcohol and 10mL of deionized water into a four-necked flask, adding 4mL of ammonia water with the mass fraction of 28%, heating to 40 ℃, keeping the constant temperature, and stirring at 600rpm for 40min; slowly dropwise adding 10mL of ethyl orthosilicate into the four-neck flask, and reacting for 5 hours at a stirring speed of 600 rpm; adding 0.6g of dopamine hydrochloride into the four-neck flask, and reacting for 24 hours; 2mL of DTMS was further added to the four-necked flask, and the reaction was carried out at a stirring speed of 600rpm for 5 hours. Centrifuging at 6000r/min, washing with deionized water and absolute ethanol to neutrality, and vacuum oven drying at 60deg.C to constant weight to obtain polydopamine/DTMS/SiO 2 A composite material.
(2) Polydopamine/DTMS/SiO 2 Synthesizing the super-hydrophobic composite material: 2.5mL of dimethyldiethoxysilane and 1.25mL of methyltriethoxysilane are weighed and dispersed in 12mL of isopropanol water solution (the ratio of isopropanol to water is 3:1 by volume) for 10min in an ultrasonic manner, and then 0.6g of polydopamine/DTMS/SiO prepared in the step (1) is added 2 The composite material reacts for 0.5h at the stirring speed of 600rpm to obtain polydopamine/DTMS/SiO 2 A superhydrophobic composite.
Polydopamine/DTMS/SiO prepared in this example 1 2 The infrared spectrum (IR) test result of the super-hydrophobic composite material is shown in FIG. 1, and the wave number is 1100cm -1 Is SiO 2 Absorption peak, 1630cm -1 、1400cm -1 Is characterized by the characteristic absorption peak of benzene ring, 3410cm -1 The broad peak is the absorption peak of hydroxyl or amino, which indicates that the polydopamine/DTMS/SiO 2 Super-hydrophobic composite materials have been successfully synthesized. FIG. 2 is a schematic diagram of polydopamine/DTMS/SiO 2 As can be seen from a field emission Scanning Electron Microscope (SEM) image of the super-hydrophobic composite material, spherical particles with uniform size are generated in the reaction process, and the spherical particles are closely arranged, so that the surface roughness is increased, and good hydrophobicity is provided. FIG. 3 is a schematic diagram of polydopamine/DTMS/SiO 2 The super-hydrophobic composite material is subjected to wear resistance experiments (poly dopamine/DTMS/SiO) 2 The super-hydrophobic composite material is loaded with 200g weight, the water contact angle is measured after the super-hydrophobic composite material is worn for 0 to 300 times on 2000-mesh sand paper and the surface is cleaned every 30 times (5 mu L of deionized water is dripped on polydopamine/DTMS/SiO by a micro-metering sample injector by adopting a sitting drip method) 2 The surface of the super-hydrophobic composite material, the contact angle change of which is measured by a water contact angle measuring instrument). The graph shows that after multiple times of abrasion, the surface of the material still has ultrahigh hydrophobicity, which proves that the composite material has good bonding performance with a substrate and is not easy to peel off.
Example 2
(1) Polydopamine/DTMS/SiO 2 Synthesis of composite materials: adding 50mL of absolute ethyl alcohol and 50mL of deionized water into a four-necked flask, adding 5mL of ammonia water with the mass fraction of 25%, heating to 35 ℃, keeping the constant temperature, and stirring for 10min at 300 rpm; 12mL of ethyl orthosilicate is slowly added dropwise into the four-necked flask, and the reaction is carried out for 7h at the stirring speed of 600 rpm; adding 0.2g of dopamine hydrochloride into the four-neck flask, and reacting for 16 hours; to the four-necked flask, 10mL of DTMS was further added, and the reaction was carried out at a stirring speed of 600rpm for 7 hours. Centrifuging at 6000r/min, washing with deionized water and absolute ethanol to neutrality, and drying in vacuum oven at 40deg.C to constant weight to obtain polydopamine/DTMS/SiO 2 A composite material.
(2) Polydopamine/DTMS/SiO 2 Synthesizing the super-hydrophobic composite material: 2.5mL of dimethyldiethoxysilane and 1mL of methyltriethoxysilane are weighed and dispersed in 12mL of isopropanol water solution (the ratio of isopropanol to water is 3:2 by volume) for 20min in an ultrasonic manner, and then 1g of polydopamine/DTMS/SiO prepared in the step (1) is added 2 The composite material reacts for 0.2h at the stirring speed of 700rpm to obtain polydopamine/DTMS/SiO 2 A superhydrophobic composite.
The generated super-hydrophobic composite material is spherical particles with uniform size, is compact in arrangement, increases in surface roughness and has good hydrophobicity.
Example 3
(1) Polydopamine/DTMS/SiO 2 Synthesis of composite materials: adding 100mL of absolute ethyl alcohol and 10mL of deionized water into a four-necked flask, adding 1mL of ammonia water with the mass fraction of 30%, heating to 45 ℃, keeping the constant temperature, and stirring for 30min at 500 rpm; slowly dripping 4mL of ethyl orthosilicate into the four-neck flask, and reacting for 9h at a stirring speed of 600 rpm; adding 0.8g of dopamine hydrochloride into the four-neck flask, and reacting for 20 hours; to the four-necked flask, 6mL of DTMS was further added, and the reaction was carried out at a stirring speed of 600rpm for 9 hours. Centrifuging at 6000r/min, washing with deionized water and absolute ethanol to neutrality, and drying in vacuum oven at 70deg.C to constant weight to obtain polydopamine/DTMS/SiO 2 A composite material.
(2) Polydopamine/DTMS/SiO 2 Synthesizing the super-hydrophobic composite material: 1.5mL of dimethyldiethoxysilane and 0.5mL of methyltriethoxysilane are weighed and dispersed in 12mL of isopropanol water solution (the ratio of isopropanol to water is 1:1 by volume) for 30min in an ultrasonic manner, and then 0.3g of polydopamine/DTMS/SiO prepared in the step (1) is added 2 The composite material reacts for 0.5h at the stirring speed of 300rpm to obtain polydopamine/DTMS/SiO 2 A superhydrophobic composite.
The generated super-hydrophobic composite material is spherical particles with uniform size, is compact in arrangement, increases in surface roughness and has good hydrophobicity.
Comparative example 1
SiO was prepared in the step (1) of example 1 2 The ratio of the absolute ethanol to the deionized water used was adjusted to 100:0, 80:20, 70:30, 60:40, 50:50. The experimental procedure of example 1 was followed, adding different proportions of absolute ethanol and deionized water, and adding 4mL of 28% ammonia by mass, heating to 40 ℃, and stirring at 600rpm for 40min; slowly dropwise adding 10mL of ethyl orthosilicate into the four-neck flask, and reacting for 5 hours at a stirring speed of 600 rpm; the subsequent procedure was the same as in example 1. The results demonstrate that the ratio of absolute ethanol to deionized water was adjusted to 100:0, 80:20, 70:30, 60:40, 50:50The best effect is obtained in example 1, in which the water contact angle is 92 degrees, 138 degrees, 130 degrees, 132 degrees, 134 degrees, and the ratio of absolute ethyl alcohol to deionized water is 90:10, and the water contact angle is 157 degrees.
Comparative example 2
Preparation of SiO by step (1) of example 1 2 The rotational speeds in the process were adjusted to 700rpm, 500rpm, 400rpm, 300rpm, respectively. The experimental procedure of example 1 was followed by adding 90mL of ethanol, 10mL of deionized water and 28% mass fraction of 4mL of aqueous ammonia to a four-necked flask, heating to 40 ℃ and stirring at different rotational speeds for 40min; slowly dripping 10mL of ethyl orthosilicate into the four-necked flask, and reacting for 5h; the subsequent procedure was the same as in example 1. As a result, it was found that the best results were obtained when the water contact angles at the rotational speeds of 700rpm, 500rpm, 400rpm and 300rpm were 142 °, 138 °, 136 ° and 130 ° respectively, and the water contact angles at the rotational speeds of 600rpm were 157 ° in example 1.
Comparative example 3
Preparation of SiO by step (1) in example 1 2 The ammonia water in the process is adjusted to be 5mL, 3mL, 2mL and 1mL. The experimental procedure of example 1 was followed by adding 90mL of ethanol, 10mL of deionized water and different amounts of 28% ammonia water by mass fraction into a four-necked flask, heating to 40 ℃, and stirring for 40min; slowly dropwise adding 10mL of ethyl orthosilicate into the four-neck flask, and reacting for 5 hours at a stirring speed of 600 rpm; the subsequent procedure was the same as in example 1. As a result, it was found that the water contact angle after the aqueous ammonia was adjusted to 5mL, 3mL, 2mL, and 1mL was 140 °, 136 °, 130 °, 134 °, and the water contact angle of example 1 in which the aqueous ammonia amount was 4mL was 157 °, and the effect was optimal.
Comparative example 4
The reaction temperature in example 1 was adjusted to 50 ℃, 45 ℃, 35 ℃,30 ℃, 25 ℃,20 ℃. The experimental procedure of example 1 was followed by adding 90mL of ethanol, 10mL of deionized water and 28% by mass of 4mL of ammonia water to each four-necked flask, heating to the above-mentioned different temperatures, and stirring at 600rpm for 40min; slowly dropwise adding 10mL of ethyl orthosilicate into the four-neck flask, and reacting for 5 hours at a stirring speed of 600 rpm; the subsequent procedure was the same as in example 1. As a result, it was confirmed that the water contact angle of example 1, in which the reaction temperature after adding ammonia water was 40℃was adjusted to be 50℃at 45℃at 35℃at 30℃at 25℃at 20℃at 125℃at 130℃at 134℃at 139℃at 136℃at 128℃and the water contact angle was 157℃at the best.
Comparative example 5
The amounts of ethyl orthosilicate used in example 1 were adjusted to 12mL, 8mL, 6mL, and 4mL. The experimental procedure of example 1 was followed by adding 90mL of ethanol, 10mL of deionized water and 4mL of 28% ammonia water by mass fraction to a four-necked flask, heating to 40℃and stirring at 600rpm for 40min; slowly dripping different amounts of ethyl orthosilicate into the four-neck flask, and reacting for 5 hours at a stirring speed of 600 rpm; the subsequent procedure was the same as in example 1. As a result, it was found that the water contact angles of 12mL, 8mL, 6mL and 4mL were 137 °, 140 °, 134 ° and 120℃and the water contact angles of example 1 in which the amount of ethyl orthosilicate was 10mL were 157℃and the best results were obtained.
Comparative example 6
The amount of dopamine hydrochloride in example 1 was adjusted to 0.1g, 0.2g, 0.4g and 0.8g. The experimental procedure of example 1 was followed by adding 90mL of ethanol and 10mL of deionized water to a four-necked flask, adding 4mL of 28% ammonia water by mass fraction, heating to 40 ℃, and stirring at 600rpm for 40min; slowly dropwise adding 10mL of ethyl orthosilicate into the four-neck flask, and reacting for 5 hours at a stirring speed of 600 rpm; the dopamine hydrochloride with different amounts is added respectively and reacted for 24 hours. The subsequent procedure was the same as in example 1. The water contact angles of 0.1g, 0.2g, 0.4g and 0.8g of dopamine hydrochloride are 120 degrees, 126 degrees, 136 degrees and 142 degrees, and the water contact angle of the example 1 with 0.6g of dopamine hydrochloride is 157 degrees, so that the best effect is achieved.
Comparative example 7
The reaction time after the addition of ethyl orthosilicate in example 1 was adjusted to 1h, 3h, 7h, 9h. The experimental procedure of example 1 was followed by adding 90mL of ethanol and 10mL of deionized water to a four-necked flask, adding 4mL of 28% ammonia water by mass, heating to 40℃and stirring at 600rpm for 40min; slowly dropwise adding 10mL of ethyl orthosilicate into the four-neck flask, wherein the reaction time is respectively as described above; the subsequent procedure was the same as in example 1. The results prove that the water contact angles after the reaction time is adjusted to 1h, 3h, 7h and 9h are 100 degrees, 116 degrees, 148 degrees and 145 degrees, the water contact angle of the example 1 with the reaction time length of 5h after the ethyl orthosilicate is added is 157 degrees, and the best effect is obtained.
Comparative example 8
The reaction time after adding dopamine hydrochloride in example 1 was adjusted to 4h, 8h, 12h, 16h, 20h. The experimental procedure of example 1 was followed by adding 90mL of ethanol and 10mL of deionized water, respectively, to a four-necked flask, adding 4mL of 28% ammonia water by mass fraction, heating to 40℃and stirring at 600rpm for 40min; slowly dripping 10mL of ethyl orthosilicate into the four-neck flask, and reacting for 5h; adding 0.6g of dopamine hydrochloride into the four-necked flask, wherein the reaction time is respectively as described above; the subsequent procedure was the same as in example 1. The results prove that the water contact angles after the reaction time is adjusted to be 4h, 8h, 12h, 16h and 20h are 105 degrees, 121 degrees, 130 degrees, 140 degrees and 147 degrees, and the water contact angle of the example 1 with the reaction time length of 24h after the dopamine hydrochloride is added is 157 degrees, so that the best effect is achieved.
Comparative example 9
The reaction time after addition of DTMS in example 1 was adjusted to 1h, 3h, 7h, 9h. The experimental procedure of example 1 was followed by adding 90mL of ethanol and 10mL of deionized water, respectively, to a four-necked flask, adding 4mL of 28% ammonia water by mass fraction, heating to 40℃and stirring at 600rpm for 40min; slowly dripping 10mL of ethyl orthosilicate into the four-neck flask, and reacting for 5h; adding 0.6g of dopamine hydrochloride into the four-neck flask, and reacting for 24 hours; then adding 2mL of DTMS into the four-neck flask, wherein the reaction time is respectively as described above; the subsequent procedure was the same as in example 1. The results prove that the water contact angles after the reaction time is adjusted to 1h, 3h, 7h and 9h are 100 degrees, 121 degrees, 146 degrees and 143 degrees, the water contact angle of the example 1 with the reaction time length of 5h after the DTMS is added is 157 degrees, and the best effect is obtained.
Comparative example 10
The amount of DTMS used in example 1 was adjusted to 4mL, 6mL, 8mL, and 10mL. The experimental procedure of example 1 was followed by adding 90mL of ethanol and 10mL of deionized water, respectively, to a four-necked flask, adding 4mL of 28% ammonia water by mass fraction, heating to 40℃and stirring at 600rpm for 40min; slowly dripping 10mL of ethyl orthosilicate into the four-neck flask, and reacting for 5h; adding 0.6g of dopamine hydrochloride into the four-neck flask, and reacting for 24 hours; respectively adding the DTMS with the dosage, and reacting for 5 hours at the stirring speed of 600 rpm; the subsequent procedure was the same as in example 1. As a result, the water contact angles of the DTMS with respect to 4mL, 6mL, 8mL and 10mL were 138 °, 136 °, 130 ° and 125 °, and the water contact angle of the DTMS with respect to 2mL was 157 °, which gave the best results.
Comparative example 11
The total concentration of dimethyldiethoxysilane and methyltriethoxysilane of the coupling agent in example 1 in the aqueous isopropanol solution was adjusted to 5%, 15%, 25%, 35%, 45% by volume, and the procedure before the addition of the coupling agent was the same as in example 1. Respectively weighing dimethyl diethoxy silane and methyl triethoxy silane, adding the dimethyl diethoxy silane and the methyl triethoxy silane into 12mL of mixed solution of isopropanol and water (the ratio of the isopropanol to the water is 3:1 by volume), and performing ultrasonic dispersion for 10min, wherein the total concentration of the mixed solution is the volume ratio. Then 0.6g of polydopamine/DTMS/SiO prepared in step (1) of example 1 was added 2 The composite material reacts for 0.5h at the stirring speed of 600rpm to obtain polydopamine/DTMS/SiO 2 A superhydrophobic composite. The best effect is obtained in example 1, wherein the water contact angles of the coupling agent in the isopropanol aqueous solution are 136 degrees, 140 degrees, 152 degrees, 148 degrees and 145 degrees, the volume ratio is 5 percent, 15 percent, 25 percent, 35 percent and 45 percent, and the total concentration of the coupling agent in the isopropanol aqueous solution is 23.8 percent.
Comparative example 12
Adding polydopamine/DTMS/SiO to step (2) of example 1 2 The amounts of the composite materials used were adjusted to 0.2g, 0.4g, 0.8g, 1.0g, and the procedure before coupling was the same as in example 1. 1.5g of dimethyldiethoxysilane and 0.75g of methyltriethoxysilane are respectively weighed into 12mL of mixed solution of isopropanol and water (the ratio of isopropanol to water is 3:1 by volume), and the mixed solution is dispersed for 10min by ultrasonic. Then adding the polydopamine/DTMS/SiO of example 1 with different quality respectively 2 The composite material reacts for 0.5h at the stirring speed of 600rpm to obtain polydopamine/DTMS/SiO 2 A superhydrophobic composite. The dosage of the composite material is adjusted to be 0.2g, 0.4g, 0.8g and 1.0g, the water contact angle is 142 degrees, 145 degrees, 148 degrees and 150 degrees, and 0.6g of polydopamine/DTMS/SiO is added 2 The composite material of example 1 had a water contact angle of 157 deg. and was most effective.
Comparative example 13
(1) The hydrophobic material was obtained by coupling the same procedure as in step (2) of example 1, except that the DTMS in example 1 was replaced with long-chain alkyl DTES, HTMS, APTES, TMMS, TMPS in an amount of 2 mL.
(2) Adding 0.6g of dopamine hydrochloride into a four-neck flask after the reaction of the ethyl orthosilicate in the embodiment 1, reacting for 24 hours, cooling the obtained substance to room temperature, centrifuging at 6000r/min, washing with deionized water and absolute ethyl alcohol to neutrality, drying in a vacuum oven at 60 ℃ to constant weight, and coupling by adopting the same method in the step (2) of the embodiment 1 to obtain the hydrophobic material.
(3) 2mL of DTMS and DTES, HTMS, APTES, TMMS, TMPS were added to each of the four-necked flasks after the reaction of ethyl orthosilicate in example 1, and the reaction was carried out at a stirring speed of 600rpm for 5 hours. Centrifuging at 6000r/min, washing with deionized water and absolute ethanol to neutrality, drying in a vacuum oven at 60deg.C to constant weight, and coupling by the same method as in step (2) of example 1 to obtain hydrophobic material.
As shown in fig. 4, under the same reaction conditions, the hydrophobicity of the hydrophobic material prepared by modifying without dopamine hydrochloride is lower than that of the hydrophobic material prepared by modifying with dopamine hydrochloride; and under the same reaction condition, the super-hydrophobic composite material obtained in the embodiment 1 has the best effect in the hydrophobic material prepared by modifying different long-chain alkyl groups with dopamine hydrochloride.
Example 3 detection of Corrosion resistance of coatings
Preparation of the coating: the preparation method comprises the steps of taking a Q235 stainless steel sheet (100 mm is 10mm is 0.5 mm) as a substrate, carrying out sand blasting and polishing on the substrate, carrying out ultrasonic treatment by using acetone, removing oil and dirt, coating the super-hydrophobic composite material prepared in the example 1 and the hydrophobic material obtained by modifying the dodecyl trimethoxysilane in the comparative example 13 on the surface of the stainless steel sheet by using a dip coating method (directly immersing the stainless steel sheet in the hydrophobic material, coating the stainless steel sheet by using a coating machine in an up-and-down motion of 30 times per minute), and then drying the stainless steel sheet under a vacuum condition to obtain two coatings.
And (3) detecting corrosion resistance of the coating: a NaCl solution with a mass fraction of 10% was prepared, and the two coatings and the Q235 stainless steel sheet were immersed in a sodium chloride solution, and their corrosion resistance was as shown in Table 1 below.
TABLE 1 Corrosion resistance test results (10% NaCl solution)
As can be seen from table 1, the average corrosion rate of the composite coating prepared from the superhydrophobic composite of example 1 was reduced by more than 50% relative to the composite coating prepared from the dodecyltrimethoxysilane modified hydrophobic material.
The data show that the super-hydrophobic composite material can be well applied to anticorrosive paint.
The above examples are preferred embodiments of the present invention, but the embodiments of the present invention are not limited to the above examples, and any other changes, modifications, substitutions, combinations, and simplifications that do not depart from the spirit and principle of the present invention should be made in the equivalent manner, and the embodiments are included in the protection scope of the present invention.
Claims (5)
1. The preparation method of the super-hydrophobic composite material is characterized by comprising the following steps of:
(1) Preparation of SiO 2 Nanoparticles
Mixing absolute ethyl alcohol, water and alkaline solution, adding tetraethoxysilane, reacting to obtain SiO 2 A nanoparticle;
(2) Preparation of composite materials
Combining dopamine hydrochloride with SiO of the step (1) 2 Mixing the nano particles, reacting, adding dodecyl trimethoxy silane, reacting again, cooling, centrifuging, washing and drying to obtain a composite material;
(3) Dissolving a coupling agent in an organic solvent, adding the composite material in the step (2), and stirring for reaction to obtain a super-hydrophobic composite material;
the dosage of the absolute ethyl alcohol in the step (1) is 90 according to the volume ratio of the absolute ethyl alcohol to the tetraethoxysilane: 10, proportioning and calculating;
the water consumption in the step (1) is 10 according to the volume ratio of the water to the tetraethoxysilane: 10, proportioning and calculating;
the alkaline solution in the step (1) is ammonia water;
the concentration of the ammonia water is 28% by mass;
the volume ratio of the ammonia water to the tetraethoxysilane is 4:10, proportioning and calculating;
the mixing condition in the step (1) is that stirring is carried out for 40min at 600rpm at 40 ℃;
the reaction in the step (1) is carried out at a stirring speed of 600 rpm;
the reaction condition in the step (1) is that the reaction is carried out at 40 ℃ for 5h;
the ratio of the amount of dopamine hydrochloride, dodecyl trimethoxysilane and ethyl orthosilicate in the step (2) to the amount of ethyl orthosilicate in the step (1) is 0.6g:2mL:10 Calculating the ratio of mL;
the reaction time in step (2) was 24h;
the time for the re-reaction in step (2) was 5h;
the re-reaction in step (2) is a reaction at a stirring speed of 600 rpm;
the coupling agent in the step (3) is methyltriethoxysilane and dimethyldiethoxysilane;
the concentration of the coupling agent in the step (3) in the organic solvent is 15-45% by volume;
the coupling agent in the step (3) and the composite material obtained in the step (2) are mixed according to the ratio of 3.75 to mL:0.6g, proportioning and calculating;
the organic solvent in the step (3) is isopropanol water solution;
the volume ratio of the isopropanol to the water in the isopropanol water solution is 1-3: 3-1;
and (3) stirring reaction at 300-700 rpm for 0.1-0.5 h.
2. The method for preparing the super-hydrophobic composite material according to claim 1, wherein,
the water in the step (1) is deionized water;
the speed of centrifugation in the step (2) is 6000 r/min;
the washing in the step (2) is to wash to neutrality by adopting deionized water and absolute ethyl alcohol;
the drying in the step (2) is vacuum drying to constant weight.
3. The method for preparing the super-hydrophobic composite material according to claim 1, wherein,
the mode of dissolving the coupling agent in the organic solvent in the step (3) is ultrasonic dispersion;
the ultrasonic dispersion time is 3-30 min.
4. A superhydrophobic composite prepared by the preparation method of any one of claims 1-3.
5. The application of the super-hydrophobic composite material in metal corrosion prevention as claimed in claim 4, wherein the application method is as follows: adding the super-hydrophobic composite material in the coating, stirring and mixing uniformly at 20-70 ℃, and coating the coating on the metal surface to form a coating;
the pH value of the paint is 2-11;
the metal is one of 304 stainless steel, low carbon steel and tinplate.
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| KR20170129336A (en) * | 2016-05-16 | 2017-11-27 | 단국대학교 산학협력단 | Superhydrophobic aluminum plate with nanoparticles coating and method of manufacturing the same |
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| KR20170129336A (en) * | 2016-05-16 | 2017-11-27 | 단국대학교 산학협력단 | Superhydrophobic aluminum plate with nanoparticles coating and method of manufacturing the same |
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