CN113105764A - Method for constructing hydrophobic material with micro-nano structure on surface by one-step method - Google Patents
Method for constructing hydrophobic material with micro-nano structure on surface by one-step method Download PDFInfo
- Publication number
- CN113105764A CN113105764A CN202110344107.8A CN202110344107A CN113105764A CN 113105764 A CN113105764 A CN 113105764A CN 202110344107 A CN202110344107 A CN 202110344107A CN 113105764 A CN113105764 A CN 113105764A
- Authority
- CN
- China
- Prior art keywords
- micro
- hydrophobic material
- nano structure
- constructing
- step method
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 230000002209 hydrophobic effect Effects 0.000 title claims abstract description 93
- 239000000463 material Substances 0.000 title claims abstract description 85
- 239000002086 nanomaterial Substances 0.000 title claims abstract description 45
- 238000000034 method Methods 0.000 title claims abstract description 39
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims abstract description 32
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 claims abstract description 29
- 229910000077 silane Inorganic materials 0.000 claims abstract description 24
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 claims abstract description 23
- 239000003607 modifier Substances 0.000 claims abstract description 22
- 238000003756 stirring Methods 0.000 claims abstract description 22
- 239000002244 precipitate Substances 0.000 claims abstract description 20
- 238000010992 reflux Methods 0.000 claims abstract description 16
- 238000006243 chemical reaction Methods 0.000 claims abstract description 14
- NBVXSUQYWXRMNV-UHFFFAOYSA-N fluoromethane Chemical compound FC NBVXSUQYWXRMNV-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000006087 Silane Coupling Agent Substances 0.000 claims abstract description 11
- 238000001291 vacuum drying Methods 0.000 claims abstract description 11
- 238000005406 washing Methods 0.000 claims abstract description 10
- 238000000227 grinding Methods 0.000 claims abstract description 9
- 230000002378 acidificating effect Effects 0.000 claims abstract description 8
- 238000007873 sieving Methods 0.000 claims abstract description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 35
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 24
- GUJOJGAPFQRJSV-UHFFFAOYSA-N dialuminum;dioxosilane;oxygen(2-);hydrate Chemical compound O.[O-2].[O-2].[O-2].[Al+3].[Al+3].O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O GUJOJGAPFQRJSV-UHFFFAOYSA-N 0.000 claims description 24
- 229910052901 montmorillonite Inorganic materials 0.000 claims description 20
- 239000008367 deionised water Substances 0.000 claims description 14
- 229910021641 deionized water Inorganic materials 0.000 claims description 14
- ZHPNWZCWUUJAJC-UHFFFAOYSA-N fluorosilicon Chemical compound [Si]F ZHPNWZCWUUJAJC-UHFFFAOYSA-N 0.000 claims description 13
- 239000002904 solvent Substances 0.000 claims description 12
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical group CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 10
- XDLMVUHYZWKMMD-UHFFFAOYSA-N 3-trimethoxysilylpropyl 2-methylprop-2-enoate Chemical compound CO[Si](OC)(OC)CCCOC(=O)C(C)=C XDLMVUHYZWKMMD-UHFFFAOYSA-N 0.000 claims description 9
- 239000000126 substance Substances 0.000 claims description 7
- 239000010445 mica Substances 0.000 claims description 6
- 229910052618 mica group Inorganic materials 0.000 claims description 6
- 239000000454 talc Substances 0.000 claims description 6
- 229910052623 talc Inorganic materials 0.000 claims description 6
- LFQCEHFDDXELDD-UHFFFAOYSA-N tetramethyl orthosilicate Chemical compound CO[Si](OC)(OC)OC LFQCEHFDDXELDD-UHFFFAOYSA-N 0.000 claims description 5
- 238000002156 mixing Methods 0.000 claims description 4
- BPSIOYPQMFLKFR-UHFFFAOYSA-N trimethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CO[Si](OC)(OC)CCCOCC1CO1 BPSIOYPQMFLKFR-UHFFFAOYSA-N 0.000 claims description 4
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 claims description 2
- 229940089951 perfluorooctyl triethoxysilane Drugs 0.000 claims description 2
- BVQYIDJXNYHKRK-UHFFFAOYSA-N trimethoxy(3,3,4,4,5,5,6,6,7,7,8,8,8-tridecafluorooctyl)silane Chemical compound CO[Si](OC)(OC)CCC(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)F BVQYIDJXNYHKRK-UHFFFAOYSA-N 0.000 claims description 2
- 229910052615 phyllosilicate Inorganic materials 0.000 abstract description 19
- 239000010410 layer Substances 0.000 abstract description 7
- 238000002360 preparation method Methods 0.000 abstract description 6
- 238000012986 modification Methods 0.000 abstract description 5
- 238000009830 intercalation Methods 0.000 abstract description 4
- 230000002687 intercalation Effects 0.000 abstract description 4
- 239000011229 interlayer Substances 0.000 abstract description 4
- 238000001308 synthesis method Methods 0.000 abstract description 4
- VDRSDNINOSAWIV-UHFFFAOYSA-N [F].[Si] Chemical group [F].[Si] VDRSDNINOSAWIV-UHFFFAOYSA-N 0.000 abstract description 3
- 230000000694 effects Effects 0.000 abstract description 3
- 230000004048 modification Effects 0.000 abstract description 3
- 229910000323 aluminium silicate Inorganic materials 0.000 description 17
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 16
- 239000000047 product Substances 0.000 description 15
- 239000011159 matrix material Substances 0.000 description 7
- 229920000642 polymer Polymers 0.000 description 7
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Inorganic materials [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 description 7
- 239000011248 coating agent Substances 0.000 description 6
- 238000000576 coating method Methods 0.000 description 6
- 230000008569 process Effects 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 5
- 238000001816 cooling Methods 0.000 description 5
- 239000000428 dust Substances 0.000 description 5
- 239000002245 particle Substances 0.000 description 5
- 230000002265 prevention Effects 0.000 description 5
- 235000012222 talc Nutrition 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- IOLCXVTUBQKXJR-UHFFFAOYSA-M potassium bromide Chemical compound [K+].[Br-] IOLCXVTUBQKXJR-UHFFFAOYSA-M 0.000 description 4
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 3
- 238000002441 X-ray diffraction Methods 0.000 description 3
- 238000010521 absorption reaction Methods 0.000 description 3
- 238000004140 cleaning Methods 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
- 239000004744 fabric Substances 0.000 description 3
- 239000011737 fluorine Substances 0.000 description 3
- 229910052731 fluorine Inorganic materials 0.000 description 3
- 238000002329 infrared spectrum Methods 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- 230000003075 superhydrophobic effect Effects 0.000 description 3
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 2
- 229910001579 aluminosilicate mineral Inorganic materials 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 229910052681 coesite Inorganic materials 0.000 description 2
- 229910052906 cristobalite Inorganic materials 0.000 description 2
- 239000004205 dimethyl polysiloxane Substances 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 239000000945 filler Substances 0.000 description 2
- -1 fluoroalkyl silane Chemical compound 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- 238000006460 hydrolysis reaction Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000010907 mechanical stirring Methods 0.000 description 2
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 230000003068 static effect Effects 0.000 description 2
- 229910052682 stishovite Inorganic materials 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 229910052905 tridymite Inorganic materials 0.000 description 2
- NNJPGOLRFBJNIW-HNNXBMFYSA-N (-)-demecolcine Chemical compound C1=C(OC)C(=O)C=C2[C@@H](NC)CCC3=CC(OC)=C(OC)C(OC)=C3C2=C1 NNJPGOLRFBJNIW-HNNXBMFYSA-N 0.000 description 1
- HJIMAFKWSKZMBK-UHFFFAOYSA-N 3,3,4,4,5,5,6,6,7,7,8,8,9,9,10,10,10-heptadecafluorodecyl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)CCC(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)F HJIMAFKWSKZMBK-UHFFFAOYSA-N 0.000 description 1
- 240000002853 Nelumbo nucifera Species 0.000 description 1
- 235000006508 Nelumbo nucifera Nutrition 0.000 description 1
- 235000006510 Nelumbo pentapetala Nutrition 0.000 description 1
- 229910018557 Si O Inorganic materials 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical group [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 238000003917 TEM image Methods 0.000 description 1
- 230000003373 anti-fouling effect Effects 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000006073 displacement reaction Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000002296 dynamic light scattering Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 230000005661 hydrophobic surface Effects 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229920002379 silicone rubber Polymers 0.000 description 1
- 238000003980 solgel method Methods 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
Images
Classifications
-
- 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
- C09D1/00—Coating compositions, e.g. paints, varnishes or lacquers, based on inorganic substances
-
- 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
- C09D183/08—Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen, and oxygen
Abstract
The invention discloses a method for constructing a hydrophobic material with a micro-nano structure on the surface by a one-step method, which comprises the following steps: reacting a silane coupling agent, polyhydroxy silane, isopropanol, fluorocarbon silane and layered silicate under an acidic condition, refluxing and stirring, centrifugally washing to obtain a precipitate, and then carrying out vacuum drying, grinding and sieving to obtain the fluorosilicone modifier/layered silicate hydrophobic material with a micro-nano structure. In the reaction process, the layered silicate with large specific surface area is used as a base material, and SiO is connected on the surface of the base material and interlayer grafting or intercalation reaction2The long-chain hydrophobic fluorine-silicon group of the core greatly improves the hydrophobicity of the phyllosilicate, and effectively increases the roughness of the surface of the phyllosilicate sheet layer through surface modification, thereby achieving stable hydrophobic performance. The preparation method of the hydrophobic material adopts a one-step synthesis method, and has controllable reaction, simple operation and high yieldAnd (5) effect.
Description
Technical Field
The invention belongs to a hydrophobic material, and particularly relates to a method for constructing a hydrophobic material with a micro-nano structure on the surface by a one-step method.
Background
In recent years, hydrophobic materials attract people to pay attention due to antifouling, anti-adhesion and hydrophobic functions, and the hydrophobic materials are widely applied to the fields of fabric water resistance, stain resistance, oil-water separation, agricultural film dust prevention and the like. However, the current large-scale application of hydrophobic materials is limited by the disadvantages of complex process, high cost, difficulty in dispersion in the substrate, etc. Therefore, the development of the hydrophobic material with simple process, low cost and excellent performance is of great significance.
Hydrophobic materials have been widely studied since the 21 st century, and two methods are generally adopted for preparing hydrophobic materials, namely, a rough micro-nano structure is constructed, and a low surface energy group is modified on the rough micro-nano structure. Liu et al 2017 prepared a transparent and self-cleaning super-hydrophobic coating from long-chain fluoroalkyl silane by a sol-gel method. The coating surface presents a rough, wrinkled, mound-like morphology, resembling the microstructure of lotus leaves (rough micro-scale papilla), with superhydrophobicity. Japanese scientists Yoshihiro Yamauchi and Masanobu Naito in 2019 constructed a wear-resistant micron-sized needle-shaped super-hydrophobic structure on the surface of a matrix by dissolving Polydimethylsiloxane (PDMS) in ethyl acetate, adding micron-sized four-pin ZnO into the solution and adopting a spraying method. The hydrophobic material has good roughness and low surface energy, but the wide application of the hydrophobic material is influenced by the problems of complex processing technology, high cost, difficult dispersion and the like.
The layered aluminosilicate is an aggregate of layered aluminosilicate minerals, and is a particulate particle of hydrous layered aluminosilicate mineral having a disordered transition structure. The basic structural units of layered aluminosilicates are divided into tetrahedral sheets and octahedral sheets. The layered aluminosilicate has lattice displacement, electronegativity and ion exchange properties which determine the expansibility and suspendability of the layered aluminosilicate in an aqueous system, but prevent the layered aluminosilicate from being compatible with a polymer matrix. Because the layered aluminosilicate has low cost and wide sources, the surface energy of the layered aluminosilicate is fully reduced, the hydrophobic property is improved, and the compatibility and the stability of the layered aluminosilicate in a polymer matrix are enhanced.
In order to improve the hydrophobic property, researches show that the nano SiO modified by fluorine silicon is found2The coating prepared by doping montmorillonite and silicon rubber has good hydrophobic effect (CN 103305122A), but the method is only simple physical mixing, the coating is easy to age under the illumination, the service life of the coating is shortened, and the application of the coating in the practical production is limited due to the severe feeding speed.
Disclosure of Invention
The purpose of the invention is as follows: aiming at the problems in the prior art, the invention provides the preparation method of the hydrophobic material which has the advantages of simple raw materials, simple synthetic steps, capability of carrying out reaction under an acidic condition, no requirement on the feeding speed and excellent hydrophobic property. The invention grafts or intercalates the fluorine-silicon modifier on the surface and among layers of the phyllosilicate in a chemical bond mode by a one-step method, so that the phyllosilicate has good and stable hydrophobic property, and can be better applied to the fields of self-cleaning, dust prevention and the like of polymers as a filler.
The invention also provides a one-step method for constructing the fluorosilicone modifier/layered silicate hydrophobic material with the micro-nano structure.
The technical scheme is as follows: in order to achieve the aim, the invention provides a method for constructing a hydrophobic material with a micro-nano structure by a one-step method, which comprises the following steps:
reacting a silane coupling agent, polyhydroxy silane, isopropanol, layered silicate and fluorocarbon silane under an acidic condition, refluxing and stirring, centrifugally washing to obtain a precipitate, and finally performing vacuum drying, grinding and sieving on the precipitate to obtain the fluorine-silicon modified layered silicate hydrophobic material with a micro-nano structure.
Wherein the mass ratio of (A) to (B) is 0.1-0.5: 2.8-4: 5-12: 3.5-10: 1.5-3.5 mixing silane coupling agent, polyhydroxy silane, isopropanol solvent, layered silicate and fluorocarbon silane, and adding concentrated hydrochloric acid to adjust the pH value to 3-5.
Further, deionized water is added in the reaction, and the mass ratio of the deionized water to the layered silicate is (1-2): 3.5 to 10.
Wherein the temperature is 60-80 ℃, and the reflux stirring is carried out for 8-12 hours.
Preferably, 0.1g to 0.5g of silane coupling agent, 2.8g to 4g of polyhydroxy silane, 5g to 12g of isopropanol solvent, 3.5g to 10g of layered silicate, 1g to 2g of deionized water and 1.5g to 3.5g of fluorocarbon silane are taken, concentrated hydrochloric acid is added to adjust the pH value to be 3 to 5, the temperature is 60 ℃ to 80 ℃, and the reflux stirring is carried out for 8 to 12 hours.
Wherein the sample adding sequence is silane coupling agent, polyhydroxy silane, isopropanol, layered aluminosilicate, deionized water, fluorocarbon silane and concentrated hydrochloric acid in sequence.
Wherein the concentration of the concentrated hydrochloric acid is 11-12mol/L, and the dripping amount is 1-2 drops.
Wherein the stirring is mechanical stirring, and the stirring speed is 300-500 r/min.
Wherein, after the centrifugal water washing is carried out for 2 to 3 times, brown precipitates are obtained.
Wherein the vacuum drying is carried out at the temperature of 40-60 ℃ for 20-24 h, the vacuum degree is 6.7-8.7 Pa, and the mesh number of the screen is 100-300 meshes.
Preferably, the vacuum drying is carried out at the temperature of 50 ℃ for 24h, the vacuum degree is 8.7Pa, and the number of the screens is 100 meshes.
Wherein the silane coupling agent is any one of gamma-aminopropyltriethoxysilane (KH-550), gamma- (2, 3-epoxypropoxy) propyltrimethoxysilane (KH-560) and gamma-methacryloxypropyltrimethoxysilane (KH-570).
Wherein the polyhydroxy silane is Tetraethoxysilane (TEOS) or methyl orthosilicate (TMOS).
Wherein the fluorocarbon silane is any one of 1H,1H,2H, 2H-Perfluorooctyltrimethoxysilane (PFOTS), 1H,2H, 2H-Perfluorooctyltriethoxysilane (PFOTS) and 1H,1H,2H, 2H-Perfluorodecyltrimethoxysilane (PFDTS).
Wherein the phyllosilicate is an inorganic substance with a lamellar structure, and comprises any one of montmorillonite, talc and mica.
Preferably, the layered silicate is an inorganic substance having a layered structure of various types in the prior art. Such as any one of montmorillonite, talc, mica, etc., can be modified by the above method of the present invention to achieve better effects. More preferably, the phyllosilicate is montmorillonite.
The fluorosilicone modifier/layered silicate hydrophobic material with the micro-nano structure prepared by the method for constructing the hydrophobic material with the micro-nano structure by the one-step method is provided.
The fluorosilicone modifier/phyllosilicate hydrophobic material with the micro-nano structure has an average particle size of about 1 mu m.
The hydrophobic material has a micro-nano structure and a low surface energy substance, wherein the fluorocarbon silane provides the low surface energy substance F. In the reaction process, the layered silicate with large specific surface area is used as a base material, and SiO is connected on the surface of the base material and interlayer grafting or intercalation reaction2The long-chain hydrophobic fluorine-silicon group of the core greatly improves the hydrophobicity of the phyllosilicate, and effectively increases the roughness of the surface of the phyllosilicate sheet layer through surface modification, thereby achieving stable hydrophobic performance. The preparation method provided by the invention is a one-step method for constructing the fluorosilicone modifier/layered silicate hydrophobic material with the micro-nano structure, and the preparation method is controllable in reaction and simple to operate.
The hydrophobic material prepared by the invention has lower surface energy and certain roughness. The fluorine-silicon modifier is combined on the sheet layer of the phyllosilicate by grafting and intercalation, provides fluorine-containing chain links with low surface energy, and then generates spherical nano SiO connected with the fluorine-containing chain links by hydrolysis2The roughness of the layered silicate is increased by the center, so that the layered silicate has hydrophobic property, and simultaneously, the layered silicate provides a rough structure, so that the hydrophobicity of the material is better ensured. Meanwhile, the hydrophobic material has a simple synthesis process, and the actual operation is simple and efficient by adopting a one-step synthesis method.
The invention explores a two-step synthesis method in the early stage, namely hydrolysis is carried out under acidic condition to firstly generate SiO with fluorine-silicon modification2Secondly, the hydrophobic material reacts with the layered aluminosilicate or the silane coupling agent, the polyhydroxy silane, the isopropanol solvent and the layered silicate react under the acidic condition, the fluorocarbon silane is added into the hydrophobic material, and the hydrophobic material is stirred under reflux to prepare the hydrophobic material with poor effect2In the process of generating the spherical structure, the spherical structure can fully react with layered aluminosilicate, and meanwhile, the stability of the spherical structure is enhanced by the form of the chemical bond, so that the hydrophobic property is greatly improved, and the application of the spherical structure in a polymer matrix is enhanced. Meanwhile, the invention simplifies the experimental steps, the reaction is carried out under the acidic condition by a mode of adding raw materials in one step, the sample adding speed has no requirement, the fluorosilicone modifier/layered aluminosilicate hydrophobic material with a remarkable micro-nano structure is synthesized, the process is simple and convenient to operate, and the hydrophobic effect is obvious. The hydrophobic material prepared by the method has good hydrophobic property and the structural characteristics of the layered aluminosilicate, and can better solve the problem that the layered aluminosilicate is not well dispersed in a polymer matrix, so that the hydrophobic material can be widely used as a filler in the fields of fabric water resistance and pollution resistance, oil-water separation, agricultural film dust prevention and the like.
Has the advantages that: compared with the prior art, the invention has the following advantages:
(1) in the reaction process, the layered silicate with a layered structure is used as a matrix, has a large specific surface area and is nano SiO with fluorine-containing silicon chain links2The center provides more carrier sites, provides a rough structure required by a hydrophobic surface, and simultaneously, silicate with a layered structure modifies fluorine-silicon groups on the surface or between layers, the layered structure can effectively protect the fluorine-silicon hydrophobic groups from being damaged, and a hydrophobic material with good hydrophobicity and more stability is generated in a chemical bond form.
(2) The one-step method has the advantages of simple reaction conditions, no requirement on sample adding speed, and better application in practical production, so that the practical operation is simple and efficient.
(3) The hydrophobic material prepared by the invention has the advantages of low cost of synthetic raw materials and simple process, and can obtain more excellent hydrophobic effect by adopting a one-step synthetic method.
(4) The hydrophobic material prepared by the invention can better disperse in a polymer matrix by improving the hydrophobicity of the layered aluminosilicate, thereby being better applied to the fields of polymer dust prevention, fabric water and dirt resistance, oil-water separation, agricultural film dust prevention, self cleaning and the like.
Drawings
FIG. 1 is a Scanning Electron Microscope (SEM) image of a hydrophobic material with a micro-nano structure;
FIG. 2 is a Transmission Electron Microscope (TEM) image of a hydrophobic material with a micro-nano structure;
FIG. 3 is a dynamic light scattering particle size Distribution (DLS) diagram of a hydrophobic material with a micro-nano structure;
FIG. 4 is an X-ray diffraction pattern (XRD) of a hydrophobic material with a micro-nano structure;
FIG. 5 is an infrared spectrum (FTIR) of a hydrophobic material with micro-nano structure;
FIG. 6 is a static water contact angle test chart (WCA) of a hydrophobic material with a micro-nano structure;
FIG. 7 is a static water contact angle test chart (WCA) of the hydrophobic material of comparative example 1.
Detailed Description
The present invention is further illustrated by the following examples.
The experimental methods described in the examples are all conventional methods unless otherwise specified; the reagents and materials are commercially available, unless otherwise specified. Wherein the phyllosilicate can be selected from conventional commercially available montmorillonite, talc, mica, etc.
Example 1
Step 1, 0.3g KH-570 and 3.4g TEOS are taken in sequence, 10g isopropanol solvent and 10g montmorillonite are added, 1.5g deionized water and 2.5g PFOTES are added, the pH value is adjusted to 4 by 12mol/L concentrated hydrochloric acid, the temperature is 60 ℃, the reflux stirring is carried out, the stirring is carried out for 12 hours, and the rotating speed is 500 r/min.
And 2, cooling the product to room temperature, and washing the product with 2 times of centrifugal water to obtain brown precipitate.
And 3, finally, carrying out vacuum drying on the brown precipitate (the temperature is 50 ℃, the time is 24 hours, the vacuum degree is 8.7Pa), and grinding and sieving by using a 100-mesh sieve to obtain the fluorosilicone modified montmorillonite hydrophobic material with the micro-nano structure.
Scanning Electron Microscope (SEM) of the fluorosilicone modifier/montmorillonite hydrophobic material with a micro-nano structure prepared in example 1 is shown in fig. 1, and a sample shows a layered structure stripped by montmorillonite and a rough surface on the surface due to grafting of the fluorosilicone modifier. Transmission Electron Micrograph (TEM) as shown in fig. 2, due to intercalation and surface grafting of the fluorosilicone modifier, a relatively dispersed lamellar structure is shown, the surface is rough, the red arrow marks the montmorillonite lamellar, the circle refers to the nano spherical SiO2And is about 47.6 nm. The hydrated particle size (DLS) results of fig. 3 show that the average particle size of the hydrophobic material is around 1 μm. XRD analysis is shown in figure 4, the angle of a 001-plane secondary diffraction peak 2 theta of original MMT is 5.83 degrees, the MMT is intercalated and moves to 5.62 degrees in the small angle direction, the spacing is increased by 0.0559nm calculated by a Bragg equation, the interlayer spacing of the montmorillonite is shown to be 1.53nm by calculation, after the surface modification and the fluorine-silicon modifier are intercalated into the montmorillonite, the montmorillonite is obviously deviated in the small angle direction, and the interlayer spacing is increased to 1.5859nm, which indicates that the fluorine-silicon modifier is successfully intercalated into a montmorillonite layer.
Example 2
Step 1, 0.3g KH-570 and 3.4g TEOS are taken in sequence, 10g isopropanol solvent and 3.5g talcum are added, 1.5g deionized water and 2.5g PFOTES are added, the pH value is adjusted to 4 by 12mol/L concentrated hydrochloric acid, the temperature is 60 ℃, the reflux stirring is carried out, the stirring is carried out for 12 hours, and the rotating speed is 500 r/min.
And 2, cooling the product to room temperature, and washing the product with 2 times of centrifugal water to obtain brown precipitate.
And 3, finally, carrying out vacuum drying on the brown precipitate (the temperature is 50 ℃, the time is 24 hours, and the vacuum degree is 8.7Pa), and grinding and sieving by using a 100-mesh sieve to obtain the fluorosilicone modified talc hydrophobic material with the micro-nano structure.
Example 3
Step 1, 0.3g of KH-570 and 3.4g of TEOS are taken in sequence, 10g of isopropanol solvent and 5.56g of mica are added, 1.5g of deionized water and 2.5g of PFOTES are added, the pH value is adjusted to 4 by 12mol/L concentrated hydrochloric acid, the temperature is 60 ℃, reflux stirring is carried out, and the stirring is carried out for 12 hours at the rotating speed of 500 r/min.
And 2, cooling the product to room temperature, and washing the product with 2 times of centrifugal water to obtain brown precipitate.
And 3, finally, carrying out vacuum drying on the brown precipitate (the temperature is 50 ℃, the time is 24 hours, and the vacuum degree is 8.7Pa), and grinding and sieving by using a 100-mesh sieve to obtain the fluorine-silicon modified mica hydrophobic material with the micro-nano structure.
Example 4
Step 1, 0.1g KH-550 and 4.0g TEOS are taken in sequence, 5g isopropanol solvent and 3.5g montmorillonite are added, 1.5g deionized water and 1.5g PFDTS are added, the pH value is adjusted to 3 by 12mol/L concentrated hydrochloric acid, the temperature is 60 ℃, reflux stirring is carried out, stirring is carried out for 12 hours, and the rotating speed is 300 r/min.
And 2, cooling the product to room temperature, and washing the product with 2 times of centrifugal water to obtain brown precipitate.
And 3, finally, carrying out vacuum drying on the brown precipitate (the temperature is 60 ℃, the time is 20 hours, and the vacuum degree is 6.7Pa), and grinding and sieving by using a 100-mesh sieve to obtain the fluorosilicone modified montmorillonite hydrophobic material with the micro-nano structure.
Example 5
Step 1, sequentially taking 0.5g KH-560 and 2.8g TMOS, adding 12g isopropanol solvent and 10g montmorillonite, adding 2g deionized water and 3.5g PFDTS, adjusting the pH value to 5 by using 12mol/L concentrated hydrochloric acid, carrying out reflux stirring at the temperature of 80 ℃, and stirring for 8 hours at the rotating speed of 300 r/min.
And 2, cooling the product to room temperature, and washing the product with 2 times of centrifugal water to obtain brown precipitate.
And 3, finally, carrying out vacuum drying on the brown precipitate (the temperature is 50 ℃, the time is 24 hours, and the vacuum degree is 8.7Pa), and grinding and sieving by using a 100-mesh sieve to obtain the fluorosilicone modified montmorillonite hydrophobic material with the micro-nano structure.
Example 6
Example 1 determination of functional groups of the fluorosilicone modifier/layered silicate hydrophobic material having a micro-nano structure prepared.
Mixing the fluorine silicon modifier/layered silicate hydrophobic material (the hydrophobic material prepared in example 1) with potassium bromide (the mass ratio of potassium bromide to the sample is 100:1), grinding, tabletting, testing by using a Brookalpha II Fourier transform infrared spectrometer, and scanning within the range of 4000-500 cm--1. Fig. 5 shows the absorption peaks of different functional groups at different wavelengths, the upper red line is the infrared spectrum of the fluorosilicone modifier/phyllosilicate montmorillonite, and the lower blue line is the infrared spectrum of phyllosilicate montmorillonite. The infrared spectrogram comparing the fluorine-silicon modifier/the phyllosilicate and the phyllosilicate of the invention is found to be 3628cm-1The position shows the stretching vibration of an O-H bond in the octahedral framework of the phyllosilicate; 3456cm-1、1643cm-1The absorption peak is the stretching vibration and bending vibration of H-O-H bond caused by crystal water or absorbed water between the layers of the phyllosilicate; 2975 and 2899cm-1Is represented by-CH3、-CH2The stretching vibration peak of (1); 1090cm-1And a strong Si-O symmetrical stretching vibration peak exists. Except that the two were found to differ primarily in the location of the fluorosilicone modifier at 1440cm-1-CF3Absorption peak of bond. In conclusion, the fluorosilicone modifier/phyllosilicate is successfully modified and prepared, namely the fluorosilicone modified montmorillonite hydrophobic material with the micro-nano structure.
Example 7
And (3) testing the water contact angle of the fluorosilicone modifier/layered silicate hydrophobic material with the micro-nano structure prepared in the embodiment 1.
First, a double-sided tape was fixed to one surface of a glass slide, 1g of a fluorosilicone modifier/layered silicate hydrophobic material (the hydrophobic material prepared in example 1) was spread on the double-sided tape, and then an excess sample was blown off using an ear-washing bulb, and a contact angle thereof was measured with deionized water. When the contact angle was measured using a droplet shape analyzer (DSA30S), the volume of the droplet was 8 μ L. The surface of the sample was tested at 5 different positions, and the average value was taken as the test value. FIG. 6 shows that the hydrophobic property of the material is good, the water contact angle reaches 147.68 degrees, the material is close to super-hydrophobic, and the material has good hydrophobic property.
Comparative experiment
Comparative example 1: (1) sequentially taking 0.3g KH-570 and 3.4g TEOS, adding 10g isopropanol solvent, 1.5g deionized water and 2.5g PFOTES, adjusting pH to 4 with 12mol/L concentrated hydrochloric acid, adjusting temperature to 60 ℃, refluxing and stirring for 6 hours at the rotating speed of 500r/min to generate the fluorine-silicon modified nano SiO2。
(2) And (3) adding 10g of montmorillonite into the product obtained in the step (1), refluxing and stirring at the temperature of 60 ℃ for 12 hours at the rotating speed of 500 r/min.
(2) After the product was cooled to room temperature, it was washed with 2 times of centrifugal water to obtain a brown precipitate.
(3) Finally, the brown precipitate is dried in vacuum (temperature: 50 ℃, time: 24h, vacuum degree: 8.7Pa), ground and sieved by a 100-mesh sieve to obtain the hydrophobic material.
Comparative example 2: (1) 0.3g KH-570 and 3.4g TEOS are taken in turn, 10g isopropanol solvent and 10g montmorillonite are added into the mixture, the pH value is adjusted to 4 by 12mol/L concentrated hydrochloric acid, the temperature is 60 ℃, the mechanical stirring is carried out for 15 minutes, and the rotating speed is 500 r/min.
(2) And (3) adding 1.5g of deionized water and 2.5g of PFOTES into the product obtained in the step (1), and stirring under reflux at the temperature of 60 ℃ for 12 hours at the rotating speed of 500 r/min.
(2) After the product was cooled to room temperature, it was washed with 2 times of centrifugal water to obtain a brown precipitate.
(3) Finally, the brown precipitate is dried in vacuum (temperature: 50 ℃, time: 24h, vacuum degree: 8.7Pa), ground and sieved by a 100-mesh sieve to obtain the hydrophobic material.
As can be seen from the above comparative experiments, the present invention adopts the existing two-step synthesis method, such as the preparation of SiO with fluorine-silicon modification2And then reacting with layered aluminosilicate to finally prepare the product with a contact angle of about 140 degrees (figure 7). The silane coupling agent, polyhydroxy silane, isopropanol solvent and phyllosilicate react under acidic condition, fluorocarbon silane is added into the silane, and the material prepared by reflux stirring has poor effect and contact angle of less than 140 degrees. The hydrophobic material prepared by the one-step method is 147.68 degrees, so that the hydrophobic property can be better improved by one-step synthesis, the reaction is more thorough, the preparation method is simpler, the layered aluminosilicate is hydrophilic, the water contact angle degree is 0 degree, and the hydrophobic material is modified by a specific method to finally reach 147.68 degrees.
Claims (10)
1. A method for constructing a hydrophobic material with a micro-nano structure by a one-step method is characterized by comprising the following steps:
reacting a silane coupling agent, polyhydroxy silane, isopropanol, layered silicate and fluorocarbon silane under an acidic condition, refluxing and stirring, centrifugally washing to obtain a precipitate, and finally performing vacuum drying, grinding and sieving on the precipitate to obtain the fluorine-silicon modified layered silicate hydrophobic material with a micro-nano structure.
2. The one-step method for constructing the hydrophobic material with the micro-nano structure according to claim 1, wherein the mass ratio of the hydrophobic material with the micro-nano structure to the hydrophobic material with the micro-nano structure is 0.1-0.5: 2.8-4: 5-12: 3.5-10: 1.5-3.5 mixing silane coupling agent, polyhydroxy silane, isopropanol solvent, layered silicate and fluorocarbon silane, and adding concentrated hydrochloric acid to adjust the pH value to 3-5.
3. The one-step method for constructing the hydrophobic material with the micro-nano structure according to claim 1 or 2, wherein deionized water is preferably added in the reaction, and the mass ratio of the deionized water to the layered silicate is 1-2: 3.5 to 10.
4. The one-step method for constructing the hydrophobic material with the micro-nano structure according to claim 1, wherein the reaction temperature is 60-80 ℃, and the reflux stirring is carried out for 8-12 hours.
5. The one-step method for constructing the hydrophobic material with the micro-nano structure according to claim 1, wherein the temperature of the vacuum drying is 40-60 ℃, the time is 20-24 h, the vacuum degree is 6.7-8.7 Pa, and the mesh number of the screen is 100-300 meshes.
6. The one-step method for constructing the hydrophobic material with the micro-nano structure according to claim 1, wherein the silane coupling agent is any one of gamma-aminopropyltriethoxysilane (KH-550), gamma- (2, 3-epoxypropoxy) propyltrimethoxysilane (KH-560) and gamma-methacryloxypropyltrimethoxysilane (KH-570).
7. The one-step method for constructing the hydrophobic material with the micro-nano structure according to claim 1, wherein the polyhydroxysilane is Tetraethoxysilane (TEOS) or methyl orthosilicate (TMOS).
8. The one-step method for constructing hydrophobic materials with micro-nano structures according to claim 1, wherein the fluorocarbon silane is any one of 1H,1H,2H, 2H-Perfluorooctyltrimethoxysilane (PFOTS), 1H,2H, 2H-Perfluorooctyltriethoxysilane (PFOTES), 1H,2H, 2H-Perfluorodecyltrimethoxysilane (PFDTS).
9. The one-step method for constructing the hydrophobic material with the micro-nano structure according to claim 1, wherein the layered silicate is an inorganic substance with a layered structure, and comprises any one of montmorillonite, talc and mica.
10. The fluorosilicone modifier/layered silicate hydrophobic material with the micro-nano structure prepared by the one-step method for constructing the hydrophobic material with the micro-nano structure according to claim 1.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110344107.8A CN113105764B (en) | 2021-03-30 | 2021-03-30 | Method for constructing hydrophobic material with micro-nano structure on surface by one-step method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110344107.8A CN113105764B (en) | 2021-03-30 | 2021-03-30 | Method for constructing hydrophobic material with micro-nano structure on surface by one-step method |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN113105764A true CN113105764A (en) | 2021-07-13 |
| CN113105764B CN113105764B (en) | 2022-10-04 |
Family
ID=76713015
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202110344107.8A Active CN113105764B (en) | 2021-03-30 | 2021-03-30 | Method for constructing hydrophobic material with micro-nano structure on surface by one-step method |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN113105764B (en) |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103305122A (en) * | 2013-07-03 | 2013-09-18 | 华北电力大学 | Montmorillonite-silicon dioxide super-hydrophobic coating and preparation method thereof |
| CN106189832A (en) * | 2016-07-13 | 2016-12-07 | 华南理工大学 | Organopolysilazane/inorganic nano material super-hydrophobic coat and preparation method thereof |
| WO2017215544A1 (en) * | 2016-06-14 | 2017-12-21 | 中国科学院理化技术研究所 | Preparation method for hydrophobic inorganic powder material |
| CN109867846A (en) * | 2019-01-14 | 2019-06-11 | 山东农业大学 | A kind of dust-proof insulating agricultural film and preparation method thereof based on super-hydrophobic hydrotalcite |
-
2021
- 2021-03-30 CN CN202110344107.8A patent/CN113105764B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103305122A (en) * | 2013-07-03 | 2013-09-18 | 华北电力大学 | Montmorillonite-silicon dioxide super-hydrophobic coating and preparation method thereof |
| WO2017215544A1 (en) * | 2016-06-14 | 2017-12-21 | 中国科学院理化技术研究所 | Preparation method for hydrophobic inorganic powder material |
| CN106189832A (en) * | 2016-07-13 | 2016-12-07 | 华南理工大学 | Organopolysilazane/inorganic nano material super-hydrophobic coat and preparation method thereof |
| CN109867846A (en) * | 2019-01-14 | 2019-06-11 | 山东农业大学 | A kind of dust-proof insulating agricultural film and preparation method thereof based on super-hydrophobic hydrotalcite |
Also Published As
| Publication number | Publication date |
|---|---|
| CN113105764B (en) | 2022-10-04 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN111534162B (en) | Montmorillonite-based photocatalytic super-hydrophobic coating and preparation method thereof | |
| CN105646944B (en) | A kind of preparation method of organically-modified molybdenum disulfide nano sheet | |
| CN108380062B (en) | High-flux hydrophilic-oleophobic oil-water separation membrane with antibacterial function and preparation and application thereof | |
| CN109943902A (en) | A kind of modified polyester fiber and preparation method | |
| CN112125335B (en) | Micro-nano titanium dioxide, preparation method and application | |
| CN108003710A (en) | A kind of super-hydrophobic visible light photocatalysis automatic cleaning coating and preparation method thereof | |
| CN115109471A (en) | Modified silica aerogel thermal insulation coating and preparation method thereof | |
| El-Nahhal et al. | Synthesis and characterization of silica-, meso-silica-and their functionalized silica-coated copper oxide nanomaterials | |
| CN113235172A (en) | Radiation refrigeration composite fiber and preparation method and application thereof | |
| CN109575732A (en) | A kind of self-cleaning nona Ti02-Si02/ fluorine-containing ester paint | |
| Zou et al. | One-step sol-gel preparation of ultralow-refractive-index porous coatings with mulberry-like hollow silica nanostructures | |
| CN109468874A (en) | A kind of super-hydrophobic transparent conductive paper and preparation method thereof | |
| CN111422877A (en) | Preparation method and surface modification method of nano silicon dioxide | |
| CN113105764B (en) | Method for constructing hydrophobic material with micro-nano structure on surface by one-step method | |
| CN113061357B (en) | Anti-reflection hydrophobic coating and preparation method thereof | |
| CN1291991C (en) | Preparation method of multihydroxy sesqui siloxane | |
| CN110386761B (en) | Preparation method of super-hydrophobic antireflection coating with high light transmittance | |
| CN108862304B (en) | Hydrophobic hybrid silicon-aluminum molecular sieve containing organic groups and having micro-nano hierarchical structure and preparation method thereof | |
| CN112194143A (en) | Preparation method of structural color-generating material with photocatalytic effect and stable structure | |
| Vero et al. | Homogeneous self-cleaning coatings on cellulose materials derived from TIP/TiO 2 P25 | |
| CN115784243A (en) | Preparation method for constructing monodisperse hollow-structure silicon oxide microsphere material by using salt as template | |
| CN114804648A (en) | Fluorine-free self-cleaning coating and preparation method and application thereof | |
| CN111073347A (en) | Preparation method of ultra-dispersed nano white carbon black for rubber filler | |
| CN113637337B (en) | Blue fluorescent carbon quantum dot modified super-hydrophobic material and preparation method and application thereof | |
| CN116135930A (en) | High-durability super-hydrophilic coating with antibacterial and antifogging properties and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |