CN105949499A - Preparation method for super-hydrophobic material - Google Patents
Preparation method for super-hydrophobic material Download PDFInfo
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- 239000000463 material Substances 0.000 title claims abstract description 66
- 230000003075 superhydrophobic effect Effects 0.000 title claims abstract description 46
- 238000002360 preparation method Methods 0.000 title claims abstract description 33
- 238000000034 method Methods 0.000 claims abstract description 23
- 239000000126 substance Substances 0.000 claims abstract description 11
- 239000002086 nanomaterial Substances 0.000 claims abstract description 6
- 239000002245 particle Substances 0.000 claims description 63
- 239000004926 polymethyl methacrylate Substances 0.000 claims description 41
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 40
- 229920003229 poly(methyl methacrylate) Polymers 0.000 claims description 39
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 36
- 239000010985 leather Substances 0.000 claims description 34
- 239000003643 water by type Substances 0.000 claims description 31
- 229960000935 dehydrated alcohol Drugs 0.000 claims description 28
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 24
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims description 23
- 239000002105 nanoparticle Substances 0.000 claims description 22
- 239000004744 fabric Substances 0.000 claims description 20
- OLGONLPBKFPQNS-UHFFFAOYSA-M sodium 2-(4-phenylphenyl)butanoate Chemical compound [Na+].CCC(C([O-])=O)c1ccc(cc1)-c1ccccc1 OLGONLPBKFPQNS-UHFFFAOYSA-M 0.000 claims description 20
- 239000004205 dimethyl polysiloxane Substances 0.000 claims description 17
- 238000004987 plasma desorption mass spectroscopy Methods 0.000 claims description 17
- 235000013870 dimethyl polysiloxane Nutrition 0.000 claims description 15
- CXQXSVUQTKDNFP-UHFFFAOYSA-N octamethyltrisiloxane Chemical compound C[Si](C)(C)O[Si](C)(C)O[Si](C)(C)C CXQXSVUQTKDNFP-UHFFFAOYSA-N 0.000 claims description 15
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 claims description 15
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 13
- 238000001035 drying Methods 0.000 claims description 11
- ABTOQLMXBSRXSM-UHFFFAOYSA-N silicon tetrafluoride Chemical compound F[Si](F)(F)F ABTOQLMXBSRXSM-UHFFFAOYSA-N 0.000 claims description 11
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 10
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 10
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 claims description 10
- 229910052681 coesite Inorganic materials 0.000 claims description 10
- 229910052906 cristobalite Inorganic materials 0.000 claims description 10
- 229910000077 silane Inorganic materials 0.000 claims description 10
- 239000000377 silicon dioxide Substances 0.000 claims description 10
- 229910052682 stishovite Inorganic materials 0.000 claims description 10
- 229910052905 tridymite Inorganic materials 0.000 claims description 10
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 9
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 claims description 9
- 229920003023 plastic Polymers 0.000 claims description 9
- 239000004033 plastic Substances 0.000 claims description 9
- 238000002156 mixing Methods 0.000 claims description 8
- FWDBOZPQNFPOLF-UHFFFAOYSA-N ethenyl(triethoxy)silane Chemical compound CCO[Si](OCC)(OCC)C=C FWDBOZPQNFPOLF-UHFFFAOYSA-N 0.000 claims description 7
- 229920000877 Melamine resin Polymers 0.000 claims description 6
- 238000013019 agitation Methods 0.000 claims description 6
- 239000000839 emulsion Substances 0.000 claims description 6
- 229960004756 ethanol Drugs 0.000 claims description 6
- 238000012986 modification Methods 0.000 claims description 6
- 230000004048 modification Effects 0.000 claims description 6
- 229910021529 ammonia Inorganic materials 0.000 claims description 5
- 239000002243 precursor Substances 0.000 claims description 4
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical class CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 3
- FPCJKVGGYOAWIZ-UHFFFAOYSA-N butan-1-ol;titanium Chemical compound [Ti].CCCCO.CCCCO.CCCCO.CCCCO FPCJKVGGYOAWIZ-UHFFFAOYSA-N 0.000 claims description 3
- 150000002823 nitrates Chemical class 0.000 claims description 3
- 229920002379 silicone rubber Polymers 0.000 claims description 3
- 239000004945 silicone rubber Substances 0.000 claims description 3
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 claims description 2
- 239000006185 dispersion Substances 0.000 claims description 2
- 208000011580 syndromic disease Diseases 0.000 claims description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 19
- 238000005516 engineering process Methods 0.000 abstract description 7
- 230000003068 static effect Effects 0.000 abstract description 4
- 239000011248 coating agent Substances 0.000 abstract description 2
- 238000000576 coating method Methods 0.000 abstract description 2
- 239000000758 substrate Substances 0.000 abstract description 2
- 238000003754 machining Methods 0.000 abstract 1
- 239000004753 textile Substances 0.000 description 22
- 229920005830 Polyurethane Foam Polymers 0.000 description 11
- 239000008367 deionised water Substances 0.000 description 10
- 229910021641 deionized water Inorganic materials 0.000 description 10
- 239000006260 foam Substances 0.000 description 10
- 238000005259 measurement Methods 0.000 description 10
- 238000012360 testing method Methods 0.000 description 10
- 241001062009 Indigofera Species 0.000 description 6
- 230000002209 hydrophobic effect Effects 0.000 description 5
- 238000010586 diagram Methods 0.000 description 3
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 239000011737 fluorine Substances 0.000 description 2
- 229910052731 fluorine Inorganic materials 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 239000011343 solid material Substances 0.000 description 2
- 229920000742 Cotton Polymers 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 238000010041 electrostatic spinning Methods 0.000 description 1
- 238000000608 laser ablation Methods 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000002210 silicon-based material Substances 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/36—After-treatment
- C08J9/40—Impregnation
-
- C—CHEMISTRY; METALLURGY
- C14—SKINS; HIDES; PELTS; LEATHER
- C14C—CHEMICAL TREATMENT OF HIDES, SKINS OR LEATHER, e.g. TANNING, IMPREGNATING, FINISHING; APPARATUS THEREFOR; COMPOSITIONS FOR TANNING
- C14C9/00—Impregnating leather for preserving, waterproofing, making resistant to heat or similar purposes
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M11/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising
- D06M11/32—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with oxygen, ozone, ozonides, oxides, hydroxides or percompounds; Salts derived from anions with an amphoteric element-oxygen bond
- D06M11/36—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with oxygen, ozone, ozonides, oxides, hydroxides or percompounds; Salts derived from anions with an amphoteric element-oxygen bond with oxides, hydroxides or mixed oxides; with salts derived from anions with an amphoteric element-oxygen bond
- D06M11/46—Oxides or hydroxides of elements of Groups 4 or 14 of the Periodic Table; Titanates; Zirconates; Stannates; Plumbates
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M11/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising
- D06M11/77—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with silicon or compounds thereof
- D06M11/79—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with silicon or compounds thereof with silicon dioxide, silicic acids or their salts
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
- D06M13/50—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with organometallic compounds; with organic compounds containing boron, silicon, selenium or tellurium atoms
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
- D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
- D06M15/21—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- D06M15/263—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of unsaturated carboxylic acids; Salts or esters thereof
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
- D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
- D06M15/37—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- D06M15/564—Polyureas, polyurethanes or other polymers having ureide or urethane links; Precondensation products forming them
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- D—TEXTILES; PAPER
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- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
- D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
- D06M15/37—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- D06M15/643—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds containing silicon in the main chain
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2361/00—Characterised by the use of condensation polymers of aldehydes or ketones; Derivatives of such polymers
- C08J2361/20—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen
- C08J2361/26—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen of aldehydes with heterocyclic compounds
- C08J2361/28—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen of aldehydes with heterocyclic compounds with melamine
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- D06M2101/00—Chemical constitution of the fibres, threads, yarns, fabrics or fibrous goods made from such materials, to be treated
- D06M2101/02—Natural fibres, other than mineral fibres
- D06M2101/04—Vegetal fibres
- D06M2101/06—Vegetal fibres cellulosic
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- D06M2200/00—Functionality of the treatment composition and/or properties imparted to the textile material
- D06M2200/10—Repellency against liquids
- D06M2200/12—Hydrophobic properties
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Textile Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
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- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- General Chemical & Material Sciences (AREA)
- Silicon Compounds (AREA)
Abstract
The invention provides a preparation method for a super-hydrophobic material. The method comprises the following steps: (1) modifying the integral three-dimensional structure of a substrate material by using a nanomaterial with a nanotechnology, so that the roughness of the integral three-dimensional structure of the material is increased; (2) coating the material with a low-surface-energy substance through a surface modifying technology to obtain the super-hydrophobic material. The static contact angle between the super-hydrophobic material and water is 152-158 degrees. The prepared super-hydrophobic material has superior hydrophobicity, the preparation process is simple, the reaction conditions are mild, and special machining equipment is not needed.
Description
Technical field
The invention belongs to super hydrophobic material and preparing technical field thereof, be specifically related to one and utilize nanotechnology and surface modification technology that various base materials (leather, cloth and melamine foamed plastic) are carried out modification to prepare the universal method of super hydrophobic material.
Background technology
Super hydrophobic material is because of the water repellency of its excellence, wide application prospect (T.Darmanin is shown in fields such as automatically cleaning, water proof anti-soil, reducing noise and drag sound, water process, etal.Recentadvancesinthepotentialapplicationsofbioinspir edsuperhydrophobicmaterials [J] .JournalofMaterialsChemistryA, 2014 (2): 16319-16359;R.Truesdell, etal.Dragreductiononapatternedsuperhydrophobicsurface [J] .PhysicalReviewLetters, 2006,97 (4): 044501-4.).At present, such new function material is respectively provided with the huge market demand in multiple fields such as national defence, building, coating.
Super hydrophobic material requires that the water droplet static contact angle on its surface is more than 150 degree.But, use traditional fluorine and silicon materials that solid material surface is simply coated, it is difficult to realize the ultra-hydrophobicity of material, its static contact angle is less than 150 degree.In recent years, the research of super hydrophobic material has had Materiality progress, various inorganic or organic super hydrophobic material in succession to be reported.These existing basic research show, it is thus achieved that super hydrophobic material needs to meet following two condition: one is to construct rough morphology at material surface；Another is, by low-surface energy substance, this rough surface is modified (X.Zhao, etal.Robustanddurablesuperhydrophobiccottonfabricsforoil/waterseparation [J] .ACSAppliedMaterials&Interfaces, 2013 (5): 7208-7214.).I.e. utilize rough morphology to amplify the hydrophobic performance of low-surface energy substance as " magnifier ", make material obtain ultra-hydrophobicity.
Along with appearance and the fast development of the nanotechnology nineties of 20th century, the most effective means obtaining rough surface morphology are become at solid material surface structure micro-enzyme electrode.Utilize the technology such as laser ablation, electrostatic spinning, galvano-cautery, template can realize the preparation (B.N.Sahoo with micro-enzyme electrode rough surface of a series of morphology controllable, etal.Recentprogressinfabricationandcharacterizationofhie rarchicalbiomimeticsuperhydrophobicstructures [J] .RSCAdvances, 2014 (4): 22053-22093.), carry out surface modification by low-surface energy substance (silicon or fluorine) the most again, can obtain that pattern is different and the different super hydrophobic material of hydrophobic performance.
But, the preparation technology of above-mentioned super hydrophobic material is more complicated, prepares the process equipment that material needs are special, and process equipment is expensive, processing cost is higher.Therefore, the research and development super hydrophobic material that preparation process is simple and hydrophobic performance is excellent is the key of development high-performance super hydrophobic material.
Summary of the invention
The present invention utilizes nano material to modify the overall three dimensional structure of base material, thus improve the roughness of base material entirety three dimensional structure, and utilize low-surface energy substance that coarse structure is wrapped up by surface modification technology, modify, prepare the super hydrophobic material that hydrophobic performance is excellent.Particularly as follows:
The preparation method of a kind of super hydrophobic material, comprises the following steps:
(1) utilizing nano material to modify the overall three dimensional structure of base material, structure micron-nanometer is combined coarse structure；
(2) by low-surface energy substance, the base material obtaining micron-nanometer and being combined coarse structure is carried out surface modification.
Described nano material be particle size range be the TiO of 15nm-150nm2Nanoparticle, SiO2Nanoparticle or CeO2Nanoparticle.
Described base material includes: leather, cloth and melamine foamed plastic.
Described step (1) is particularly as follows: be immersed in TiO by base material2The precursor solution of nanoparticle or the solution containing nanoparticle or the lyosol containing nanoparticle process, is then dried, obtains micron-nanometer and be combined the base material of coarse structure.
Described TiO2The precursor solution of nanoparticle be concentration be the ethanol solution of the butyl titanate of 5mmol/L-1mol/L.
The described solution containing nanoparticle is containing nano-TiO2PU and/or the PMMA solution of particle；Or nano si-containing O2PU and/or the PMMA solution of particle.
The described lyosol containing nanoparticle is nano si-containing O2The lyosol of particle or the O Han nano Ce2The lyosol of particle.
In the described solution containing nanoparticle, the concentration of its nanoparticle is 0.02g/L-3g/L.
Described containing nano-TiO2The PU solution of particle is prepared by following methods: by the TiO of a diameter of for 1g 15nm-150nm2Particle is dispersed in 1L PU solution, obtains containing nano-TiO2The PU solution of particle；
Described nano si-containing O2The lyosol of particle is to be prepared by following methods: by volume part proportioning meter, 3 parts of isopyknic tetraethyl orthosilicates and ammonia is joined in 50 parts of dehydrated alcohol, and under room temperature, magnetic agitation system i.e. obtains nano si-containing O2The lyosol of particle；Described ammonia mass concentration is 28%-33%；
Described nano si-containing O2The PMMA solution of particle is to be prepared by following methods: by the SiO of a diameter of for 1g 15nm-150nm2Particle is dispersed in 1L PMMA solution, obtains nano si-containing O2The PMMA solution of particle；
Described containing nano Ce O2The lyosol of particle is to be prepared by following methods: the ethanol solution of 25 parts of 0.06mol/L cerous nitrates of preparation, adds 4 parts of 0.1mol/L sodium hydroxide solutions, prepares nano Ce O under magnetic agitation2The lyosol of particle.
Described low-surface energy substance is solution of silane.
Described solution of silane includes silicon fluoride solution, the substance withdrawl syndrome silane coupler solution more than 0.05mol/L that volumetric concentration is more than 0.5%.
The method that in described step (2), surface is modified is:
The base material having micron-nanometer and being combined coarse structure is immersed directly in toluene solution or the silicon fluoride solution of VTES, can be prepared by super hydrophobic material the most after drying；
Or
First by have micron-nanometer be combined the base material of coarse structure soak in PMMA solution or PDMS solution, dried, place in silane coupler solution or silicon fluoride solution and soak, can be prepared by super hydrophobic material the most after drying；Described silane coupler solution is the toluene solution of VTES.
Described silicon fluoride solution is prepared by following preparation method: by volume part proportioning meter, by least 1 part of FAS, 39 parts of deionized waters and 59 parts of dehydrated alcohol mixing, obtains silicon fluoride solution；
Described PU solution is prepared by following preparation method: by volume part proportioning meter, is dispersed in 96 parts of deionized waters by 4 parts of polyaminoester emulsions, obtains PU solution；
Described PMMA solution is prepared by following preparation method: by volume part proportioning meter, by 1-5 part polymethyl methacrylate emulsion dispersion in 30 parts of deionized waters and 18 parts of dehydrated alcohol, obtains PMMA solution；
Described PDMS solution is prepared by following preparation method: is dispersed in the isopropanol of 95 parts of quality by sylgard 184 silicone rubber of 5 parts of quality, obtains PDMS solution.
The super hydrophobic material of the present invention and the static contact angle of water are 152-158 °.The super hydrophobic material being prepared by the method for the present invention, its hydrophobic performance is excellent, and preparation technology is simple, and reaction condition is gentle, it is not necessary to special process equipment.
Accompanying drawing explanation
Fig. 1 is the contact angle photo schematic diagram of the super-hydrophobic leather of embodiment of the present invention 1-3 and 5 L water.
Fig. 2 is the contact angle photo schematic diagram of the super-hydrophobic foam of embodiment of the present invention 4-6 and 8 L water.
Fig. 3 is the contact angle photo schematic diagram of embodiment of the present invention 7-10 ultra-hydrophobic cloth and 10 L water.
Detailed description of the invention
Below by embodiment, the present invention is specifically described, and technical solution of the present invention is not limited to the detailed description of the invention of act set forth below, also includes the combination in any between each detailed description of the invention.
Be necessary it is pointed out here that be; the present embodiment is served only for being further described the present invention; it is not intended that limiting the scope of the invention; some nonessential improvement and the adjustment done according to foregoing invention content for those skilled in the art, are also considered as being within the scope of the present invention.It is emphasized that the substrate sizes in specific embodiment described herein, only in order to describe present invention in detail, is not intended to limit the present invention.
A kind of method preparing high stability super hydrophobic material that the present invention provides, the processing step of the method and condition are following (number of material used by following example if no special instructions, is parts by volume):
Embodiment 1
By 6cm × 6cm × 1.5mm indigo plant leather deionized water, dehydrated alcohol rinse successively and be dried.Being subsequently adding the ethanol solution of 10mL0.1mol/L butyl titanate, after solution is absorbed by indigo plant leather, drying can be prepared by loading nano-TiO2Leather (the TiO of particle2-Leather).
By TiO2-Leather is immersed in 24h in the toluene solution of 0.1mol/L VTES (VTEO), can be prepared by super-hydrophobic leather VTEO-TiO after drying2-Leather。
By the VTEO-TiO of gained2-Leather tests its surface wettability with 5 μ L deionized waters on DSA100 contact angle measurement.Sample takes 10 diverse locations at random, surveys its contact angle, average, be 153 °.
Embodiment 2
By 6cm × 6cm × 1.5mm indigo plant leather deionized water, dehydrated alcohol rinse successively and be dried.According to parts by volume proportioning meter, 3 parts of isopyknic tetraethyl orthosilicates and ammonia (mass concentration 28%-33%) being joined in 50 parts of dehydrated alcohol, under room temperature, magnetic agitation prepares Nano-meter SiO_22The lyosol of particle.Indigo plant leather is immersed in 10min in above-mentioned lyosol, takes out and be dried, can be prepared by being loaded with Nano-meter SiO_22Leather (the SiO of particle2-Leather).
According to parts by volume proportioning meter, 2 parts of polymethyl methacrylate emulsions (PMMA) are dispersed in 30 parts of deionized waters and 18 parts of dehydrated alcohol, obtain PMMA solution, by SiO2-Leather is immersed in 10min in above-mentioned PMMA solution, takes out and is dried, and obtains the SiO processed through PMMA2-Leather(PMMA-SiO2-Leather).
Again by PMMA-SiO2-Leather is immersed in 24h in the toluene solution of 10mmol/L VTEO, takes out and is dried, and can be prepared by super-hydrophobic leather VTEO-PMMA-SiO2-Leather。
By prepared VTEO-PMMA-SiO2-Leather tests its surface wettability with 5 μ L deionized waters on DSA100 contact angle measurement.Sample takes 10 diverse locations at random, surveys its contact angle, average, be 154 °.
Embodiment 3
6cm × 6cm × 1.5mm indigo plant leather through deionized water, dehydrated alcohol successively rinse and is dried.The ethanol solution of 25 parts of 0.06mol/L cerous nitrates of preparation, adds 4 parts of 0.1mol/L sodium hydroxide solutions, prepares nano Ce O under magnetic agitation2The lyosol of particle.Indigo plant leather is immersed in 5min in above-mentioned lyosol, takes out and be dried, can be prepared by being loaded with nano Ce O2Leather (the CeO of particle2-Leather).
The sylgard184 silicone rubber (PDMS) of 5 parts of quality is dispersed in the isopropanol of 95 parts of quality, obtains the solution of PDMS, by CeO2-Leather is immersed in above-mentioned PDMS solution process 5min, takes out and is dried, and obtains the CeO processed through PDMS2-Leather(PDMS-CeO2-Leather).
According to parts by volume proportioning meter, by 2 parts of silicon fluorides (FAS), 39 parts of deionized waters and 59 parts of dehydrated alcohol mixing, obtain FAS solution, then by PDMS-CeO2-Leather is immersed in 48h in above-mentioned FAS solution, takes out and is dried, and can be prepared by super-hydrophobic leather FAS-PDMS-CeO2-Leather。
By the FAS-PDMS-CeO of gained2-Leather tests its surface wettability with 5 μ L deionized waters on DSA100 contact angle measurement.Sample takes 10 diverse locations at random, surveys its contact angle, average, be 158 °.
Embodiment 4
According to parts by volume proportioning meter, 2 parts of PMMA are dispersed in 30 parts of deionized waters and 18 parts of dehydrated alcohol, obtain PMMA solution, by the SiO of a diameter of for 1g 30nm2Particle is dispersed in 1L above-mentioned PMMA solution, obtains nano si-containing O2The PMMA solution of particle.By 3cm × 3cm × 2cm melamine foamed plastic successively through deionized water, dehydrated alcohol rinse, after drying foam is immersed in above-mentioned nano si-containing O210min in the PMMA solution of particle, takes out and is dried, and i.e. can obtain being loaded with Nano-meter SiO_22Melamine foamed plastic (the SiO of particle2/ PMMA-Foam).According to parts by volume proportioning meter, by 4 parts of FAS, 39 parts of deionized waters and 59 parts of dehydrated alcohol mixing, obtain FAS solution.By SiO2/ PMMA-Foam is immersed in 48h in above-mentioned FAS solution, takes out and is dried, and can obtain super-hydrophobic foam FAS-SiO2/PMMA-Foam。
By the FAS-SiO of gained2/ PMMA-Foam tests its surface wettability with 8 μ L deionized waters on DSA100 contact angle measurement.Sample takes 10 diverse locations at random, surveys its contact angle, average, be 156 °.
Embodiment 5
According to parts by volume proportioning meter, 4 parts of polyaminoester emulsions (PU) are dispersed in 96 parts of deionized waters, obtain PU solution, by the TiO of a diameter of for 1g 40nm2Particle is dispersed in 1L above-mentioned PU solution, obtains containing nano-TiO2The PU solution of particle.By 3cm × 3cm × 2cm melamine foamed plastic successively through deionized water, dehydrated alcohol rinse, after drying, foam is immersed in above-mentioned containing nano-TiO210min in the PU solution of particle, takes out and is dried, and i.e. can obtain being loaded with nano-TiO2Melamine foamed plastic (the TiO of particle2/ PU-Foam).
By TiO2/ PU-Foam is immersed in 24h in the toluene solution of 10mmol/LVTEO, after drying, can obtain the TiO processed through low-surface-energy material2/ PU-Foam(VTEO-TiO2/ PU-Foam).
By the VTEO-TiO of gained2/ PU-Foam tests its surface wettability with 8 μ L deionized waters on DSA100 contact angle measurement.Sample takes 10 diverse locations at random, surveys its contact angle, average, be 157 °.
Embodiment 6
According to parts by volume proportioning meter, 4 parts of PU are dispersed in 96 parts of deionized waters, obtain PU solution, by the TiO of a diameter of for 1g 100nm2Particle is dispersed in 1L above-mentioned PU solution, obtains containing nano-TiO2The PU solution of particle.By 3cm × 3cm × 2cm melamine foamed plastic successively through deionized water, dehydrated alcohol rinse, after drying, foam is immersed in above-mentioned containing nano-TiO210min in the PU solution of particle, takes out and is dried, and i.e. can obtain being loaded with nano-TiO2Melamine foamed plastic (the TiO of particle2/ PU-Foam).
According to parts by volume proportioning meter, the PDMS of 5 parts of quality is dispersed in the isopropanol of 95 parts of quality, obtains PDMS solution, by TiO2/ PU-Foam is immersed in 10min in PDMS solution, takes out and is dried, obtains PDMS-TiO2/PU-Foam。
According to parts by volume proportioning meter, by 2 parts of FAS, 39 parts of deionized waters and 59 parts of dehydrated alcohol mixing, obtain FAS solution.By PDMS-TiO2/ PU-Foam is immersed in 48h in above-mentioned FAS solution, takes out and is dried, and can obtain prepared super-hydrophobic foam FAS-PDMS-TiO2/PU-Foam。
By the FAS-PDMS-TiO of gained2/ PU-Foam tests its surface wettability with 8 μ L deionized waters on DSA100 contact angle measurement.Sample takes 10 diverse locations at random, surveys its contact angle, average, be 156 °.
Embodiment 7
By the yarn weaved fabric of 6cm × 6cm × 0.9mm through deionized water, dehydrated alcohol successively rinse, then it is dried.According to parts by volume proportioning meter, 4 parts of PU are dispersed in 96 parts of deionized waters, obtain PU solution, by the TiO of a diameter of for 1g 25nm2Particle is dispersed in 1L above-mentioned PU solution, obtains containing nano-TiO2The PU solution of particle；Cloth is immersed in above-mentioned containing nano-TiO210min in the PU solution of particle, takes out and is dried, and obtains being loaded with Nano-meter SiO_22Cloth (the TiO of particle2/ PU-Textile).
According to parts by volume proportioning meter, by 4 parts of FAS, 39 parts of deionized waters and 59 parts of dehydrated alcohol mixing, obtain FAS solution.By TiO2/ PU-Textile is immersed in 48h in this FAS solution, takes out and is dried, and can be prepared by ultra-hydrophobic cloth FAS-TiO2/PU-Textile。
By the FAS-TiO of gained2/ PU-Textile tests its surface wettability with 10 μ L deionized waters on DSA100 contact angle measurement.Sample takes 10 diverse locations at random, surveys its contact angle, average, be 155 °.
Embodiment 8
By the yarn weaved fabric of 6cm × 6cm × 0.9mm through deionized water, dehydrated alcohol successively rinse, then it is dried.According to parts by volume proportioning meter, 4 parts of PU are dispersed in 96 parts of deionized waters, obtain containing PU solution, by the TiO of a diameter of for 1g 60nm2Particle is dispersed in 1L above-mentioned PU solution, obtains containing nano-TiO2The PU solution of particle；Cloth is immersed in above-mentioned containing nano-TiO210min in the PU solution of particle, takes out and is dried, and obtains being loaded with nano-TiO2Cloth (the TiO of particle2/ PU-Textile).
According to parts by volume proportioning meter, 2 parts of PMMA are dispersed in 30 parts of deionized waters and 18 parts of dehydrated alcohol, obtain PMMA solution.By TiO2/ PU-Textile is immersed in 10min in above-mentioned PMMA solution, takes out and is dried, and obtains the TiO processed through PMMA2/ PU-Textile(PMMA-TiO2/ PU-Textile).
Then by PMMA-TiO2/ PU-Textile is immersed in 24h in the toluene solution of 10mmol/LVTEO, after drying, can be prepared by ultra-hydrophobic cloth VTEO-PMMA-TiO2/PU-Textile。
By the VTEO-PMMA-TiO of gained2/ PU-Textile tests its surface wettability with 10 μ L deionized waters on DSA100 contact angle measurement.Sample takes 10 diverse locations at random, surveys its contact angle, average, be 152 °.
Embodiment 9
By the yarn weaved fabric of 6cm × 6cm × 0.9mm through deionized water, dehydrated alcohol successively rinse, then it is dried.According to parts by volume proportioning meter, 2 parts of PMMA are dispersed in 30 parts of deionized waters and 18 parts of dehydrated alcohol, obtain PMMA solution, by the SiO of a diameter of for 1g 50nm2Particle is dispersed in 1L above-mentioned PMMA solution, obtains nano si-containing O2The PMMA solution of particle；Cloth is immersed in above-mentioned nano si-containing O210min in the PU solution of particle, takes out and is dried, and obtains being loaded with Nano-meter SiO_22Cloth (the SiO of particle2/ PMMA-Textile).
According to parts by volume proportioning meter, by 4 parts of FAS, 39 parts of deionized waters and 59 parts of dehydrated alcohol mixing, obtain FAS solution.By SiO2/ PMMA-Textile is immersed in 48h in above-mentioned FAS solution, takes out and is dried, and can be prepared by ultra-hydrophobic cloth FAS-SiO2/PMMA-Textile。
By the FAS-SiO of gained2/ PMMA-Textile tests its surface wettability with 10 μ L deionized waters on DSA100 contact angle measurement.Sample takes 10 diverse locations at random, surveys its contact angle, average, be 156 °.
Embodiment 10
By the purified cotton cloth of 6cm × 6cm × 0.9mm through deionized water, dehydrated alcohol successively rinse, then it is dried.According to parts by volume proportioning meter, 2 parts of PMMA are dispersed in 30 parts of deionized waters and 18 parts of dehydrated alcohol, obtain PMMA solution, by the SiO of a diameter of for 1g 15nm2Particle is dispersed in 1L above-mentioned PMMA solution, obtains nano si-containing O2The PMMA solution of particle；Cloth is immersed in above-mentioned nano si-containing O210min in the PMMA solution of particle, takes out and is dried, and obtains being loaded with Nano-meter SiO_22Cloth (the SiO of particle2/ PMMA-Textile).
According to parts by volume proportioning meter, the PDMS of 5 parts of quality is dispersed in the isopropanol of 95 parts of quality, obtains PDMS solution；By SiO2/ PMMA-Textile is immersed in 5min in above-mentioned PDMS solution, takes out and is dried, and obtains the SiO processed through PDMS2/ PMMA-Textile(PDMS-SiO2/ PMMA-Textile).
According to parts by volume proportioning meter, by 2 parts of FAS, 39 parts of deionized waters and 59 parts of dehydrated alcohol mixing, obtain FAS solution.By PDMS-SiO2/ PMMA-Textile processes 48h by this FAS solution soaking, takes out and is dried, can be prepared by ultra-hydrophobic cloth FAS-PDMS-SiO2/PMMA-Textile.
By the FAS-PDMS-SiO of gained2/ PMMA-Textile tests its surface wettability with 10 μ L deionized waters on DSA100 contact angle measurement.Sample takes 10 diverse locations at random, surveys its contact angle, average, be 158 °.
Claims (12)
1. the preparation method of a super hydrophobic material, it is characterised in that: this preparation method comprises the following steps:
(1) utilizing nano material to modify the overall three dimensional structure of base material, structure micron-nanometer is combined coarse structure；
(2) by low-surface energy substance, the base material obtaining micron-nanometer and being combined coarse structure is carried out surface modification.
The preparation method of super hydrophobic material the most according to claim 1, it is characterised in that: described nano material be particle size range be the TiO of 15nm-150nm2Nanoparticle, SiO2Nanoparticle or CeO2Nanoparticle.
The preparation method of super hydrophobic material the most according to claim 1, it is characterised in that: described base material includes: leather, cloth and melamine foamed plastic.
4. according to the preparation method of the super hydrophobic material described in claim 1 or 2 or 3, it is characterised in that: described step (1) is particularly as follows: be immersed in TiO by base material2The precursor solution of nanoparticle, the solution containing nanoparticle or the lyosol containing nanoparticle process, is then dried, obtains micron-nanometer and be combined the base material of coarse structure.
The preparation method of super hydrophobic material the most according to claim 4, it is characterised in that: described TiO2The precursor solution of nanoparticle be concentration be the ethanol solution of the butyl titanate of 5mmol/L-1mol/L；The described solution containing nanoparticle is containing nano-TiO2PU and/or the PMMA solution of particle or nano si-containing O2PU and/or the PMMA solution of particle；The described lyosol containing nanoparticle is nano si-containing O2The lyosol of particle or the O Han nano Ce2The lyosol of particle.
6. according to the preparation method of the super hydrophobic material described in claim 4 or 5, it is characterised in that: in the described solution containing nanoparticle, the concentration of its nanoparticle is 0.02g/L-3g/L.
The preparation method of super hydrophobic material the most according to claim 5, it is characterised in that:
Described containing nano-TiO2The PU solution of particle is prepared by following methods: by the TiO of a diameter of for 1g 15nm-150nm2Particle is dispersed in 1L PU solution, obtains containing nano-TiO2The PU solution of particle；
Described nano si-containing O2The lyosol of particle is to be prepared by following methods: by volume part proportioning meter, 3 parts of isopyknic tetraethyl orthosilicates and ammonia is joined in 50 parts of dehydrated alcohol, and under room temperature, magnetic agitation system i.e. obtains nano si-containing O2The lyosol of particle；Described ammonia mass concentration is 28%-33%；
Described nano si-containing O2The PMMA solution of particle is to be prepared by following methods: by the SiO of a diameter of for 1g 15nm-150nm2Particle is dispersed in 1L PMMA solution, obtains nano si-containing O2The PMMA solution of particle；
Described containing nano Ce O2The lyosol of particle is to be prepared by following methods: the ethanol solution of 25 parts of 0.06mol/L cerous nitrates of preparation, adds 4 parts of 0.1mol/L sodium hydroxide solutions, prepares nano Ce O under magnetic agitation2The lyosol of particle.
The preparation method of super hydrophobic material the most according to claim 1, it is characterised in that: described low-surface energy substance is solution of silane.
The preparation method of super hydrophobic material the most according to claim 8, it is characterised in that: described solution of silane includes that volumetric concentration is more than the silicon fluoride solution of 0.5%, substance withdrawl syndrome is more than 0.05 mol/L silane coupler solution.
The preparation method of super hydrophobic material the most according to claim 1, it is characterised in that: the method that in described step (2), surface is modified is:
The base material having micron-nanometer and being combined coarse structure is immersed directly in toluene solution or the silicon fluoride solution of VTES, can be prepared by super hydrophobic material the most after drying；
Or
First by have micron-nanometer be combined the base material of coarse structure soak in PMMA solution or PDMS solution, dried, place in silane coupler solution or silicon fluoride solution and soak, can be prepared by super hydrophobic material the most after drying；Described silane coupler solution is the toluene solution of VTES.
11. according to the preparation method of the super hydrophobic material described in claim 7 or 9 or 10, it is characterised in that:
Described silicon fluoride solution is prepared by following preparation method: by volume part proportioning meter, by least 1 part of FAS, 39 parts of deionized waters and 59 parts of dehydrated alcohol mixing, obtains silicon fluoride solution；
Described PU solution is prepared by following preparation method: by volume part proportioning meter, is dispersed in 96 parts of deionized waters by 4 parts of polyaminoester emulsions, obtains PU solution；
Described PMMA solution is prepared by following preparation method: by volume part proportioning meter, by 1-5 part polymethyl methacrylate emulsion dispersion in 30 parts of deionized waters and 18 parts of dehydrated alcohol, obtains PMMA solution；
Described PDMS solution is prepared by following preparation method: is dispersed in the isopropanol of 95 parts of quality by sylgard 184 silicone rubber of 5 parts of quality, obtains PDMS solution.
Super hydrophobic material obtained by the preparation method of 12. 1 kinds of super hydrophobic materials as according to any one of claim 1-11.
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Application publication date: 20160921 |