CN104069750A - A super-hydrophobic biomimic membrane material and a preparing method and applications thereof - Google Patents
A super-hydrophobic biomimic membrane material and a preparing method and applications thereof Download PDFInfo
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Abstract
The invention discloses a super-hydrophobic biomimic membrane material and a preparing method and applications thereof, in particular, the invention discloses a super-hydrophobic membrane comprising a dopamine polymer membrane, silver nanometer particles and mercaptan, a preparing method of the super-hydrophobic membrane and applications of the super-hydrophobic membrane. The super-hydrophobic membrane has an excellent hydrophobic property, and can be used for biofuel separation or enrichment, metal corrosion resistance, curtain self-purification or seagoing vessel drag reduction, and other fields.
Description
Technical field
The invention belongs to hydrophobic biomimetic material field.Particularly, the present invention relates to a kind of super-hydrophobic bionic membrane material and its production and use.
Background technology
Along with China's sustained economic development, the contradiction of energy demand, this has had a strong impact on China's economic society comprehensive coordinate and sustainable development.Develop the novel renewable energy such as living beings ethanol and living beings butanols, to alleviating domestic petroleum short supply contradiction and reducing China, the dependence of international petroleum is had to great strategic importance.Biomass ferment is the main path that bio-fuel is produced at present, but biomass ferment method can only be produced the bio-fuel of 3～10wt%.And as vehicle alternative fuel, allow bio-fuel maximum water content 1wt%, therefore bio-fuel must be separated from fermentation tank.
Research shows, the traditional separating and purifying technology cost such as distillation, absorption is very high, accounts for the more than 60% of whole bio-fuel production cost.Therefore, explore a kind of efficiently easily bio-fuel purify and concentration technique extremely urgent.Compare traditional isolation technics (as distillation, rectifying, extraction, recrystallization, absorption etc.), that film separation has is as low in energy consumption, small investment, pollution-free, simple to operate, be convenient to amplify and many advantages such as integrated.Infiltration evaporation is a kind of novel membrane separation technique, and it utilizes in mixed system each component in infiltrating and vaporizing membrane, to adsorb that to cause different permeance properties to realize separated with the difference of diffusion rate.The outstanding advantage of infiltration evaporation is to realize with lower energy consumption the separated task that the methods such as distillation, rectifying, extraction, absorption have been difficult to, be particularly suitable for the way of distillation and be difficult to the separation of separated or indissociable nearly boiling point, constant boiling point mixture and isomer, to minor amount of water in organic solvent and mixed solvent remove and the aqueous solution in high value organic component recovery, concentrated separated etc. there are obvious technical advantage and economic advantages with purifying, be expected to substitute in industry traditional isolation technics such as the extensively distillation of employing, rectifying.Compare with constant boiling rectification method, the operating cost of pervaporation method can be saved more than 50%.In addition, infiltration evaporation process does not need to add other organic solvent, and clean environment firendly, has avoided secondary pollution.So Pervaporation Technology has broad application prospects and market in the fields such as petrochemical industry, medicine, food, environmental protection.
Adopting Pervaporation Technology key concentrated and purification bio-fuel is the hydrophobic membrane material that preparation has high separating property.Can be used at present bio-fuel infiltration vaporization separation film concentrated and that purify and include organic polymeric membrane and inoranic membrane.The easy film forming of organic high molecular layer, but the heat endurance of organic high molecular layer and chemical stability are poor, and Swelling easily occurs, and can affect the selection separating power of diffusion barrier to bio-fuel.Compare with organic high molecular layer, inoranic membrane has higher permeation flux and selective as MFI molecular screen membrane, and the aspect such as heat endurance, chemical stability degree is all better than organic high molecular layer simultaneously.But MFI molecular screen membrane is synthetic, need to use template, when high temperature removal template, easily produce defect, can affect the separation selectivity of MFI molecular screen membrane.In addition, the MFI molecular screen membrane thickness thicker (40～80 microns) of preparation, has reduced MFI molecular sieve permeability of the membrane conventionally.
Thereby the super-hydrophobic film material of developing a kind of high osmosis, high selectivity has great importance.
Summary of the invention
One object of the present invention is to provide the super-hydrophobic film material of a kind of high osmosis, high selectivity.
Another object of the present invention is to provide method for making and the purposes of above-mentioned super-hydrophobic film material.
In a first aspect of the present invention, a kind of super-hydrophobic film is provided, described super-hydrophobic film comprises dopamine polymeric film layer (PD layer); The mercapto that described dopamine polymeric film layer contains dopamine polymeric layer, silver-colored particulate layer and is combined with silver-colored particulate; Wherein, described mercapto is R-S; R is C
8-22the C of alkyl or halo
8-22alkyl.
In another preference, in described dopamine polymeric layer, dopamine polymer is combined with mercaptan; Described mercaptan is R-SH, and R is C
8-22the C of alkyl or halo
8-22alkyl.
In another preference, in described dopamine polymeric layer, dopamine polymer is combined with described mercapto.
In another preference, described super-hydrophobic film has class lotus leaf hierarchy.
In another preference, described silver-colored particulate layer is positioned at described dopamine polymeric layer surface.
In another preference, described silver-colored particulate is Nano silver grain.
In another preference, in described silver-colored particulate (preferably Nano silver grain) layer, part or all of silver-colored particulate passes through chemical bond (Ag-S-R) combination with described mercapto (R-S).
In another preference, in described dopamine polymeric layer, partly or entirely dopamine polymer passes through covalent bond or Hydrogenbond with described mercaptan (R-SH).
In another preference, R comprises: the octadecyl of the cetyl of the myristyl of the dodecyl of dodecyl or halo, myristyl or halo, cetyl or halo, octadecyl or halo.
In another preference, the dodecyl of described halo is the dodecyl that fluorine replaces; Preferably, be 1H, 1H, 2H, 2H-perfluor dodecyl.
In another preference, the water contact angle of described super-hydrophobic film is 140～175 degree.
In another preference, the water contact angle of described super-hydrophobic film is 150～175 degree.
In another preference, the thickness of described super-hydrophobic film is 100～1000nm, preferably 150～500nm.
In another preference, described super-hydrophobic film also comprises the matrix that supports described dopamine polymeric film layer.
In another preference, described matrix is selected from lower group: porous or the dense substrate such as alumina substrate, stainless steel base, stainless (steel) wire, glass basis, filter paper matrix or sponge matrix.
In another preference, described super-hydrophobic film is made by the preparation method described in following second aspect present invention.
In a second aspect of the present invention, the preparation method of the super-hydrophobic film described in a kind of first aspect present invention is provided, comprise step:
(1) matrix is placed in to dopamine cushioning liquid and carries out polymerisation, thereby obtain being supported on the dopamine polymeric membrane of matrix surface;
(2) the dopamine polymeric membrane that is supported on matrix surface step (1) being obtained is placed in liquor argenti nitratis ophthalmicus, and silver ion is separated out silver-colored particulate after redox reaction, thereby obtains being supported on the dopamine polymeric membrane that contains silver-colored particulate of matrix surface;
(3) the dopamine polymeric membrane that contains silver-colored particulate that is supported on matrix surface step (2) Suo Shu is reacted with mercaptan, thereby form the super-hydrophobic film described in first aspect present invention.
In another preference, described super-hydrophobic film comprises the matrix that supports described dopamine polymeric film layer.
In another preference, described mercaptan (R-SH) is C
8-22the C of mercaptan or halo
8-22mercaptan.
In another preference, described matrix is to be selected from porous or the dense substrate of lower group: alumina substrate, stainless steel base, stainless (steel) wire matrix, glass basis, filter paper matrix, sponge matrix.
In another preference, described dopamine buffer solution has following feature:
(i) pH is 7.5～9.5; And/or
(ii) concentration of dopamine is 2～5g/L.
In another preference, described dopamine pH of buffer is 8～9.
In another preference, in described step (1), reaction temperature is that 20～50 ℃ (being preferably 25 ℃) and/or reaction time are 5～24h; And/or
In described step (2), reaction temperature is that 20～50 ℃ (being preferably 25 ℃) and/or reaction time are 5～24h; And/or
In described step (3), reaction temperature is that 20～50 ℃ (being preferably 25 ℃) and/or reaction time are 5～24h.
In a third aspect of the present invention, a kind of goods are provided, described goods contain the super-hydrophobic film described in first aspect present invention; Or described goods are made by the super-hydrophobic film described in first aspect present invention.
In fourth aspect present invention, the purposes of the super-hydrophobic film as described in first aspect present invention is provided, for the separation of bio-fuel film or enrichment, anti-corrosion of metal, curtain wall self-cleaning, seagoing vessel drag reduction, or for the preparation of self-cleaning surface.
In another preference, described bio-fuel comprises methyl alcohol, ethanol, propyl alcohol, butanols.
In fifth aspect present invention, a kind of bio-fuel separation method is provided, comprise step: for containing the raw material of bio-fuel, adopt super-hydrophobic film described in first aspect present invention as diffusion barrier, thus separating bio fuel.
In another preference, the described raw material containing bio-fuel is the mixture of bio-fuel and water.
In another preference, described bio-fuel comprises methyl alcohol, ethanol, propyl alcohol, butanols.
In should be understood that within the scope of the present invention, above-mentioned each technical characterictic of the present invention and can combining mutually between specifically described each technical characterictic in below (eg embodiment), thus form new or preferred technical scheme.As space is limited, at this, tire out and state no longer one by one.
Accompanying drawing explanation
Fig. 1 is the stereoscan photograph of the super-hydrophobic bionic membrane material that makes of embodiment 1.
Fig. 2 is the water contact angle test photo of the super-hydrophobic bionic membrane material that makes of embodiment 1.
The photo of standing that Fig. 3 is the super-hydrophobic bionic membrane material surface water drops that supports in different matrix.
Fig. 4 is the super-hydrophobic Biomimetic membranes of the embodiment 1 preparation separating property figure to different bio-fuels.
The specific embodiment
The inventor is through extensive and deep research, be surprised to find that and have the dopamine polymeric membrane of Nano silver grain to react with mercaptan load, the super-hydrophobic film of the present invention obtaining has excellent hydrophobic performance, can be widely used in the many-sides such as the separation of bio-fuel or enrichment.And super-hydrophobic film method for making of the present invention is easy, be applicable to suitability for industrialized production.On this basis, inventor has completed the present invention.
As used herein, described " matrix " comprising: various porous or the dense substrate such as alumina substrate, stainless steel base, stainless (steel) wire, glass basis, filter paper matrix, sponge matrix.
As used herein, described " mercaptan " can be (R-SH) multiple chain alkyl mercaptan or its similar substance (as the chain alkyl mercaptan of halo).Preferably, R is that the alkyl with 8～22 carbon atoms (is C
8-22alkyl) or the C of halo
8-22alkyl; More preferably, for dodecyl (is C
12alkyl) or the dodecyl of the halo (lauryl mercaptan replacing as fluorine; Be preferably 1H, 1H, 2H, 2H-perfluor dodecyl), the octadecyl of cetyl, octadecyl or the halo of myristyl, cetyl or the halo of myristyl or halo.Wherein, " lauryl mercaptan " also can be described as " lauryl mercaptan ", and other (as Stearyl mercaptan etc.) can do similar exchange.
As used herein, term of the present invention " mercapto " refers to the part of mercaptan (R-SH) removal hydrogen atom, i.e. " R-S ".
Super-hydrophobic film
As used herein, described " super-hydrophobic film " also can be called " super-hydrophobic Biomimetic membranes ", and described super-hydrophobic film comprises dopamine polymeric film layer (PD layer); The mercapto that described dopamine polymeric film layer contains dopamine polymeric layer, silver-colored particulate layer and is combined with silver-colored particulate; Wherein, described mercapto is R-S; R is C
8-22the C of alkyl or halo
8-22alkyl.
In another preference, described super-hydrophobic film has class lotus leaf hierarchy.
In another preference, in described dopamine polymeric layer, dopamine polymer is combined with mercaptan.
In another preference, in described dopamine polymeric layer, dopamine polymer is combined with mercapto.
In another preference, described silver-colored particulate layer is positioned at described dopamine polymeric layer surface.
In another preference, in described silver-colored particulate (preferably Nano silver grain) layer, part or all of silver-colored particulate passes through chemical bond (Ag-S-R) combination with described mercapto.
In another preference, in described dopamine polymeric layer, partly or entirely dopamine polymer passes through covalent bond or Hydrogenbond with described mercaptan.
In another preference, the water contact angle of described super-hydrophobic film is 140～175 degree; Be preferably 150～175 degree.
In another preference, the thickness of described super-hydrophobic film is 100～1000nm, preferably 150～500nm.
In another preference, described super-hydrophobic film also comprises the matrix that supports described dopamine polymeric film layer.
Preparation method
The invention provides a kind of preparation method of preferred super-hydrophobic film of the present invention, described method comprises step:
Step (1), under uniform temperature (as 20～50 ℃), is placed in dopamine cushioning liquid by matrix and carries out polymerisation a period of time (as 5～24h), thereby obtains being supported on the dopamine polymeric membrane of matrix surface;
Wherein, described dopamine buffer solution can be the dopamine buffer solution of any combination, such as the cushioning liquid etc. that is dopamine and trishydroxymethylaminomethane.Preferably described dopamine pH of buffer is 7.5～9.5 (preferably, pH is 8～9).In described dopamine buffer solution, the concentration of dopamine is preferably 2～5g/L.
Step (2) is under uniform temperature (as 20～50 ℃), the dopamine polymeric membrane that is supported on matrix surface that step (1) is obtained is placed in liquor argenti nitratis ophthalmicus, silver ion is separated out silver-colored particulate after redox reaction a period of time (as 5～24h), thereby obtains being supported on the dopamine polymeric membrane that contains silver-colored particulate of matrix surface;
Wherein, described liquor argenti nitratis ophthalmicus can be the liquor argenti nitratis ophthalmicus of any concentration, is preferably the liquor argenti nitratis ophthalmicus of 1～5g/L.
Step (3) is under uniform temperature (as 20～50 ℃), the dopamine polymeric membrane that contains silver-colored particulate that is supported on matrix surface step (2) Suo Shu is reacted a period of time to (as 5～24h) with mercaptan, thereby obtain super-hydrophobic film of the present invention, described super-hydrophobic film comprises matrix.
The preparation method who the invention provides another kind of preferred super-hydrophobic film of the present invention, described method comprises step:
(a) will clean and dry matrix (as Woelm Alumina etc.) is put into dopamine buffer solution, at room temperature react 5～24h, after reaction finishes, obtain being supported on the dopamine polymeric membrane of matrix surface, then with at room temperature dry after distilled water flushing.
(b) the dopamine polymeric membrane that is supported on matrix surface is put into 1～5g/L liquor argenti nitratis ophthalmicus, at room temperature react 5～24h, after reaction finishes, obtain being supported on the dopamine polymeric membrane that contains silver-colored particulate of matrix surface, then with at room temperature dry after distilled water and ethanol washing.
(c) the dopamine polymeric membrane that contains silver-colored particulate and the mercaptan that are supported on matrix surface are at room temperature reacted to 24h, thereby make the super-hydrophobic film with class lotus leaf structure that comprises matrix.
Purposes
Super-hydrophobic film of the present invention has excellent hydrophobic performance, is therefore with a wide range of applications.
Preferably, super-hydrophobic film of the present invention can be used for bio-fuel separation or enrichment.For example, for the raw material containing bio-fuel, adopt super-hydrophobic film of the present invention as diffusion barrier, thus separating bio fuel.Wherein, described bio-fuel can be methyl alcohol, ethanol, propyl alcohol (as isopropyl alcohol), butanols (as isobutanol) etc.In another preference, the described raw material containing bio-fuel is the mixture of bio-fuel and water.
Preferably, the present invention also provides a kind of goods that contain super-hydrophobic film of the present invention or made by described super-hydrophobic film or hydrophobic material.
Major advantage of the present invention comprises:
(1) provide a kind of super-hydrophobic film of hydrophobic performance excellence.Described super-hydrophobic film is separation easily or enriched biological fuel efficiently, also can be used for clean curtain wall, prevents the many-sides such as metal erosion.
(2) provide the preparation method of above-mentioned super-hydrophobic film, described preparation method's condition is simple, easy and simple to handle, financial cost is low, is applicable to suitability for industrialized production.
Below in conjunction with concrete enforcement, further set forth the present invention.Should be understood that these embodiment are only not used in and limit the scope of the invention for the present invention is described.The experimental technique of unreceipted actual conditions in the following example, conventionally according to normal condition, or the condition of advising according to manufacturer.Unless otherwise indicated, otherwise percentage and umber calculate by weight.Room temperature of the present invention is about 20 ℃.
Method of testing
Water contact angle: 3 μ l water droplets, on prepared super-hydrophobic film, are measured to the water contact angle of super-hydrophobic film by video optics contact angle measurement (German Data physics OCA20).
The super-hydrophobic Biomimetic membranes 1 of embodiment 1
Step 1: 0.2g dopamine is dissolved in 100mL distilled water, adds trishydroxymethylaminomethane after stirring is mixed evenly, the pH value of controlling solution is 8.5, obtains dopamine cushioning liquid.
Step 2: the Woelm Alumina matrix after cleaning-drying is put into above-mentioned dopamine cushioning liquid, at room temperature react after 24h, dry under room temperature after distilled water flushing, obtain and be combined in the dopamine polymeric membrane (being designated as materials A 1) on Woelm Alumina matrix.
Step 3: the dopamine polymeric membrane that Woelm Alumina matrix is supported is put into the liquor argenti nitratis ophthalmicus of 1g/L, at room temperature after redox reaction 24, dry under room temperature after distilled water and ethanol washing, obtain the dopamine polymeric membrane (being designated as materials A 2) that is combined in load Nano silver grain on Woelm Alumina matrix.
Step 4: by dopamine polymeric membrane and the 1H of load Nano silver grain, 1H, 2H, 2H-perfluor dodecyl mercaptans at room temperature reacts 24h, at Woelm Alumina matrix surface, prepare the super-hydrophobic Biomimetic membranes 1 (as shown in Figure 1) with class lotus leaf structure, its thickness is about 200nm.
The water contact angle that records the hydrophobic Biomimetic membranes making is about 172 degree (the test photo of water contact angle as shown in Figure 2).
Table 1
| ? | Matrix | Materials A 1 | Materials A 2 | Super-hydrophobic Biomimetic membranes 1 |
| Water contact angle | 0 degree | 0 degree | 50 degree | Approximately 172 degree |
The super-hydrophobic Biomimetic membranes 2 of embodiment 2
Step 1: 0.5g dopamine is dissolved in 100mL distilled water, adds trishydroxymethylaminomethane after stirring is mixed evenly, the pH value of controlling solution is 8.5.
Step 2: the Woelm Alumina matrix after cleaning-drying is put into above-mentioned dopamine cushioning liquid, at room temperature react after 24h, dry under room temperature after distilled water flushing.
Step 3: the dopamine polymeric membrane that Woelm Alumina matrix is supported is put into the liquor argenti nitratis ophthalmicus of 1g/L, at room temperature reacts after 24h, dry under room temperature after distilled water and ethanol washing.
Step 4: by dopamine polymeric membrane and the 1H of load Nano silver grain, 1H, 2H, 2H-perfluor dodecyl mercaptans at room temperature reacts 24h, at Woelm Alumina matrix surface, prepare the super-hydrophobic Biomimetic membranes 2 with class lotus leaf structure, the water contact angle that records the hydrophobic Biomimetic membranes making is about 170 degree.
The super-hydrophobic Biomimetic membranes 3 of embodiment 3
Step 1: 0.5g dopamine is dissolved in 100mL distilled water, adds trishydroxymethylaminomethane after stirring is mixed evenly, the pH value of controlling solution is 8.5.
Step 2: the Woelm Alumina matrix after cleaning-drying is put into above-mentioned dopamine cushioning liquid, at room temperature react after 24h, dry under room temperature after distilled water flushing.
Step 3: the dopamine polymeric membrane that Woelm Alumina matrix is supported is put into the liquor argenti nitratis ophthalmicus of 1g/L, at room temperature reacts after 20h, dry under room temperature after distilled water and ethanol washing.
Step 4: by dopamine polymeric membrane and the 1H of load Nano silver grain, 1H, 2H, 2H-perfluor dodecyl mercaptans at room temperature reacts 24h, at Woelm Alumina matrix surface, prepare the super-hydrophobic Biomimetic membranes 3 with class lotus leaf structure, the water contact angle that records the hydrophobic Biomimetic membranes making is about 160 degree.
The super-hydrophobic Biomimetic membranes 4-7 of embodiment 4
Method for making is with embodiment 1, and difference is, adopts following different matrix: stainless steel, glass, filter paper, sponge.
In stainless steel-based surface, prepare super-hydrophobic Biomimetic membranes 4;
On glass basis surface, prepare super-hydrophobic Biomimetic membranes 5;
At filter paper matrix surface, prepare super-hydrophobic Biomimetic membranes 6;
At sponge matrix surface, prepare super-hydrophobic Biomimetic membranes 7;
The water contact angle of these hydrophobic Biomimetic membranes is all about 170 degree.
Embodiment 5
First group: the super-hydrophobic Biomimetic membranes 1 that Woelm Alumina matrix and Woelm Alumina matrix support
Second group: the super-hydrophobic Biomimetic membranes 5 that glass basis and glass basis support
The 3rd group: the super-hydrophobic Biomimetic membranes 6 that filter paper matrix and filter paper matrix support
The 4th group: the super-hydrophobic Biomimetic membranes 7 that sponge matrix and sponge matrix support
After the surface of above-mentioned four groups of materials contacts with water, the globule is stood effect as shown in Figure 3 each group material surface.Result shows: the super-hydrophobic film making at unlike material matrix surface all has fine hydrophobic performance.
The super-hydrophobic Biomimetic membranes 8 of embodiment 6
Step 1: 0.3g dopamine is dissolved in 100mL distilled water, adds trishydroxymethylaminomethane after stirring is mixed evenly, the pH value of controlling solution is 8.5.
Step 2: the Woelm Alumina matrix after cleaning-drying is put into above-mentioned dopamine cushioning liquid, at room temperature react after 24h, dry under room temperature after distilled water flushing.
Step 3: the dopamine polymeric membrane that Woelm Alumina matrix is supported is put into the liquor argenti nitratis ophthalmicus of 1g/L, at room temperature reacts after 24h, dry under room temperature after distilled water and ethanol washing.
Step 4: the dopamine polymeric membrane of load Nano silver grain and stearylmercaptan are at room temperature reacted to 24h, prepare super-hydrophobic Biomimetic membranes 8 at Woelm Alumina matrix surface, the water contact angle that records the hydrophobic Biomimetic membranes making is about 154 degree.
The separating property of embodiment 7 super-hydrophobic Biomimetic membranes
Experimental technique:
Adopt sealing ring that the super-hydrophobic Biomimetic membranes of embodiment 1 preparation is sealed on film osmotic cell, a side of film passes into respectively ethanol water, isopropanol water solution and the isobutanol aqueous solution of 5wt%, and the opposite side of film vacuumizes osmotic engine is provided with mechanical pump.Adopt cooled with liquid nitrogen to collect penetrating fluid, and form by the component of gas chromatographic analysis penetrating fluid.Between sample at regular intervals, weigh, analyze composition.
The composition of material liquid and penetrating fluid is measured by gas chromatographic analysis, and the performance of super-hydrophobic film sieve membrane infiltration evaporation is evaluated by saturating amount and separation.Total amount (J) thoroughly, minute saturating amount (Ji) and separation (α) is following is determined by formula:
In formula, the quality that W is penetrating fluid (Kg), Δ t is sample interval (h), effective infiltrating area (m that A is film
2);
J
ifor the saturating amount of i species, x
ip(x
jp) be the quality percentage compositions of i (j) species in penetrating fluid;
α
i,jfor the separation of i species and j species, x
if(x
jf) be the quality percentage compositions of i (j) species in material liquid.
As shown in Figure 4, result shows result, and super-hydrophobic Biomimetic membranes of the present invention has very high separation to ethanol/water, isopropanol/water, isobutanol/water, and flow is fast.
Comparative example alcohol water separable performance can compare
As shown in table 2, to compare with existing hydrophobic membrane, super-hydrophobic Biomimetic membranes prepared by the present invention has better separating property: flow is fast, separation is high.
Table 2 alcohol water separable performance can compare
5 notes:
(i) "/" represents not provide data;
(ii) b represents " ethanol ";
(iii) c represents " butanols ";
(iv) literature reference:
The people such as 101.T.Sano, J.Membr.Sci.1994,95,221;
The people such as 2.X.Lin, AIChE J.2003,49,237;
The people such as 3.M.Nomura, J.Membr.Sci.1998,144,161;
The people such as 4.L.Shan, J.Membr.Sci.2011,378,319;
The people such as 5.H.Chen, Microporous Mesoporous Mater.2007,102,249;
The people such as 6.X.Lin, Ind.Eng.Chem.Res.2001,40,4069;
The people such as 7.G.S.Li, Microporous Mesoporous Mater.2003,58,137;
The people such as 8.A.G.Fadeev, J.Membr.Sci.2001,186,205;
The people such as 9.K.Srinivasan, Chem.Eng.Sci.2007,62,2905;
The people such as 10.N.Qureshi, J.Membr.Sci.1999,158,115;
The people such as 11.J.Huang, J.Membr.Sci.1999,192,231;
The people such as 12.A.Jonquieres, J.Membr.Sci.1997,125,245;
The people such as 13.S.Li, J.Membr.Sci.2010,363,287;
The people such as 14.X.Liu, Angew.Chem.Int.Ed.2011,50,10636.
All documents of mentioning in the present invention are all quoted as a reference in this application, just as each piece of document, are quoted as a reference separately.In addition should be understood that those skilled in the art can make various changes or modifications the present invention after having read above-mentioned instruction content of the present invention, these equivalent form of values fall within the application's appended claims limited range equally.
Claims (11)
1. a super-hydrophobic film, is characterized in that, described super-hydrophobic film comprises dopamine polymeric film layer (PD layer); The mercapto that described dopamine polymeric film layer contains dopamine polymeric layer, silver-colored particulate layer and is combined with silver-colored particulate; Wherein, described mercapto is R-S; R is C
8-22the C of alkyl or halo
8-22alkyl.
2. super-hydrophobic film as claimed in claim 1, is characterized in that, described silver-colored particulate layer is positioned at described dopamine polymeric layer surface.
3. super-hydrophobic film as claimed in claim 1, is characterized in that, the water contact angle of described super-hydrophobic film is 140～175 degree.
4. super-hydrophobic film as claimed in claim 1, is characterized in that, described super-hydrophobic film also comprises the matrix that supports described dopamine polymeric film layer.
5. a preparation method for super-hydrophobic film claimed in claim 1, is characterized in that, comprises step:
(1) matrix is placed in to dopamine cushioning liquid and carries out polymerisation, thereby obtain being supported on the dopamine polymeric membrane of matrix surface;
(2) the dopamine polymeric membrane that is supported on matrix surface step (1) being obtained is placed in liquor argenti nitratis ophthalmicus, and silver ion is separated out silver-colored particulate after redox reaction, thereby obtains being supported on the dopamine polymeric membrane that contains silver-colored particulate of matrix surface;
(3) the dopamine polymeric membrane that contains silver-colored particulate that is supported on matrix surface step (2) Suo Shu is reacted with mercaptan, thereby form super-hydrophobic film claimed in claim 1.
6. preparation method as claimed in claim 5, is characterized in that, described matrix is to be selected from porous or the dense substrate of lower group: alumina substrate, stainless steel base, stainless (steel) wire matrix, glass basis, filter paper matrix, sponge matrix.
7. preparation method as claimed in claim 5, is characterized in that, described dopamine buffer solution has following feature: (i) pH is 7.5～9.5; And/or (ii) concentration of dopamine is 2～5g/L.
8. preparation method as claimed in claim 5, is characterized in that,
In described step (1), reaction temperature is that 20～50 ℃ and/or reaction time are 5～24h; And/or
In described step (2), reaction temperature is that 20～50 ℃ and/or reaction time are 5～24h; And/or
In described step (3), reaction temperature is that 20～50 ℃ and/or reaction time are 5～24h.
9. goods, is characterized in that, described goods contain super-hydrophobic film claimed in claim 1; Or described goods are made by super-hydrophobic film claimed in claim 1.
10. the purposes of super-hydrophobic film as claimed in claim 1, is characterized in that, for the separation of bio-fuel film or enrichment, anti-corrosion of metal, curtain wall self-cleaning, seagoing vessel drag reduction, or for the preparation of self-cleaning surface.
11. 1 kinds of bio-fuel separation methods, is characterized in that, comprise step: the raw material for containing bio-fuel, and adopt super-hydrophobic film claimed in claim 1 as diffusion barrier, thus separating bio fuel.
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| CN104562709A (en) * | 2015-01-27 | 2015-04-29 | 南昌航空大学 | Preparation method of durable super-hydrophobic fabric |
| CN104988737A (en) * | 2015-07-14 | 2015-10-21 | 陕西科技大学 | Super-hydrophobic textile prepared from modified polyester fiber based on dopamine and preparation method thereof |
| CN105013336A (en) * | 2015-06-30 | 2015-11-04 | 天津大学 | Preparation method of nano silver/poly dopamine composite membrane |
| CN107904935A (en) * | 2017-11-28 | 2018-04-13 | 苏州大学 | Hydrophobic silk fabric and its preparation method and application |
| CN107915857A (en) * | 2017-11-20 | 2018-04-17 | 华南理工大学 | A kind of compliant conductive super-hydrophobic coat and preparation method thereof |
| CN108707248A (en) * | 2018-04-24 | 2018-10-26 | 天津大学 | A kind of preparation method of fire-retardant super-hydrophobic melamine sponge |
| CN108722200A (en) * | 2018-06-01 | 2018-11-02 | 天津大学 | A kind of preparation method of the super-hydrophobic oleophobic membrane of double bionical membrane distillations with photo-thermal effect |
| CN108822332A (en) * | 2018-04-24 | 2018-11-16 | 天津大学 | The preparation method of super-hydrophobic sponge for absorbing organic solvent |
| CN109722900A (en) * | 2019-01-28 | 2019-05-07 | 扬州大学 | Ultra-hydrophobic conductive compound fabric with electromagnetic shielding performance and preparation method thereof |
| CN110141887A (en) * | 2019-04-26 | 2019-08-20 | 华东师范大学 | A kind of super-hydrophobic COF film and preparation method and application of stainless (steel) wire support |
| CN110746641A (en) * | 2019-11-21 | 2020-02-04 | 齐鲁工业大学 | High-oil-absorption-rate nano porous starch-based material and preparation method and application thereof |
| CN111871003A (en) * | 2020-07-31 | 2020-11-03 | 西南石油大学 | Bionic mussel-based super-hydrophobic metal net and preparation method and application thereof |
| CN112755795A (en) * | 2021-01-04 | 2021-05-07 | 南开大学 | Anti-wetting and anti-pollution lyophobic film aiming at film distillation process and preparation method and application thereof |
| CN113521297A (en) * | 2021-07-14 | 2021-10-22 | 湖南万欧科技有限公司 | Bionic nano material and preparation method and application thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101199918A (en) * | 2006-12-14 | 2008-06-18 | 上海世龙科技有限公司 | Process for preparing polymer microporous membrane and usage of same |
| EP2433704A1 (en) * | 2010-09-27 | 2012-03-28 | Stichting IMEC Nederland | Humidity barrier |
| CN102925877A (en) * | 2012-11-13 | 2013-02-13 | 中国科学院化学研究所 | Hollow-out container with special invasion and preparation method and application of hollow-out container |
-
2013
- 2013-03-26 CN CN201310100511.6A patent/CN104069750A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101199918A (en) * | 2006-12-14 | 2008-06-18 | 上海世龙科技有限公司 | Process for preparing polymer microporous membrane and usage of same |
| EP2433704A1 (en) * | 2010-09-27 | 2012-03-28 | Stichting IMEC Nederland | Humidity barrier |
| CN102925877A (en) * | 2012-11-13 | 2013-02-13 | 中国科学院化学研究所 | Hollow-out container with special invasion and preparation method and application of hollow-out container |
Non-Patent Citations (1)
| Title |
|---|
| HAESHIN LEE等: ""Mussel-ixspired Surface chemistry for Multifunctional Coatings"", 《SCIENCE》 * |
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| CN104562709A (en) * | 2015-01-27 | 2015-04-29 | 南昌航空大学 | Preparation method of durable super-hydrophobic fabric |
| CN105013336A (en) * | 2015-06-30 | 2015-11-04 | 天津大学 | Preparation method of nano silver/poly dopamine composite membrane |
| CN104988737A (en) * | 2015-07-14 | 2015-10-21 | 陕西科技大学 | Super-hydrophobic textile prepared from modified polyester fiber based on dopamine and preparation method thereof |
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| CN108722200B (en) * | 2018-06-01 | 2021-08-27 | 天津大学 | Preparation method of super-hydrophobic and oleophobic membrane with photo-thermal effect for double-bionic membrane distillation |
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| CN109722900B (en) * | 2019-01-28 | 2021-09-17 | 扬州大学 | Super-hydrophobic conductive composite fabric with electromagnetic shielding performance and preparation method thereof |
| CN110141887A (en) * | 2019-04-26 | 2019-08-20 | 华东师范大学 | A kind of super-hydrophobic COF film and preparation method and application of stainless (steel) wire support |
| CN110141887B (en) * | 2019-04-26 | 2021-08-20 | 华东师范大学 | Stainless steel mesh supported super-hydrophobic COF film and preparation method and application thereof |
| CN110746641A (en) * | 2019-11-21 | 2020-02-04 | 齐鲁工业大学 | High-oil-absorption-rate nano porous starch-based material and preparation method and application thereof |
| CN110746641B (en) * | 2019-11-21 | 2022-06-17 | 齐鲁工业大学 | High-oil-absorption-rate nano porous starch-based material and preparation method and application thereof |
| CN111871003A (en) * | 2020-07-31 | 2020-11-03 | 西南石油大学 | Bionic mussel-based super-hydrophobic metal net and preparation method and application thereof |
| CN112755795A (en) * | 2021-01-04 | 2021-05-07 | 南开大学 | Anti-wetting and anti-pollution lyophobic film aiming at film distillation process and preparation method and application thereof |
| CN113521297A (en) * | 2021-07-14 | 2021-10-22 | 湖南万欧科技有限公司 | Bionic nano material and preparation method and application thereof |
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