CN102199263A - Amphiphobic fluoro-containing crosslinkable block copolymer and preparation method and application thereof - Google Patents
Amphiphobic fluoro-containing crosslinkable block copolymer and preparation method and application thereof Download PDFInfo
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Abstract
The invention discloses amphiphobic fluoro-containing crosslinkable block copolymer and a preparation method and application thereof. The block copolymer can be used for preparing a super-amphiphobic coating on the surface of glass or printing paper, and the super-amphiphobic coating is prepared by the following steps of: (1) putting silica nano spheres into benzotrifluoride to obtain solution of silica nano spheres; (2) adding solution of amphiphobic fluoro-containing crosslinkable block copolymer, tetrahydrofuran, hydochloric acid solution and water into the solution of silica nano spheres, and reacting for 7 to 12 hours to obtain a crude product of modified silica nano spheres; (3) washing the crude product of modified silica nano spheres to obtain modified silica nano spheres; and (4) dispersing the modified silica nano spheres into the benzotrifluoride to obtain solution, dripping the solution onto a glass sheet, and after the solvent is volatilized, forming the super-amphiphobic coating on the surface of the glass sheet, or soaking the printing paper in the solution, taking the paper out, and drying the paper to obtain the super-amphiphobic coating on the surface of the paper. The amphiphobic fluoro-containing crosslinkable block copolymer can endow a material with good superhydrophobic and oleophobic properties; and the coating has high stability and hardly falls off and denatures.
Description
Technical field
The invention belongs to the organic materials field, be specifically related to a kind of two fluorine-containing crosslinkable block copolymers of thin property and preparation method thereof and application.
Background technology
Super hydrophobic surface is meant when the surface of material obliquity with respect to the horizontal plane during less than 5 ° the class surface that water droplet can tumble from its surface at an easy rate; The surface of lotus leaf is exactly the common a kind of super hydrophobic surface of nature.
If at certain material surface, oil droplet also can produce above-mentioned phenomenon, and the surface of this material is exactly super two (hydrophobic, oleophobic) surface of dredging.Super-double-hydrophobic surface has good self-cleaning performance.
Perfluoro hydro carbons and fluorinated polymer have very low surface energy, with these compounds material are carried out modification and can make material obtain well two thin performances, and the pot that for example has polytetrafluorethylecoatings coatings just shows hydrophobic oleophobic performance preferably.
The cost of fluorochemicals and fluoropolymer is generally all very expensive.So, plate the most cost-effective method that one deck fluorochemicals film just becomes preparation fluorine surface at material surface, do the composition and the character that can also keep material internal like this.
Silane coupling agent, such as 1H, 1H, 2H, 2H-perfluor decyl triethoxyl silane [CF
3(CF
2)
7CH
2CH
2Si (OC
2H
5)
3Perhaps PFTS], a kind of exactly material that well has two thin performances.PFTS can react the surface that is grafted to material in the sol-gel method of material surface by triethoxyl silane, and the fluorinated alkyl chain will finally cover the surface of material.Because the fluorinated alkyl chain has very low surface tension, the material surface of process PFTS modification presents certain ultra-amphosphobic energy.In theory, only need can realize two thinization of material in the unimolecular layer of material surface grafting PFTS.
In fact, with the small molecules fluorochemicals that is similar to PFTS material is carried out modification and have a lot of shortcomings.At first, the two thin performance of the material of micromolecular compound modification can be too not desirable.By less than ten CF
2The film thickness maximum that unitary alkyl chain unimolecular layer is formed can only reach 1.5 nanometers, and the film of little thickness like this is easy to be permeated by spot.Secondly, micromolecular compound is difficult in the film that material surface forms even compact.With PFTS is example, because the steric hindrance between the molecular chain contains fluoroalkyl chain and be difficult to neatly be arranged in densely material surface in reaction process, film forming thickness of institute and homogeneity also are difficult to be guaranteed.Once more, the micromolecular compound film lacks permanent stability at material surface.Micromolecular compound fixes a long alkyl chain with a silane group often, and in the process of using, single reactive force is easy to be overcome.The two thin performance of material will weaken along with containing coming off of fluoroalkyl chain and disappear gradually.At last, micromolecular compound also should not be as the modification of spray material.The length of alkyl chain is very little in the micromolecular compound, and the reactive force between the coating particle can not strengthen because of the mutual winding of alkyl chain, and spray material just is easy to come off from matrix.
If use the segmented copolymer of being made up of fluorine-containing polymer blocks and crosslinkable polymer blocks to replace the small molecules coupling agent, above shortcoming all will be readily solved.
At present not about the report of the segmented copolymer that contains fluorine-containing block and crosslinkable block simultaneously, just there are some scientists to report the preparation of the trackless multipolymer of fluorochemical monomer and crosslinkable monomers, as vinylidene fluoride (CH
2=CF
2) and 1,1,2-trifluoro vinyl-ethyl-trialkoxy silane (CF
2=CF-(CH
2)
3Si (OR)
3) multipolymer (Guiot, J.; Ameduri, B.; Boutevin, B.; Lannuzel, T.J.Polym.Sci.:Part A:Polym.Chem.2006,44,3896.Lannuzel, T.; Meunier, V.; Faig, R.; Vedberg, O.US Patent, 2003,0176608 A1); Tetrafluoroethylene (CF
2=CF
2) and 1,1, the multipolymer of 2-trifluoro vinyl-ethyl-trialkoxy silane (Kabeta, K.; Zenbayashi, M.; Shinohara, K.Japanese Patent No 3-17087-A, 1989.); R 1216 (CF
2=CF-CF
3) and 1,1, the multipolymer of 2-trifluoro vinyl-ethyl-trialkoxy silane (Ibid Patent 3-17088-A).Also having some reports is preparations of relevant fluoropolymer or crosslinkable polymer, the two is not connected.
Summary of the invention
For the shortcoming and deficiency that overcomes prior art, primary and foremost purpose of the present invention is to provide a kind of two fluorine-containing crosslinkable block copolymers of thin property.
Another object of the present invention is to provide the preparation method of above-mentioned two fluorine-containing crosslinkable block copolymers of thin property.
A further object of the present invention is to provide the application of above-mentioned two fluorine-containing crosslinkable block copolymers of thin property.
Purpose of the present invention is achieved through the following technical solutions:
A kind of two fluorine-containing crosslinkable block copolymers of thin property has suc as formula the structure shown in the I:
SI
k-FL
n
(I)
Wherein, SI is the structural unit of (perhaps two) organoalkoxysilane that contains three, has suc as formula the structure shown in the II:
R wherein
1And R
5For hydrogen, alkyl or contain the aromatic group of phenyl ring; R
2And R
7Be alkylene; R
3Be alkyl; R
4For-OR
3The perhaps alkoxyl group of other types; R
6Be aromatic nucleus, pyridine ring, pyranoid ring or furan nucleus.Preferably, SI can be methacrylic acid (3-(three isopropoxies are silica-based)) trimethylene ester (IPSMA);
What FL referred to is the structural unit that contains fluorine element; Preferably, FL can be methacrylic acid (17 fluorine octyl group) ethylene ester (F
8H
2MA);
1＜k＜200；1＜n＜200。
Preferably, SI
k-FL
nBe (IPSMA)
10-(F
8H
2MA)
10, i.e. polymethyl acrylic acid (3-(three isopropoxies are silica-based)) trimethylene ester-block-polymethyl acrylic acid (17 fluorine octyl group) ethylene ester, two kinds of monomeric number of repeat unit are 10.
A kind of two fluorine-containing crosslinkable block copolymers of thin property can prepare by (controlled) radical polymerization and active anionic polymerization.
Under a kind of two fluorine-containing crosslinkable block copolymers room temperature of thin property is white powder, and density is 1.2～1.7 gram per centimeters
3, not fluorine-containing organic solvent such as water insoluble, methyl alcohol, ethanol dissolves in α, α, and α-phenylfluoroform, perfluor hexanaphthene etc. is fluoridized organic solvent.If the n in the polymkeric substance is less than 30, polymkeric substance can be dissolved in general organic solvent, as tetrahydrofuran (THF), chloroform etc.
Above-mentioned two fluorine-containing crosslinkable block copolymers of thin property can be used for preparing the super two open coats of glass or printer paper surface, and its application may further comprise the steps:
A, the fluorine-containing crosslinkable block copolymers of two thin property are to the modification of nano silicon spheres
(1) nano silicon spheres is placed α, α, in α-phenylfluoroform, ultrasonic dissolution makes the silicon ball be dispersed in α, and α in α-phenylfluoroform, obtains nano silicon spheres solution;
(2) under agitation, add two fluorine-containing crosslinkable block copolymers solution of thin property, tetrahydrofuran (THF), hydrochloric acid soln and water in nano silicon spheres solution, 20～25 ℃ were reacted 7～12 hours down, and reaction product is centrifugal, and taking precipitate obtains modified Nano silicon ball crude product;
(3) use α, α, α-phenylfluoroform washing modified Nano silicon ball crude product is dried then, obtains the modified Nano silicon ball of white powder;
The preparation of super two open coats of B, polymer modification silicon ball
(4) modified Nano silicon ball is distributed to α again, α, in α-phenylfluoroform, being made into modified Nano silicon ball concentration is the solution of 0.5～5 mg/ml; Solution directly is added drop-wise on the sheet glass, just forms super two coating of dredging in glass sheet surface after the solvent evaporates; Perhaps directly printer paper is immersed in the solution, take out the scraps of paper and treat that scraps of paper drying just forms super two open coats on its surface later on.
The described nano silicon spheres of step (1) is by Stober method (Stober, W.; Fink, A.; Bohn, E.J.Colloid Interf.Sci.1968,26:62-﹠amp; .) preparation; In Virahol, catalysis by ammoniacal liquor, the hydrolysis of tetraethyl-silica alkane can obtain having the nano silicon spheres of certain particle diameter, the product centrifugation later on washed with isopropyl alcohol three times to remove catalyzer, unreacted reactant and by product, vacuum-drying obtains white powder later on;
In the step (2), the fluorine-containing crosslinkable block copolymers of two thin property accounts for 8～35% of nano silicon spheres quality, and described two fluorine-containing crosslinkable block copolymers solution of thin property are tetrahydrofuran solutions that two fluorine-containing crosslinkable block copolymers concentration of thin property are 5.0 mg/ml;
In the step (2), the volume content of tetrahydrofuran (THF) in reaction system is 9%, and the mol ratio of nano silicon spheres, water and hydrochloric acid is 1: 2: 1, and described hydrochloric acid soln is that concentration of hydrochloric acid is the tetrahydrofuran solution of 0.2 mol;
Preferred 10 hours of described reaction times of step (2);
The described crude product drying temperature of step (3) is 100 ℃, and be 2 hours time of drying;
The described modified Nano silicon of step (4) ball α, α, in α-phenylfluoroform solution, preferred 2 mg/ml of modified Nano silicon ball concentration.
Mechanism of the present invention is: the crosslinkable polymer block can be grafted on the matrix by crosslinking reaction.Initiated polymerization thing crosslinked factor on matrix can be the light-wave irradiation of certain wavelength, also can be acid or alkali.Crosslinking reaction may occur between the structural unit of polymer chain inside, also may occur between polymeric chain and the matrix.Have on the polymer chain a plurality of can cross-linking structural units, have a more than structural unit and substrate reaction in them, so just make the polymers grafted film very firm.Fluorine-containing polymer blocks can stretch out and cover material surface from crosslinked part, makes material have very low surface energy.Simultaneously, the length of fluorine-containing block and crosslinkable block can also be adjusted according to different needs, can increase the interaction force between polymkeric substance and the matrix by the length that increases the crosslinkable block, also can increase the thickness of fluoride film by the length that increases fluorine-containing block.
The present invention has following advantage and effect with respect to prior art:
(1) two fluorine-containing crosslinkable block copolymers of thin property of the present invention can give material good super-hydrophobic oleophobic performance.
(2) the present invention introduces fluorine-containing block and crosslinkable block simultaneously in the fluorine-containing crosslinkable block copolymers of two thin property, when utilizing fluorine-containing block to give material ultra-amphosphobic energy, can carry out crosslinked fixing to upper layer.
(3) the present invention adopts (controlled) radical polymerization and the two fluorine-containing crosslinkable block copolymers of thin property of active anionic polymerization preparation, accurate parameter such as controlling polymers chain length, polymer chain number, thereby prepare segmented copolymer, give material accurate performance perameter with accurate structure.
(4) the coating stability of preparing with the two fluorine-containing crosslinkable block copolymers of thin property of the present invention is strong, difficult drop-off and sex change.
Description of drawings
Fig. 1 is the proton nmr spectra of the fluorine-containing crosslinkable block copolymers of two thin property of embodiment 1.
Embodiment
The present invention is described in further detail below in conjunction with embodiment and accompanying drawing, but embodiments of the present invention are not limited thereto.
One, the preparation of the fluorine-containing crosslinkable block copolymers of two thin property
Below used material derive from respectively:
IPSMA document (Ozaki, H.; Hirao, A.; Nakahama, S.Macromolecules 1992,25:1391-1395.) reported method preparation;
F
8H
2MA buys from Aldrich company, uses document (Ishizone, T. before using; Sugiyama, K.; Sakano, Y.; Mori, H.; Hirao, A.; Nakahama, S.Polymer Journal 1999,31:983-988.) underpressure distillation of report method is purified;
The preparation process of the fluorine-containing crosslinkable block copolymers of two thin property is as follows:
Under-78 ℃ (dry ice acetone bath), in the there-necked flask that 250 milliliters of anhydrous tetrahydro furans are housed, add 0.19 milliliter of (1.09 mmole) 1, then add the hexane solution of the s-butyl lithium of 0.6 milliliter of 1.4 mol.Add 2.59 milliliters of (7.3 mmole) IPSMA after 15 minutes, polyreaction carries out adding later in 2 hours 2.60 milliliters of (7.8 mmole) F
8H
2MA, polyreaction continues to add after 2 hours 1.0 milliliters of anhydrous methanols again and stops polyreaction.Underpressure distillation was concentrated into 100 milliliters after reaction system was warmed up to 23 ℃, then with polymer precipitation in excessive methyl alcohol, filter also dryly in vacuum drying oven, obtain two fluorine-containing crosslinkable block copolymers of thin property.
Product after super-dry, the productive rate and the basically identical that feeds intake.
Gel exclusion chromatography to the characterization result of polymkeric substance is: the number-average molecular weight of polymkeric substance is 8.6 * 10
3Gram/mole, dispersed index are 1.16.
The characterization result (see figure 1) of proton nmr spectra shows IPSMA and PF in the polymkeric substance
8H
2The MA mol ratio is 1.0/1.0.
Result in conjunction with chromatogram and nucleus magnetic resonance can determine that the structure of polymkeric substance is (IPSMA)
10-(F
8H
2MA)
10
Two, the application of the fluorine-containing crosslinkable block copolymers of two thin property
The fluorine-containing crosslinkable block copolymers of two thin property carries out modification to nano silicon spheres
Used nano silicon spheres is by Stober method (Stober, W.; Fink, A.; Bohn, E.J.Colloid Interf.Sci.1968,26:62-﹠amp; .Sheen, Y.C.; Huang, Y.C.; Liao, C.S.; Chou, H.Y.; Chang, F.C.Journal Of Polymer Science Part B-Polymer Physics 2008,46:1984-1990.) preparation: in Virahol, by the catalysis of ammoniacal liquor, the hydrolysis of tetraethyl-silica alkane can obtain having the nano silicon spheres of certain particle diameter.The product centrifugation later on washed with isopropyl alcohol three times to remove catalyzer, unreacted reactant and by product.Vacuum-drying obtains white powder later on.Again after being distributed to white powder in the ethanol, the hydromeehanics diameter of the silicon ball that records with the dynamic laser scattering of light is 328 nanometers.
The fluorine-containing crosslinkable block copolymers of two thin property is as follows to the modifying process of nano silicon spheres:
Get 3.0 milliliters α, α, α-phenylfluoroform and 5.0 milligrams of nano silicon spheres place 20 milliliters of bottles, and bottle is put into the ultrasonic cleaning instrument made the silicon ball be dispersed in α in ultrasonic 60 seconds, and α is in α-phenylfluoroform.Segmented copolymer P (IPSMA)
10-(PF
8H
2MA)
10Be made into the tetrahydrofuran solution of 5.0 mg/ml.4.0 the hydrochloric acid dioxane solution of mol is diluted to the solution of 0.2 mol with tetrahydrofuran (THF).Under agitation, progressively add 0.08 milliliter of polymers soln, 0.14 milliliter of tetrahydrofuran (THF), 0.08 milliliter of hydrochloric acid soln and 3.0 microliters of water in the solution of nano silicon spheres, 22 ℃ of reactions 10 hours down obtain modified Nano silicon ball crude product.The crude product centrifugation is later with 2.0 milliliters of α, α, and α-phenylfluoroform washed twice is to remove unreacted polymkeric substance, catalyzer and by product.Product drying in 100 ℃ of baking ovens obtained white powder, i.e. modified Nano silicon ball in 2 hours.
Super two open coat preparation:
Modified Nano silicon ball is distributed to α again, and α in α-phenylfluoroform, is made into the solution of 2.0 mg/ml.This solution can also can prepare two open coats at the two open coats of glass surface preparation on printer paper.Solution directly is added drop-wise on the sheet glass, just forms super two coating of dredging in glass sheet surface after the solvent evaporates; Directly printer paper is immersed in the solution, take out the scraps of paper and treat that scraps of paper drying just can form super two open coats on its surface later on.
The ultra-amphosphobic of coating can be tested:
Liquid is finished under room temperature with KRUSS tensiometer K12 in the contact angle test of coatingsurface, and instrument carries IMAQ and analysis software, and the volume of drop is 5 microlitres.Three kinds of liquid have been adopted in this experiment respectively: deionized water (20 ℃ of surface tension are 72.8 milli ox/rice), methylene iodide (20 ℃ of surface tension are 50.8 milli ox/rice), n-Hexadecane (20 ℃ of surface tension are 27.5 milli ox/rice).The result shows that water, methylene iodide and the n-Hexadecane static contact angle on the glass coating surface is respectively 166 °, 157 ° and 150 °.So the coating that the silicon ball after the modification forms at glass surface has super two thin performance.Paper surface forms after the coating, and water droplet also greater than 150 °, illustrates also have good super hydrophobic performance at its surperficial contact angle.
The stability test of coating
Substitute (IPSMA) with micromolecular compound PFTS
10-(F
8H
2MA)
10Nano silicon spheres is carried out modification, then modified Nano silicon ball drips of solution is added to glass surface and makes coating.
Experiment shows that this coating has super two performance of dredging equally.Yet, if this coating is placed in the sodium hydroxide solution of 1.0 mol 3 hours, washing, 100 ℃ of dryings are after 15 minutes, less than 90 °, coating has become wetting ability to water at its surperficial contact angle.Its reason may be because the thickness of micromolecular coating is less, and fluorine-containing section PFO film is also very thin.Sodium hydroxide is easy to penetrate this layer film and destroys siloxane bond, thereby destroys coating, loses its ultra-amphosphobic energy to such an extent as to part PFTS coating is come off from silicon ball surface.
To (IPSMA)
10-(F
8H
2MA)
10The silicon ball coating of di-block copolymer modification has also been done identical experiment.Coating is soaked after 3 hours in the sodium hydroxide solution of 1.0 mol, its surface property does not change, soak after 5 hours, but the wrinkling water of coating at its surperficial contact angle still greater than 130 °, illustrate that the nano silicon spheres with polymeric coating has very high stability.
The foregoing description is a preferred implementation of the present invention; but embodiments of the present invention are not restricted to the described embodiments; other any do not deviate from change, the modification done under spirit of the present invention and the principle, substitutes, combination, simplify; all should be the substitute mode of equivalence, be included within protection scope of the present invention.
Claims (10)
1. two fluorine-containing crosslinkable block copolymers of thin property is characterized in that having the structure suc as formula shown in the I:
SI
k-FL
n
(I)
Wherein, SI has suc as formula the structure shown in the II; R wherein
1And R
5For hydrogen, alkyl or contain the aromatic group of phenyl ring; R
2And R
7Be alkylene; R
3Be alkyl; R
4For-OR
3The perhaps alkoxyl group of other types; R
6Be aromatic nucleus, pyridine ring, pyranoid ring or furan nucleus;
FL is methacrylic acid (17 a fluorine octyl group) ethylene ester;
1＜k＜200；1＜n＜200。
2. according to the described a kind of two fluorine-containing crosslinkable block copolymers of thin property of claim 1, it is characterized in that: described SI is methacrylic acid (3-(three isopropoxies are silica-based)) trimethylene ester.
3. according to the described a kind of two fluorine-containing crosslinkable block copolymers of thin property of claim 1, it is characterized in that: described two fluorine-containing crosslinkable block copolymers of thin property are polymethyl acrylic acid (3-(three isopropoxies are silica-based)) trimethylene ester-block-polymethyl acrylic acid (17 fluorine octyl group) ethylene esters, and two kinds of monomeric number of repeat unit are 10.
4. according to the described a kind of two fluorine-containing crosslinkable block copolymers of thin property of claim 3, it is characterized in that: described polymethyl acrylic acid (3-(three isopropoxies are silica-based)) trimethylene ester-block-polymethyl acrylic acid (17 fluorine octyl group) ethylene ester is to be prepared by following method:
Under-78 ℃, in 250 milliliters of anhydrous tetrahydro furans, add 0.19 milliliter of 1, then add the hexane solution of the s-butyl lithium of 0.6 milliliter of 1.4 mol; Add 2.59 milliliters of methacrylic acids (3-(three isopropoxies are silica-based)) trimethylene ester after 15 minutes, polyreaction carries out adding later in 2 hours 2.60 milliliters of methacrylic acids (17 fluorine octyl group) ethylene ester, and polyreaction continues to add after 2 hours 1.0 milliliters of anhydrous methanols again and stops polyreaction; Underpressure distillation was concentrated into 100 milliliters after reaction system was warmed up to 23 ℃, then with polymer precipitation in methyl alcohol, filter and drying, obtain polymethyl acrylic acid (3-(three isopropoxies are silica-based)) trimethylene ester-block-polymethyl acrylic acid (17 fluorine octyl group) ethylene ester.
5. the application of each described a kind of two fluorine-containing crosslinkable block copolymers of thin property of claim 1-4.
6. according to the application of the described a kind of two fluorine-containing crosslinkable block copolymers of thin property of claim 5, it is characterized in that: described two fluorine-containing crosslinkable block copolymers of thin property are used to prepare the super two open coats of glass or printer paper surface.
7. according to the application of the described a kind of two fluorine-containing crosslinkable block copolymers of thin property of claim 6, it is characterized in that: described two fluorine-containing crosslinkable block copolymers of thin property are used to prepare the super two open coats of glass or printer paper surface and may further comprise the steps:
(1) nano silicon spheres is placed α, α, in α-phenylfluoroform, ultrasonic dissolution obtains nano silicon spheres solution;
(2) under agitation, add two fluorine-containing crosslinkable block copolymers solution of thin property, tetrahydrofuran (THF), hydrochloric acid soln and water in nano silicon spheres solution, 20～25 ℃ were reacted 7～12 hours down, and reaction product is centrifugal, and taking precipitate obtains modified Nano silicon ball crude product;
(3) use α, α, α-phenylfluoroform washing modified Nano silicon ball crude product is dried then, obtains modified Nano silicon ball;
(4) modified Nano silicon ball is distributed to α again, α, in α-phenylfluoroform, being made into modified Nano silicon ball concentration is the solution of 0.5～5 mg/ml; Solution directly is added drop-wise on the sheet glass, forms super two coating of dredging in glass sheet surface after the solvent evaporates; Perhaps directly printer paper is immersed in the solution, take out the scraps of paper and treat to form super two open coats on its surface after the scraps of paper drying.
8. according to the application of the described a kind of two fluorine-containing crosslinkable block copolymers of thin property of claim 7, it is characterized in that: in the step (2), described two fluorine-containing crosslinkable block copolymers of thin property accounts for 8～35% of nano silicon spheres quality, and described two fluorine-containing crosslinkable block copolymers solution of thin property are tetrahydrofuran solutions that two fluorine-containing crosslinkable block copolymers concentration of thin property are 5.0 mg/ml.
9. according to the application of the described a kind of two fluorine-containing crosslinkable block copolymers of thin property of claim 7, it is characterized in that: in the step (2), the volume content of described tetrahydrofuran (THF) in reaction system is 9%, the mol ratio of described nano silicon spheres, water and hydrochloric acid is 1: 2: 1, and described hydrochloric acid soln is that concentration of hydrochloric acid is the tetrahydrofuran solution of 0.2 mol; The described reaction times is 10 hours.
10. according to the application of the described a kind of two fluorine-containing crosslinkable block copolymers of thin property of claim 7, it is characterized in that:
The described crude product drying temperature of step (3) is 100 ℃, and be 2 hours time of drying;
The described modified Nano silicon of step (4) ball α, α, in α-phenylfluoroform solution, modified Nano silicon ball concentration is 2 mg/ml.
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| CN 201110090620 CN102199263B (en) | 2011-04-12 | 2011-04-12 | Amphiphobic fluoro-containing crosslinkable block copolymer and preparation method and application thereof |
| JP2014504127A JP2014513174A (en) | 2011-04-12 | 2012-04-12 | Amphiphobic block copolymers and uses thereof |
| US13/445,430 US20120264884A1 (en) | 2011-04-12 | 2012-04-12 | Amphiphobic Surfaces from Block Copolymers |
| EP12770543.2A EP2697275A4 (en) | 2011-04-12 | 2012-04-12 | Amphiphobic block copolymers and applications thereof |
| PCT/CA2012/000357 WO2012139207A1 (en) | 2011-04-12 | 2012-04-12 | Amphiphobic block copolymers and applications thereof |
| AU2012243394A AU2012243394A1 (en) | 2011-04-12 | 2012-04-12 | Amphiphobic block copolymers and applications thereof |
| BR112013026045A BR112013026045A2 (en) | 2011-04-12 | 2012-04-12 | amphiphobic block copolymer; amphiphobic coating on a substrate; method for preparing amphiphobic coating on a substrate; amphiphobic coating; article; composition for applying amphiphobic coating to a substrate; fabric, fiber or textile; ink; particle |
| CA2833046A CA2833046A1 (en) | 2011-04-12 | 2012-04-12 | Amphiphobic block copolymers and applications thereof |
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| CN103626403A (en) * | 2012-08-27 | 2014-03-12 | 中国科学院兰州化学物理研究所 | Preparation method of transparent super-amphiphobic coating |
| CN105985501A (en) * | 2015-03-18 | 2016-10-05 | 斯沃奇集团研究和开发有限公司 | Substrate comprising a surface covered with an epilamization agent and method for epilaming such a substrate |
| CN106084580A (en) * | 2016-06-20 | 2016-11-09 | 安徽荣达阀门有限公司 | A kind of carbon nanotube/polytetrafluoroethylcomposite valve sealing ring of double thin property |
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| CN103626403A (en) * | 2012-08-27 | 2014-03-12 | 中国科学院兰州化学物理研究所 | Preparation method of transparent super-amphiphobic coating |
| CN103626403B (en) * | 2012-08-27 | 2015-08-26 | 中国科学院兰州化学物理研究所 | A kind of preparation method of transparent super two open coat |
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| CN105985501B (en) * | 2015-03-18 | 2018-10-12 | 斯沃奇集团研究和开发有限公司 | Including being coated with the matrix on the surface of grease proofing diffusant and the grease proofing method of diffusion of the matrix |
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| WO2023083144A1 (en) * | 2021-11-10 | 2023-05-19 | 中国石油大学(华东) | Amphiphobic fluorine-containing nanofluid, preparation method therefor and application thereof |
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