CN102432742A - Super-amphiphobic polymer and super-amphiphobic surface prepared from super-amphiphobic polymer - Google Patents
Super-amphiphobic polymer and super-amphiphobic surface prepared from super-amphiphobic polymer Download PDFInfo
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- CN102432742A CN102432742A CN2011102668979A CN201110266897A CN102432742A CN 102432742 A CN102432742 A CN 102432742A CN 2011102668979 A CN2011102668979 A CN 2011102668979A CN 201110266897 A CN201110266897 A CN 201110266897A CN 102432742 A CN102432742 A CN 102432742A
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Abstract
The invention belongs to the field of macromolecule super-amphiphobic materials and discloses a super-amphiphobic polymer and a super-amphiphobic surface. The super-amphiphobic polymer is a random copolymer composed of structural units shown as a formula I and a formula II. The super-amphiphobic surface is obtained by comprising the following steps of: pre-processing a substrate material; placing a micro-balloon in a fluorine-containing solvent, and ultrasonically dissolving to obtain a micro-balloon supernatant solution; adding the super-amphiphobic polymer, a hydrochloric acid tetrahydrofuran solution and water into the micro-balloon solution while stirring, placing the substrate material, and reacting for 5-24 h; and taking out the substrate material, washing by using the fluorine-containing solvent, methanol and water in turn, drying in vacuum, and obtaining the super-amphiphobic surface. The super-amphiphobic polymer disclosed by the invention can give good surface hydrophobic ability and oleophobic ability to the substrate. Because the polymer has the characteristics of the fluorine-containing polymer so that the polymer can be chemically bonded with the surface of the substrate, the obtained super-amphiphobic surface has good scrubbing resistant property and corrosion resistant property.
Description
Technical field
The invention belongs to the ultra two thin field of materials of polymer, be specifically related to a kind of two thin property polymkeric substance and preparation method thereof, and the ultra-amphosphobic surface that obtains by the thin property of this pair polymer manufacture.
Background technology
The topmost characterization parameter of moistened surface behavior is a contact angle, if the surface static contact angle less than 10 °, we are referred to as ultra-hydrophilic surface, if the surface have contact angle greater than 150 °, we are referred to as super hydrophobic surface.If the surface had both had super-hydrophobicity, ultra oleophobic performance is arranged again, we are referred to as super-double-hydrophobic surface.
Super hydrophobic surface is because its unique hydrophobic oleophobic performance, is supposed to or has been applied to a lot of aspects.Super-double-hydrophobic surface has self-cleaning function and can be used for sun power electroplax or some minute surfaces that need keep clean, such as the surface of gas kitchen ranges.Moreover metallic surface formation super-double-hydrophobic surface also can improve the corrosion resistance of metallic surface greatly.If on electric wire or high-voltage fence, construct super-double-hydrophobic surface in addition, can avoid electric wire to form cryosphere, thereby cause that short circuit causes cutting off the power supply plant downtime on a large scale, even cause the interruption of communications and transportation circuits such as railway at ice storm or Character of Snowstorm surface.
Super-double-hydrophobic surface can form through a lot of methods; But the most basic condition is to let the surface have very low surface tension; Therefore consider fluorochemicals and fluoropolymer; Plate the most cost-effective method that one deck fluorochemicals film just becomes preparation fluorine surface at material surface, can also keep the composition and the character of material internal like this.Fluorochemicals can form fluorine-containing thin layer at substrate surface, even can be combined in substrate surface through the chemically bonded mode, thereby gives the surface ultra two thin characteristics, but this thin layer is owing to be that unimolecular layer is easy to receive pollution and perhaps damages.And applications of fluoropolymers then can provide surperficial one deck thicker fluorine-containing thin layer in super-double-hydrophobic surface, is not vulnerable to corrosion such as solvent in actual use; Simultaneously; Difficult damage, but present used fluoropolymer is difficult between polymkeric substance and the substrate really be bonded together through the chemically bonded effect when forming super-double-hydrophobic surface; And mainly be physisorption, therefore there is potential hidden danger.Not only have the fluoropolymer characteristic but also can carry out the chemically bonded polymkeric substance if can develop, then can form real bonding, thereby super-double-hydrophobic surface and substrate are integrally formed with the surface.
For the good practical again super-double-hydrophobic surface material of processability, many investigators have carried out number of research projects.Chinese patent file CN 101492829A has proposed a kind of method for preparing ultra two thin materials in the metallic surface; Metal or metal alloy and copper or copper alloy are inserted in the perfluorinated aliphatic acid organic electrolyte solution as negative electrode and anode; Carry out electrochemical reaction; Can be at the super-double-hydrophobic surface of metal or metal alloy surface deposition one deck perfluorinated aliphatic acid mantoquita; Same research group has proposed a kind of method at metallic copper or the ultra two thin materials of its alloy surface preparation at patent document CN 101492815A, base material is directly put into perfluorinated aliphatic acid organic solution soak, and can obtain having the self-cleaning surface of super-double-thinning property.Chinese patent CN102021628A has proposed the preparation method of a kind of metal titanium or the ultra oleophobic surface of titanium alloy.Mainly be that titanium or titanium alloy surface are carried out obtaining the micrometer structure uneven surface after an anodize; And then on micrometer structure, forming the layer of titanium dioxide nano-tube array structure through two-step anodization, the modification of passing through the low surface energy material then obtains ultra oleophobic and super-double-hydrophobic surface.Though above method raw material is simple and easy to, need integral surface through electrochemical reaction, surface be the unimolecular layer of low surface energy simultaneously, is easy to receive pollute perhaps damage.
Chinese patent CN 101748461A has proposed a kind of aluminium or aluminum alloy sheet to be carried out obtaining the surface that the surface has super-double-thinning property with perfluor chain alkyl trichlorosilane or the processing of perfluor Rohm tech inc again after two-step electrochemical is handled.There is the problem that cohesive strength is not enough or the surface is damaged easily equally in this method.Chinese patent CN 1379128A has proposed a kind of array structure thin film that has the ultra-amphosphobic ability with the chemical gaseous phase depositing process preparation, but technology is relatively harsher, is not easy to suitability for industrialized production and uses.
Summary of the invention
For the shortcoming and deficiency that overcome prior art, primary and foremost purpose of the present invention is to provide a kind of ultra-amphosphobic polymkeric substance.
Another object of the present invention is to provide the preparation method of above-mentioned ultra-amphosphobic polymkeric substance.
A purpose more of the present invention is to provide a kind of ultra-amphosphobic surface, and this ultra-amphosphobic surface is obtained by above-mentioned ultra-amphosphobic polymer manufacture.
The object of the invention is realized through following technical proposals:
A kind of ultra-amphosphobic polymkeric substance, the random copolymers of forming by formula I and formula II structural unit; Wherein, the number of formula I structural unit is 1-500, and the number of formula II structural unit is 1-500;
(formula I) (formula II)
Among the formula I, R
1Be Wasserstoffatoms or methyl, R
2Be organoalkoxysilane or acyloxy organoalkoxysilane, organoalkoxysilane is partly crosslinked through carrying out bonding with substrate after the hydrolysis, perhaps make can carrying out between polymer molecule;
Preferably, formula I structural unit can carry out bonding for the structural unit of (perhaps two) organoalkoxysilane that contains three with substrate after its hydrolysis, perhaps its intermolecular can carry out crosslinked;
Particularly preferably, formula I structural unit is a kind of in vinyltrimethoxy silane, vinyltriethoxysilane, vinyl tripropoxy silane, methacryloxypropyl trimethoxy silane, methacryloxypropyl triethoxyl silane or the methacryloxypropyl three isopropoxy silane;
Most preferably, formula I structural unit is a methacryloxypropyl trimethoxy silane;
Among the formula II, R
3Be Wasserstoffatoms or methyl, R
4Be perfluorophenyl, perfluor oxyalkyl, perfluoroalkyl or alkyl perfluoroalkyl ester, can give surface super hydrophobic oleophobic performance;
Preferably, formula II structural unit is a kind of in perfluoro styrene, perfluor n-propyl vinyl ether, perfluoro hexyl ethene, perfluorobutyl ethylene, perfluor dodecyl ethyl propylene acid esters, perfluor decyl ethyl propylene acid esters, perfluoro capryl ethyl propylene acid esters, perfluor heptyl ethyl propylene acid esters, perfluor dodecyl ethyl-methyl propenoate, perfluor decyl ethyl-methyl propenoate, perfluoro capryl ethyl-methyl propenoate or the perfluor heptyl ethyl-methyl propenoate;
Particularly preferably, formula II structural unit is a perfluoro capryl ethyl propylene acid esters.
Above-mentioned ultra-amphosphobic polymkeric substance prepares through radical polymerization, ATRP or method of emulsion polymerization.
A kind of ultra-amphosphobic surface is prepared by following method:
(1) base material pre-treatment;
(2) microballoon is placed contain fluorous solvent, supersound process is dispersed in microballoon and contains in the fluorous solvent, obtains the microballoon aaerosol solution;
(3) stirring adds above-mentioned ultra-amphosphobic polymkeric substance, hydrochloric acid tetrahydrofuran solution and water down in microspheres solution, puts into base material again, and 20-30 ℃ is reacted 5-24h down; Base material is taken out, and with containing fluorous solvent, methyl alcohol, water washing, vacuum-drying then promptly obtains the ultra-amphosphobic surface successively;
The described base material of step (1) is a kind of in glass, filter paper, plastics, cotton or the pottery;
The pre-treatment of glass is: glass surface is cleaned up, remove greasy dirt; The pre-treatment of filter paper, plastics and cotton is: use ethanol, water washing successively, and dry then; The pre-treatment of pottery is: use the diluted acid soaked overnight, use ethanol, water washing, final drying then successively;
The said microballoon of step (2) is that a kind of in the organic polymer microballoon of hydroxyl contained on silicon dioxide microsphere, titanium dioxide microballoon sphere or surface;
Silicon dioxide microsphere can be through traditional Stober method (Stober, W.; Fink, A.; Bohn; E.J.Colloid Interf.Sci.1968,26:62) preparation is in ethanol and aqueous systems; Catalysis through ammoniacal liquor; Positive tetraethyl orthosilicate hydrolysis can obtain having the nano silicon spheres of certain grain size, the product spinning later on washing with alcohol three times to remove catalyzer, unreacted reactant and by product, vacuum freezedrying obtains the white powder silicon dioxide microsphere later on;
Titanium dioxide microballoon sphere can be through the sol-gel process preparation;
The organic polymer microballoon of surface hydroxyl can combine the atom transfer radical polymerization method preparation through letex polymerization;
The particle diameter of said microballoon is 10-1000nm;
Silicon dioxide microsphere can be regulated size through the ratio of regulating ammoniacal liquor and water;
Titanium dioxide microballoon sphere can be through adjusting size such as strength of solution;
The organic polymer microballoon of surface hydroxyl can change size through changing the reaction charging capacity;
Step (2) and (3) are described to contain a kind of in the preferred phenylfluoroform of fluorous solvent, perfluor benzene or the HFC-143a;
The time of the said ultrasonic dissolution of step (2) is 1-5min, is as the criterion so that microballoon is dispersed in to contain in the fluorous solvent;
The concentration of microballoon is 2.5-75mg/ml in the said microspheres solution of step (2);
The mass ratio of described ultra-amphosphobic polymkeric substance of step (3) and microballoon is 0.13-9: 1;
The concentration of the said hydrochloric acid tetrahydrofuran solution of step (3) is 0.05-0.4mol/L;
The add-on of the said hydrochloric acid tetrahydrofuran solution of step (3) is the 2-9% of fluorine-containing solvent volume;
The add-on of the said water of step (3) is the 1.5-2.5 ‰ of fluorine-containing solvent volume.
Principle of the present invention is: adopting the fluorochemical monomer with long-chain is raw material with having (potential) crosslinkable functionality monomer; Utilize various free radical polymerisation process; The synthetic polymkeric substance that had not only had the fluoropolymer characteristic but also can carry out chemically bonded with substrate surface; Through having the functional groups reaction of (potential) crosslinkable functionality monomer and substrate, make ultra-amphosphobic polymkeric substance and substrate form real bonding, super-double-hydrophobic surface and substrate just can be integrally formed like this.
Because excellent chemical stability and thermostability that fluorine-containing composition itself is had make the surface of crossing with ultra-amphosphobic polymer treatment of the present invention have good thermotolerance and chemicalstability.In temperature is 200 ℃ of heating one hour, the surface property no change.Comprise immersions such as THF, chloroform, acetone with various organic solvents after 360 hours, surperficial no change and performance no change.Soak 5h, surperficial no change and performance no change with 1M hydrochloric acid soln or 1M sodium hydroxide solution.The super-double-hydrophobic surface that this surface obtains with the said method of patent of the present invention has good chemical stability and thermostability.
The present invention has following advantage and effect with respect to prior art:
(1) the existing fluoropolymer characteristic of ultra-amphosphobic polymkeric substance of the present invention can be carried out chemically bonded with substrate surface again, thereby has guaranteed that gained ultra-amphosphobic surface has good scrubbing resistance and erosion resistance.
(2) ultra-amphosphobic polymkeric substance of the present invention can be given good surface hydrophobicity ability of substrate and oleophobic ability.
(3) preparation method on ultra-amphosphobic of the present invention surface is simple, and the surface that obtains have good stability and good ultra-amphosphobic can, therefore, can be widely used in all respects of productive lifes such as electric power, military affairs, building and kitchen guarding's apparatus.
Description of drawings
Fig. 1 is the nuclear magnetic resonance map of the random copolymers for preparing of embodiment 1.
Embodiment
Below in conjunction with embodiment and accompanying drawing the present invention is described in further detail, but embodiment of the present invention is not limited thereto.
Embodiment 1
A kind of preparation method of ultra-amphosphobic polymkeric substance may further comprise the steps:
In the round-bottomed flask of 100ml, add 15g perfluoro capryl ethyl propylene acid esters, 1.852g methacryloxypropyl trimethoxy silane, 0.203g2-isobutyl bromide mono methoxy glycol ester, 0.737g 4,4 '-dinonyl-2,2 '-dipyridyl and 4ml phenylfluoroform; With the reaction system stirring and dissolving, logical argon gas bubbling 30min, deoxygenation again; Then reaction system is transferred in the round-bottomed flask of the 100ml that the 0.1294g cuprous bromide is housed; Carry out polyreaction 8h at 90 ℃, reaction product is deposited in the methyl alcohol, and methyl alcohol is washed the back and washed with normal hexane; Vacuum-drying 24h obtains product to constant weight under 40 ℃ of conditions then.
Spectrum Analysis to product is following:
1H-NMR (phenyl-hexafluoride/CDCl
3=2/1 volume ratio): 2.60 (m ,-CH
2-(CF
2)
7CF
3, 2H), 3.42 (m ,-O-CH
3, 3H), 0.65 (m ,-CH
2-Si (OCH
3)
3, 2H); Specifically as shown in Figure 1, the product structure that can infer present embodiment in conjunction with Fig. 1 can infer that from Fig. 1 wherein m is 43 shown in formula III, and n is 9, and it is 25274 that calculating can get prepared polymericular weight.
Formula (III)
A kind of preparation method of ultra-amphosphobic polymkeric substance may further comprise the steps:
In the round-bottomed flask of 100ml, add 15g perfluoro capryl ethyl propylene acid esters, 1.852g methacryloxypropyl trimethoxy silane, 0.174g AIBN as initiator and 50ml phenylfluoroform; With the reaction system stirring and dissolving, logical argon gas bubbling 30min carries out polyreaction 8h at 90 ℃; Reaction product is deposited in the methyl alcohol; Methyl alcohol is washed the back and is washed with normal hexane, and vacuum-drying 24h obtains product to constant weight under 40 ℃ of conditions then.
Spectrum Analysis to product is following:
1H-NMR (phenyl-hexafluoride/CDCl
3=2/1 volume ratio): 2.60 (m ,-CH
2-(CF
2)
7CF
3, 2H), 3.42 (m ,-O-CH
3, 3H), 0.65 (m ,-CH
2-Si (OCH
3)
3, 2H); Concrete nuclear-magnetism figure chemical shift is identical with Fig. 1, and the syncaryon magnetic chart can be inferred the same formula III of the product structure of present embodiment, can infer that wherein m is 80, and n is 17, and it is 47107 that calculating can get prepared polymericular weight.
Embodiment 3
The preparation of the polymer nano-microspheres of hydroxyl is contained on the surface:
Under agitation; In 500 milliliters there-necked flask, progressively add 130 ml distilled waters; 4.80 the mixture of gram (48.0 mmole) TEB 3K and 0.4 gram (2.0 mmole) TGM 1, and 41 milligrams of (0.15 micromole) peroxy-disulfuric acid aqueous solutions of potassium (5 milliliters).Reaction system 25 ℃ down drum nitrogen 15 minutes with the oxygen in the removal system.Then be heated to 90 ℃ in the oil bath, and reacted 2 hours.
From above-mentioned system, take out 43 ml solns, join in 250 milliliters of there-necked flasks that are filled with nitrogen, and add 0.5 milliliter and be dissolved with 2.4 milligrams of (14.6 micromole) Diisopropyl azodicarboxylate tetrahydrofuran solutions.Stir under 25 ℃ and be heated to 90 ℃ later in 15 minutes.Slowly add subsequently and contain 0.4 gram (1.9 mmole) 2-chloropropionic acid terepthaloyl moietie diester, the mixed solution of 40 microlitres (0.21 micromole) TGM 1 and 0.67 gram (6.7 mmole) TEB 3K.Add the polymer microballoon that obtained having nucleocapsid structure with the continued reaction in 4 hours.
In 50 milliliters reaction flask, it is in 1: 1 the mixed solution of second alcohol and water that 13.6 milligrams of above-mentioned hud typed polymer microballoons are distributed to 5 ml volumes ratio.Add 23 milligrams of (0.16 mmole) cuprous bromides then successively; 2.3 milligram (0.010 mmole) cupric bromide; 64.5 milligram (0.28 mmole) three-(N, N-dimethylaminoethyl) amine (Me6TREN) and 0.3728 gram (3.21 mmole) vinylformic acid hydroxyl ethylene ester.System through three times freezing-vacuumize-melt-rouse after the circulation of nitrogen in 75 ℃ of reactions 10 hours down.Product is dialysed in water to remove catalystsystem and other small molecular weight impurities.The hydroxy polymer microballoon is contained on the surface that obtains having the nucleocapsid shell mould after the drying.
The preparation of silicon dioxide microsphere:
In the round-bottomed flask of 100ml, add 50ml absolute ethyl alcohol, 2ml deionized water and 2ml ammoniacal liquor; Drip the positive tetraethyl orthosilicate of 2ml then; After reacting 24 under 25 ℃; Product is with absolute ethyl alcohol centrifuge washing three times, and the silicon dioxide microsphere that obtains carries out vacuum freezedrying, and final gained silicon dioxide microsphere particle diameter is 150 ± 7nm.
Embodiment 5
The preparation of silicon dioxide microsphere:
In the round-bottomed flask of 100ml, add 50ml absolute ethyl alcohol, 3ml deionized water and 3ml ammoniacal liquor; Drip the positive tetraethyl orthosilicate of 2ml then; After reacting 24 under 25 ℃; Product is with absolute ethyl alcohol centrifuge washing three times, and the silicon dioxide microsphere that obtains carries out vacuum freezedrying, and final gained silicon dioxide microsphere particle diameter is 350 ± 10nm.
The preparation on a kind of ultra-amphosphobic surface may further comprise the steps:
(1) glass surface is used washing earlier, clean with methanol wash then, vacuum-drying, subsequent use.
(2) silicon dioxide microsphere of getting among the 5mg embodiment 5 places the 2ml phenylfluoroform, through the 5min ultrasonic dissolution, microballoon is dispersed in the phenylfluoroform, obtains microspheres solution.
(3) under agitation, in microspheres solution, add embodiment 1 prepared ultra-amphosphobic polymkeric substance 20mg, hydrochloric acid tetrahydrofuran solution 40 microlitres of 0.2mol/L and the water of 5 microlitres, simultaneously; Put into pretreated clean sheet glass, 25 ℃ are reacted 24h down, sheet glass are taken out; With phenylfluoroform washing three times, methanol wash three times is used water washing three times then; Vacuum-drying obtains having the surperficial sheet glass of ultra-amphosphobic.The water contact angle of glass sheet surface is 153 °, and oily contact angle is 141 °.After THF rinsing 10 times, contact angle is constant.
Embodiment 7
The preparation on a kind of ultra-amphosphobic surface may further comprise the steps:
(1) get filter paper and use ethanol, water washing successively, dry, subsequent use then;
(2) silicon dioxide microsphere among the 5mg embodiment 4 is placed the 2ml phenylfluoroform,, microballoon is dispersed in the phenylfluoroform, obtain microspheres solution through the 3min ultrasonic dissolution.
(3) under agitation, in microspheres solution, add embodiment 1 prepared ultra-amphosphobic polymkeric substance 20mg, hydrochloric acid tetrahydrofuran solution 40 microlitres of 0.4mol/L and the water of 3 microlitres, simultaneously; Put into clean filter paper, 25 ℃ are reacted 12h down, filter paper are taken out; With phenylfluoroform washing three times, methanol wash three times is used water washing three times then; Vacuum-drying obtains having the surperficial filter paper of ultra-amphosphobic.Filter paper surface water contact angle is 162 °, and oily contact angle is 153 °.After THF rinsing 10 times, contact angle is constant.
The preparation on a kind of ultra-amphosphobic surface may further comprise the steps:
(1) get the cotton bar and use ethanol, water washing successively, dry, subsequent use then;
(2) silicon dioxide microsphere among the 5mg embodiment 5 is placed the 2ml phenylfluoroform,, microballoon is dispersed in the phenylfluoroform, obtain microspheres solution through the 3min ultrasonic dissolution.
(3) under agitation, in microspheres solution, add embodiment 1 prepared ultra-amphosphobic polymkeric substance 20mg, hydrochloric acid tetrahydrofuran solution 40 microlitres of 0.2mol/L and the water of 5 microlitres, simultaneously; Put into clean cotton bar, 25 ℃ are reacted 12h down, the cotton bar are taken out; With phenylfluoroform washing three times, methanol wash three times is used water washing three times then; Vacuum-drying obtains having the surperficial cotton bar of ultra-amphosphobic.The water contact angle on cotton bar surface is 159 °, and oily contact angle is 152 °.After THF rinsing 10 times, contact angle is constant.
Embodiment 9
The preparation on a kind of ultra-amphosphobic surface may further comprise the steps:
(1) get filter paper and use ethanol, water washing successively, dry, subsequent use then;
(2) silicon dioxide microsphere among the 5mg embodiment 5 is placed the 2ml phenylfluoroform,, microballoon is dispersed in the phenylfluoroform, obtain microspheres solution through the 3min ultrasonic dissolution.
(3) under agitation, in microspheres solution, add embodiment 1 prepared ultra-amphosphobic polymkeric substance 20mg, hydrochloric acid tetrahydrofuran solution 40 microlitres of 0.05mol/L and the water of 5 microlitres, simultaneously; Put into the clean scraps of paper, 25 ℃ are reacted 5h down, filter paper are taken out; With phenylfluoroform washing three times, methanol wash three times is used water washing three times then; Vacuum-drying obtains having the surperficial filter paper of ultra-amphosphobic.The water contact angle on filter paper surface is 145 °, and oily contact angle is 132 °.After THF rinsing 10 times, contact angle is constant.
Embodiment 10
The preparation on a kind of ultra-amphosphobic surface may further comprise the steps:
(1) get filter paper and use ethanol, water washing successively, dry, subsequent use then;
(2) silicon dioxide microsphere among the 5mg embodiment 4 is placed the 2ml phenylfluoroform,, microballoon is dispersed in the phenylfluoroform, obtain microspheres solution through the 5min ultrasonic dissolution.
(3) under agitation, in microspheres solution, add embodiment 2 prepared ultra-amphosphobic polymkeric substance 20mg, hydrochloric acid tetrahydrofuran solution 40 microlitres of 0.4mol/L and the water of 3 microlitres, simultaneously; Put into clean filter paper, 25 ℃ are reacted 12h down, filter paper are taken out; With phenylfluoroform washing three times, methanol wash three times is used water washing three times then; Vacuum-drying obtains having the surperficial filter paper of ultra-amphosphobic.The water contact angle on filter paper surface is 161 °, and oily contact angle is 151 °.After THF rinsing 10 times, contact angle is constant.
Embodiment 11
The preparation on a kind of ultra-amphosphobic surface may further comprise the steps:
(1) get the cotton bar and use ethanol, water washing successively, dry, subsequent use then;
(2) silicon dioxide microsphere among the 5mg embodiment 5 is placed the 2ml phenylfluoroform,, microballoon is dispersed in the phenylfluoroform, obtain microspheres solution through the 3min ultrasonic dissolution.
(3) under agitation, in microspheres solution, add embodiment 1 prepared ultra-amphosphobic polymkeric substance 20mg, hydrochloric acid tetrahydrofuran solution 40 microlitres of 0.2mol/L and the water of 5 microlitres, simultaneously; Put into clean cotton bar, 20 ℃ are reacted 12h down, the cotton bar are taken out; With phenylfluoroform washing three times, methanol wash three times is used water washing three times then; Vacuum-drying obtains having the surperficial cotton bar of ultra-amphosphobic.The water contact angle on cotton bar surface is 155 °, and oily contact angle is 146 °.After THF rinsing 10 times, contact angle is constant.
Embodiment 12
The preparation on a kind of ultra-amphosphobic surface may further comprise the steps:
(1) get filter paper and use ethanol, water washing successively, dry, subsequent use then;
(2) silicon dioxide microsphere among the 5mg embodiment 4 is placed the 2ml phenylfluoroform,, microballoon is dispersed in the phenylfluoroform, obtain microspheres solution through the 3min ultrasonic dissolution.
(3) under agitation, in microspheres solution, add embodiment 2 prepared ultra-amphosphobic polymkeric substance 20mg, hydrochloric acid tetrahydrofuran solution 40 microlitres of 0.4mol/L and the water of 3 microlitres, simultaneously; Put into clean filter paper, 25 ℃ are reacted 12h down, filter paper are taken out; With phenylfluoroform washing three times, methanol wash three times is used water washing three times then; Vacuum-drying obtains having the surperficial filter paper of ultra-amphosphobic.The water contact angle on filter paper surface is 159 °, and oily contact angle is 151 °.After THF rinsing 10 times, contact angle is constant.
Embodiment 13
The preparation on a kind of ultra-amphosphobic surface may further comprise the steps:
(1) get filter paper and use ethanol, water washing successively, dry, subsequent use then;
(2) polymer nano-microspheres that hydroxyl is contained on the surface among the 5mg embodiment 3 places the 2ml phenylfluoroform, through the 1min ultrasonic dissolution, microballoon is dispersed in the phenylfluoroform, obtains microspheres solution.
(3) under agitation, in microspheres solution, add embodiment 2 prepared ultra-amphosphobic polymkeric substance 20mg, hydrochloric acid tetrahydrofuran solution 40 microlitres of 0.4mol/L and the water of 3 microlitres, simultaneously; Put into clean filter paper, 30 ℃ are reacted 12h down, filter paper are taken out; With phenylfluoroform washing three times, methanol wash three times is used water washing three times then; Vacuum-drying obtains having the surperficial filter paper of ultra-amphosphobic.The water contact angle on filter paper surface is 162 °, and oily contact angle is 152 °.After THF rinsing 10 times, contact angle is constant.
Embodiment 14
The preparation on a kind of ultra-amphosphobic surface may further comprise the steps:
(1) get filter paper and use ethanol, water washing successively, dry, subsequent use then;
(2) silicon dioxide microsphere among the 50mg embodiment 4 is placed the 2ml phenylfluoroform,, microballoon is dispersed in the phenylfluoroform, obtain microspheres solution through the 5min ultrasonic dissolution.
(3) under agitation, in microspheres solution, add embodiment 2 prepared ultra-amphosphobic polymkeric substance 10mg, hydrochloric acid tetrahydrofuran solution 40 microlitres of 0.4mol/L and the water of 3 microlitres, simultaneously; Put into clean filter paper, 25 ℃ are reacted 12h down, filter paper are taken out; With phenylfluoroform washing three times, methanol wash three times is used water washing three times then; Vacuum-drying obtains having the surperficial filter paper of ultra-amphosphobic.The water contact angle on filter paper surface is 157 °, and oily contact angle is 150 °.After THF rinsing 10 times, contact angle is constant.
Embodiment 15
The preparation on a kind of ultra-amphosphobic surface may further comprise the steps:
(1) get filter paper and use ethanol, water washing successively, dry, subsequent use then;
(2) silicon dioxide microsphere among the 150mg embodiment 4 is placed the 2ml phenylfluoroform,, microballoon is dispersed in the phenylfluoroform, obtain microspheres solution through the 5min ultrasonic dissolution.
(3) under agitation, in microspheres solution, add embodiment 2 prepared ultra-amphosphobic polymkeric substance 20mg, hydrochloric acid tetrahydrofuran solution 40 microlitres of 0.4mol/L and the water of 3 microlitres, simultaneously; Put into clean filter paper, 25 ℃ are reacted 12h down, filter paper are taken out; With phenylfluoroform washing three times, methanol wash three times is used water washing three times then; Vacuum-drying obtains having the surperficial filter paper of ultra-amphosphobic.The water contact angle on filter paper surface is 145 °, and oily contact angle is 133 °.After THF rinsing 10 times, contact angle is constant.
Embodiment 16
The preparation on a kind of ultra-amphosphobic surface may further comprise the steps:
(1) get filter paper and use ethanol, water washing successively, dry, subsequent use then;
(2) silicon dioxide microsphere among the 5mg embodiment 4 is placed the 2ml phenylfluoroform,, microballoon is dispersed in the phenylfluoroform, obtain microspheres solution through the 5min ultrasonic dissolution.
(3) under agitation, in microspheres solution, add embodiment 2 prepared ultra-amphosphobic polymkeric substance 45mg, hydrochloric acid tetrahydrofuran solution 180 microlitres of 0.4mol/L and the water of 3 microlitres, simultaneously; Put into clean filter paper, 25 ℃ are reacted 12h down, filter paper are taken out; With phenylfluoroform washing three times, methanol wash three times is used water washing three times then; Vacuum-drying obtains having the surperficial filter paper of ultra-amphosphobic.The water contact angle on filter paper surface is 147 °, and oily contact angle is 139 °.After THF rinsing 10 times, contact angle is constant.
Each embodiment final product performance of table 1 is summed up
| |
6 | 7 | 8 | 9 | 10 | 11 | 12 | 13 | 14 | 15 | 16 |
| WCA | 153 | 162 | 159 | 145 | 161 | 155 | 159 | 162 | 149 | 145 | 147 |
| OCA | 141 | 153 | 152 | 132 | 151 | 146 | 151 | 152 | 141 | 133 | 139 |
| SA | 5 | 3 | 3 | 7 | 3 | 3 | 3 | 3 | 15 | 30 | 24 |
Annotate: WCA, water contact angle, OCA, oily contact angle, SA oil roll angle.Multipolymer contact angle and roll angle are measured down at 25 ℃, and water contact angle is measured with deionized water, and the drop amount is 6 μ l, and oily contact angle is measured with edible oil, and the drop amount is 8 μ l, and roll angle adopts the tilted plate method to measure.
Can know utilize the ultra-amphosphobic polymkeric substance of patent preparation of the present invention and the surperficial nanoparticle that contains reactive group can be assembled into surface, and oil droplet to have less roll angle from the teeth outwards with super-hydrophobic/ultra oleophobic performance according to last table.
The foregoing description is a preferred implementation of the present invention; But embodiment of the present invention is 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. ultra-amphosphobic polymkeric substance is characterized in that: the random copolymers of being made up of formula I and formula II structural unit; Wherein, the number of formula I structural unit is 1-500, and the number of formula II structural unit is 1-500;
(formula I) (formula II)
Among the formula I, R
1Be Wasserstoffatoms or methyl, R
2Be organoalkoxysilane or acyloxy organoalkoxysilane;
Among the formula II, R
3Be Wasserstoffatoms or methyl, R
4Be perfluorophenyl, perfluor oxyalkyl, perfluoroalkyl or alkyl perfluoroalkyl ester.
2. ultra-amphosphobic polymkeric substance according to claim 1 is characterized in that:
Described formula I structural unit is a kind of in vinyltrimethoxy silane, vinyltriethoxysilane, vinyl tripropoxy silane, methacryloxypropyl trimethoxy silane, methacryloxypropyl triethoxyl silane or the methacryloxypropyl three isopropoxy silane;
Described formula II structural unit is a kind of in perfluoro styrene, perfluor n-propyl vinyl ether, perfluoro hexyl ethene, perfluorobutyl ethylene, perfluor dodecyl ethyl propylene acid esters, perfluor decyl ethyl propylene acid esters, perfluoro capryl ethyl propylene acid esters, perfluor heptyl ethyl propylene acid esters, perfluor dodecyl ethyl-methyl propenoate, perfluor decyl ethyl-methyl propenoate, perfluoro capryl ethyl-methyl propenoate or the perfluor heptyl ethyl-methyl propenoate.
3. ultra-amphosphobic polymkeric substance according to claim 1 is characterized in that:
Described formula I structural unit is a methacryloxypropyl trimethoxy silane;
Described formula II structural unit is a perfluoro capryl ethyl propylene acid esters.
4. ultra-amphosphobic surface is characterized in that it being to be prepared by following method:
(1) base material pre-treatment;
(2) microballoon is placed contain fluorous solvent, supersound process obtains the microballoon aaerosol solution;
(3) stirring adds each described ultra-amphosphobic polymkeric substance of claim 1-3, hydrochloric acid tetrahydrofuran solution and water down in microspheres solution, puts into base material again, and 20-30 ℃ is reacted 5-24h down; Base material is taken out, and with containing fluorous solvent, methyl alcohol, water washing, vacuum-drying then promptly obtains the ultra-amphosphobic surface successively.
5. ultra-amphosphobic according to claim 4 surface is characterized in that:
The described base material of step (1) is a kind of in glass, filter paper, plastics, cotton or the pottery;
The pre-treatment of glass is: glass surface is cleaned up, remove greasy dirt; The pre-treatment of filter paper, plastics and cotton is: use ethanol, water washing successively, and dry then; The pre-treatment of pottery is: use the diluted acid soaked overnight, use ethanol, water washing, final drying then successively.
6. ultra-amphosphobic according to claim 4 surface is characterized in that:
The particle diameter of the said microballoon of step (2) is 10-1000nm;
Said microballoon is that a kind of in the organic polymer microballoon of hydroxyl contained on silicon dioxide microsphere, titanium dioxide microballoon sphere or surface.
7. ultra-amphosphobic according to claim 4 surface is characterized in that: step (2) and (3) are described, and to contain fluorous solvent be a kind of in phenylfluoroform, perfluor benzene or the HFC-143a.
8. ultra-amphosphobic according to claim 4 surface is characterized in that:
The time of the said ultrasonic dissolution of step (2) is 1-5min;
The concentration of microballoon is 2.5-75mg/ml in the said microspheres solution of step (2).
9. ultra-amphosphobic according to claim 4 surface is characterized in that:
The mass ratio of described ultra-amphosphobic polymkeric substance of step (3) and microballoon is 0.13-9: 1;
The concentration of the said hydrochloric acid tetrahydrofuran solution of step (3) is 0.05-0.4mol/L.
10. ultra-amphosphobic according to claim 4 surface is characterized in that:
The add-on of the said hydrochloric acid tetrahydrofuran solution of step (3) is the 2-9% of fluorine-containing solvent volume;
The add-on of the said water of step (3) is the 1.5-2.5 ‰ of fluorine-containing solvent volume.
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