CN102977292A - Amphiphilic cross-linked fluoropolymer and application thereof in preparation of ultra-amphiphobic surface - Google Patents
Amphiphilic cross-linked fluoropolymer and application thereof in preparation of ultra-amphiphobic surface Download PDFInfo
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Abstract
The present invention discloses an amphiphilic cross-linked fluoropolymer and application thereof. The amphiphilic cross-linked fluoropolymer has a general formula shown below, wherein, polymerization degree of an A segment is 40-1000, polymerization degree of a B segment is 10-100, polymerization degree of a C segment is 20-400; the chain segment A is polymerized by monomer as, the chain segment B is polymerized by monomer bs, and the chain segment C is polymerized by monomer cs. The amphiphilic cross-linked fluoropolymer prepared by the present invention has an epoxy group. Therefore the advantage that the epoxy group has an adhesive force with vast majority surfaces of substrates can be used, and an ultra-amphiphobic surface can be constructed on the vast majority of the substrates. The oxysilane in the present invention is a group which can make a crosslinking reaction with the substrate having the surfaces grafted with active groups such as hydroxy, amino or carboxyl, so the fluoropolymer can also make crosslinking reaction with the vast majority of the substrate surfaces. The amphiphilic cross-linked fluoropolymer of the present invention overcome the defects that the adhesive force between the conventional fluoropolymers and the surfaces of the substrates is not strong, and non-toxic environmental-friendly solvents cannot be dispersants. A-B-(B-r-C).
Description
Technical field
The invention belongs to super two thin Material Field, be specifically related to a kind of amphipathic crosslinkable fluoropolymer and the application in the preparation super-double-hydrophobic surface thereof.
Background technology
Super-double-hydrophobic surface is because its unique hydrophobic oleophobic performance can be applicable to a lot of aspects.Super-double-hydrophobic surface has self-cleaning function and can be used for sun power electroplax or minute surface that some need to keep clean, such as the surface of gas kitchen ranges.Moreover metallic surface formation super-double-hydrophobic surface also can greatly improve the corrosion resistance of metallic surface.In addition, if construct super-double-hydrophobic surface at electric wire or high-voltage fence, can avoid electric wire to form cryosphere at ice storm or Character of Snowstorm surface, thereby cause that short circuit causes cutting off the power supply plant downtime on a large scale, even cause the interruption of the communications and transportation circuits such as railway.
Super-double-hydrophobic surface can be constructed by a lot of methods and form, but the most basic condition is to allow the surface have very low surface energy, therefore consider fluorochemicals and fluoropolymer, plate the most cost-effective method that one deck fluorochemicals film just becomes preparation fluorine surface at material surface, so also can keep composition and the character of material internal.Fluorochemicals can form fluorine-containing thin layer at substrate surface, even can be combined in substrate surface by the chemical bonding mode, thereby gives the surface super two thin characteristics, but this thin layer is owing to being that unimolecular layer is easy to be polluted or damage.
And applications of fluoropolymers is in super-double-hydrophobic surface, then can provide surperficial one deck thicker fluorine-containing thin layer, be not vulnerable in actual use the corrosion such as solvent, simultaneously, difficult damage, but present used fluoropolymer is when forming super-double-hydrophobic surface, be difficult between polymkeric substance and the substrate really be bonded together by the chemical bonding effect, and mainly be physisorption, therefore, under outer field action, lose easily established super-double-hydrophobic surface.If can develop the polymkeric substance that not only has the fluoropolymer feature but also can carry out with the surface chemical bonding, then can form real bonding, thereby make super-double-hydrophobic surface and substrate form one.
For the good again super-double-hydrophobic surface material of practicality of processability, many investigators have carried out a large amount of research work.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 polymethacrylate again after two-step electrochemical is processed.There is cohesive strength in this method not equally or the surface holds flimsy problem.Patent CN 1379128A proposed a kind of with chemical gaseous phase depositing process preparation have ultra-amphosphobic can array structure thin film, but technique is relatively harsher, is not easy to suitability for industrialized production and uses.
Patent 201110131477.X has proposed a kind of preparation of fluorine-containing difunctional microballoon and has been applied to construct super-double-hydrophobic surface.But fluorine-contained surface partly is the unit molecule thin layer, therefore is easy to be polluted or damage.Chinese patent 201110090620.5 has proposed a kind of preparation of two fluorine-containing crosslinkable block copolymers of thin property and formed fluorine-containing Nano microsphere after the silica sphere assembling, and is applied to construct super-double-hydrophobic surface.This method needs the preparation of the segmented copolymer of complex process, needs simultaneously harsh assembling condition.
Patent 201110266897.9 has proposed a kind of fluorine-containing silicon-containing copolymer and silicon-dioxide of utilizing and has carried out assembling film forming on the surface of containing active group after the blend, can give well ultra-amphosphobic energy of surface, this method is utilized more fluorine-containing silicon-containing copolymer, and need blend assembling reaction when using, the technique more complicated.
Although in recent years, it is more to utilize fluoropolymer to construct the report of super-double-hydrophobic surface, but most of fluoropolymer and the bonding force between the substrate surface of bibliographical information are not strong at present, thereby it is insecure to cause constructed super-double-hydrophobic surface to exist, the shortcomings such as rub resistance, washing fastness are not strong.
On the other hand, it mainly is oil-soluble constructing at present the fluoropolymer that super-double-hydrophobic surface adopts, and this oil soluble fluoropolymer need to be used a large amount of organic solvents, therefore has certain environmental issue in its application process.
Summary of the invention
In order to overcome the defective that bonding force between existing fluoropolymer and the substrate surface is strong and can't make of the solvent of asepsis environment-protecting dispersion agent, primary and foremost purpose of the present invention is to provide a kind of amphipathic crosslinkable fluoropolymer.
The synthetic method of the amphipathic crosslinkable fluoropolymer that another object of the present invention is to provide above-mentioned.
The application of the amphipathic crosslinkable fluoropolymer that a further object of the present invention is to provide above-mentioned in the preparation super-double-hydrophobic surface.
Purpose of the present invention is achieved through the following technical solutions:
A kind of amphipathic crosslinkable fluoropolymer has general formula as follows:
A-b-(B-r-C)
Wherein, the A segment is fluoropolymer, and the B segment is crosslinkable polymer, and the C segment is hydrophilic polymer, and b represents block, and r represents random copolymerization.
Described amphipathic crosslinkable fluoropolymer, the polymerization degree of A segment is 40-1000, and the polymerization degree of B segment is 10-100, and the polymerization degree of C segment is 20-400.
Described amphipathic crosslinkable fluoropolymer, the A segment is to be polymerized by monomer a, and the B segment is to be polymerized by monomer b, and the C segment is to be polymerized by monomer c.
The structure of described monomer a, b, c is successively suc as formula shown in I, formula II, the formula III:
In formula I, formula II and formula III, R
1, R
2, R
3Be H or CH
3, R
4Be CH
2, O, COOCH
2Or C
6H
6N, m, z are respectively the integer between the 0-10, and q is the integer between the 4-10; Y is 1; X is epoxide group or TMOS;
Described monomer b preferable methyl acryllic acid glycidyl ether, propenyl glycidyl ether, 1,2-epoxy group(ing)-5-hexene or methacryloxypropyl triisopropyl TMOS;
The preferred 3-of described monomer a (perfluor-5-methyl hexyl)-2-hydroxy propyl methacrylate, tetrahydrochysene perfluoro hexyl methacrylic ester, tetrahydrochysene perfluor decyl methacrylic ester, tetrahydrochysene perfluor dodecyl methyl acrylate, hexafluoro isopropylacrylic acid ester, hexafluoro isopropyl methyl acrylate, tetrafluoro propyl methyl acid esters, the perfluoro propyl methacrylic ester, the vinylformic acid trifluoro ethyl ester, methacrylic acid five fluorine ethyl esters, trifluoroethyl methacrylate, perfluoro styrene, the 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 acrylate, perfluor decyl ethyl-methyl acrylate, a kind of in perfluoro capryl ethyl-methyl acrylate or the perfluor heptyl ethyl-methyl acrylate.
It is synthetic that above-mentioned amphipathic crosslinkable fluoropolymer can pass through the methods such as atom transition free radical polymerization reaction, reversible addition-fracture chain transfer polymerization reaction, anionic polymerisation, and its synthetic method specifically may further comprise the steps:
(1) first monomer a polymerization is obtained fluoropolymer A;
(2) with fluoropolymer A as macromole evocating agent, trigger monomer b and monomer c carry out random copolymerization, obtain amphipathic crosslinkable fluoropolymer A-b-(B-r-C).
Above-mentioned amphipathic crosslinkable fluoropolymer can be used for preparing super-double-hydrophobic surface, specifically may further comprise the steps:
(1) gets above-mentioned amphipathic crosslinkable fluoropolymer, be dissolved among the solvent E, stir; The mass ratio 1:(10-100 of amphipathic crosslinkable fluoropolymer and solvent E wherein);
(2) drip water in the stirring in the reaction system of step (1), rate of addition is per minute 1-10ml, obtains the aqueous solution of fluoropolymer after dropwising; Wherein the mass ratio of water and solvent E is 1:(0.0001-0.1);
(3) base material is dipped in the aqueous solution of fluoropolymer, stirs 5-20min, then add catalyzer, restir 30-60min takes out base material, will namely make super-double-hydrophobic surface at base material after the base material oven dry;
The mass ratio of described catalyzer and amphipathic crosslinkable fluoropolymer is 1:(0.01-0.1);
The described solvent E of step (1) is a kind of in tetrahydrofuran (THF), dimethyl sulfoxide (DMSO), dimethyl formamide, n-formyl sarcolysine base pyrrolidone or the N,N-DIMETHYLACETAMIDE;
The described catalyzer of step (3) is a kind of in 2-ethyl-4-methylimidazole, triethylamine, diethylenetriamine, triethylene tetramine, ammoniacal liquor or the hydrochloric acid;
The described base material of step (3) is cotton, the scraps of paper or timber.
Above-mentioned amphipathic crosslinkable fluoropolymer also can be applicable to prepare skin protection, the outer field water-tight corrosion-proof of oil pipeline, the non-resistance coating of preparation oleophobic pipeline lining and the yarn fabric of preparation hydrophobic oleophobic type of the hydrophobic oleophobic coating of water proof anti-corrosive paint, steel surface processing, preparation windshield, the self-cleaning coating for preparing exterior wall self-cleaning coating, preparation sculpture, military industry equipment.
Principle of the present invention is:
Epoxide group is easily open loop under the conditions such as catalyzer, ultraviolet, heat, can be crosslinked with most substrate surfaces generations, form a firmly chemical bond.Therefore, epoxide group is referred to as again multi-purpose adhesive, is widely used in as a kind of surface bonding group in the various fields of modern industry.Therefore select among the present invention to be rich in the monomer of epoxide group as crosslink part.
The TMOS of selecting in this patent also is a kind of group that the base material generation crosslinking reaction of hydroxyl, amino or carboxyl isoreactivity group can be arranged with surface grafting, therefore also is used as cross-linked polymer, with cotton, and the reaction of the base materials such as the scraps of paper or timber.
Fluoropolymer often is used to prepare various low surface energies interface as the lower base polymer of surface energy in the polymkeric substance.Therefore, also select in this article the acrylate containing fluorine material as the low surface energy interface.
Construct at present super-double-hydrophobic surface, poisonous organic solvent is used in general all needing, and not only causes the price of super two thin materials very expensive, and can cause certain environmental pollution.In this patent, introduce and have hydrophilic polyethylene glycol acrylate class material as hydrophilic parts, the dispersion of fluoropolymer in water among realization the present invention.
Super-double-hydrophobic surface refers to the surface of the similar lotus leaf in a kind of interface, water droplet can't flood its surface, can only form on its surface contact angle greater than 150 ° spherical water droplet, and have less roll angle, therefore this surface not only has the water-tight corrosion-proof function, has simultaneously certain self-cleaning function.Construct super-double-hydrophobic surface and generally need to possess two two, the first coarse surface, the secondth, the low surface energy interface, if therefore material surface itself is coarse, such as cotton, timber, paper, then only need directly the low surface energy material to be spread thereon, just can realize the hydrophobic oleophobic effect, therefore, directly fluoropolymer is layered on the material surface with certain degree of roughness in this patent.Utilize centre that epoxide group or TMOS be dispersed in hydrophilic segment as linking agent, utilize fluorine-containing material as the low surface energy material, thereby in water, construct super two thin interface.Final the hydrophobic of this material, the high adhesion and water-soluble realized.
The present invention has following advantage and effect with respect to prior art:
(1) contain epoxide group in the amphipathic crosslinkable fluoropolymer of the present invention's preparation, therefore can utilize epoxide group and most substrate surface to have the advantage of bonding force, can be at the super-double-hydrophobic surface of constructing of most substrate surfaces.
(2) TMOS of selecting in this patent also is a kind of group that the base material generation crosslinking reaction of hydroxyl, amino or carboxyl isoreactivity group can be arranged with surface grafting, therefore also can carry out crosslinking reaction with most of base material tables.
(3) will have the Racemic glycidol ethers acrylate of crosslinked function and TMOS and hydrophilic polyethylene glycol acrylate among the present invention and carry out random copolymerization, realize the water-soluble of crosslinked segment so that epoxide group can be in water with substrate surface on active group carry out chemical reaction.
(4) adopt controlled reactive polymer ATRP to realize the amphipathic fluoride synthetic polymer among the present invention, pass through the method, can regulate very easily different properties segment (hydrophobic part, hydrophilic segment and crosslink part) length, thereby can according to the actual demand of application process, regulate chain length and the composition of difference in functionality part.
(5) to prepare the method for super-double-hydrophobic surface simple in the present invention, only needs to adopt the catalysis epoxy additions such as catalyzer or photo-thermal get final product, so be a kind of preparation method of super-double-hydrophobic surface of simple possible.
(6) utilize the super-double-hydrophobic surface of amphipathic crosslinkable fluoropolymer preparation of the present invention, itself and base material bonding are firm, rub resistance, wash resistant.
Embodiment
The present invention is described in further detail below in conjunction with embodiment, but embodiments of the present invention are not limited to this.
Embodiment 1
ATRP method synthesizing amphipathic crosslinkable type fluoropolymer may further comprise the steps:
In the round-bottomed flask of 100ml, add 1.852g trifluoroethyl methacrylate, 0.203g 2-isobutyl bromide mono methoxy glycol ester, 0.237g 4,4'-dinonyl-2,2'-dipyridyl and 3ml methyl-phenoxide, with the reaction system stirring and dissolving, logical argon gas Gu bubble 30min, again deoxygenation, then reaction system is transferred in the round-bottomed flask of the 50ml that the 0.1124g cuprous bromide is housed, carry out polyreaction 2h at 40 ℃, reaction product is deposited in the methyl alcohol, methyl alcohol is washed and is washed with normal hexane afterwards, and then at room temperature vacuum-drying 24h obtains product P TFEMA-Br to constant weight.
In the round-bottomed flask of 100ml, add above-mentioned synthetic 1.5g polymethyl acrylic acid trifluoro ethyl ester (PTFEMA-Br), 1.052g methyl propenoic acid glycidyl ether (GMA), 1.252g polyoxyethylene glycol methyl propenoic acid glycidyl ether (PEGMA), 0.737g 4,4'-dinonyl-2,2'-dipyridyl and 4ml phenylfluoroform, with the reaction system stirring and dissolving, logical argon gas Gu bubble 30min, again deoxygenation, 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, methyl alcohol is washed and is washed with normal hexane afterwards, and then vacuum-drying 24h obtains PTFEMA-b-P (GMA-r-PEGMA) to constant weight under 40 ℃ of conditions.
The structure of PTFEMA-b-P (GMA-r-PEGMA) is as follows:
Utilize above-mentioned amphipathic crosslinkable fluoropolymer to prepare super-double-hydrophobic surface, may further comprise the steps: (1) gets above-mentioned synthetic amphipathic crosslinkable fluoropolymer
PTFEMA-b-P (GMA-r-PEGMA) 0.1g is dissolved in the tetrahydrofuran (THF), controls stirring velocity at 100rpm, continuously stirring 2 hours; The mass ratio 1:10 of fluoropolymer and tetrahydrofuran (THF) wherein;
(2) drip water in the amphipathic fluoride polymkeric substance that is stirring in the step (1) with the speed of 1ml/min, stirred 1 day after dropwising, obtain the aqueous solution of fluoropolymer.Wherein the mass ratio of water and tetrahydrofuran (THF) is 10:1;
(3) filter paper is joined in the middle aqueous solution of step (2), behind the stirring 5min, add triethylamine again, wherein the mass ratio of triethylamine and amphipathic fluoride polymkeric substance is 1:0.01;
(4) reactant in the step (3) is stirred after the 30min, again filter paper is taken out, after room temperature is dried, be placed on dry 10min in the vacuum drying oven, namely make super-double-hydrophobic surface at filter paper.Wherein oven temperature is controlled at 80 ℃.
Embodiment 2
Anionic polymerization synthesizing amphipathic crosslinkable type fluoropolymer may further comprise the steps:
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 1，1-diphenylethylene, then add the hexane solution of the s-butyl lithium of 0.6 milliliter of 1.4 mol/L.Add 25.19 milliliters of methacrylic acid five fluorine ethyl esters after 25 minutes, polyreaction carries out adding simultaneously later in 1 hour 21.24 milliliters of vinylformic acid glycidyl ethers (GA) and 25 polyethylene glycol methacrylate-styrene polymers (PEGMA), and polyreaction continues to add 1.0 milliliters of anhydrous methanols after 2 hours again again and stops polyreaction.After reaction system is warmed up to 23 ℃, distillation and concentration to 100 milliliter, then with polymer precipitation in excessive methyl alcohol, filter also dryly in vacuum drying oven, obtain needed polymer P FEMA-b-P (GA-r-PEGMA).
The structure of PFEMA-b-P (GA-r-PEGMA) is as follows:
Utilize above-mentioned amphipathic crosslinkable fluoropolymer to prepare super-double-hydrophobic surface, may further comprise the steps:
(1) gets above-mentioned synthetic amphipathic crosslinkable fluoropolymer PFEMA-b-P (GA-r-PEGMA) 0.12g, be dissolved in the dimethyl formamide, control stirring velocity at 500rpm, continuously stirring 4 hours; The mass ratio 1:100 of fluoropolymer and dimethyl formamide wherein;
(2) drip water in the amphipathic fluoride polymkeric substance that is stirring in the step (1) with the speed of 10ml/min, stirred 4 days after dropwising, obtain the aqueous solution of fluoropolymer.Wherein the mass ratio of water and dimethyl formamide is 1:0.0001;
(3) the sheet timber with 120mg joins in the middle aqueous solution of step (2), behind the stirring 20min, adds the catalyzer 2-ethyl-4-methylimidazole again, and wherein the mass ratio between 2-ethyl-4-methylimidazole and the amphipathic fluoride polymkeric substance is 1:0.1;
(4) reaction solution in the step (3) is stirred after the 60min, again timber is taken out, after room temperature is dried, be placed on dry 100min in the vacuum drying oven, namely make super-double-hydrophobic surface at timber.Wherein oven temperature is controlled at 120 ℃.
Embodiment 3
" Click " method of employing synthesizing amphipathic crosslinkable fluoropolymer may further comprise the steps:
In the round-bottomed flask of 100ml, add 2.852g methacrylic acid five fluorine ethyl esters, 0.103g trimethyl silicane ATRP initiator, 0.237g 4,4'-dinonyl-2,2'-dipyridyl and 3ml methyl-phenoxide, with the reaction system stirring and dissolving, logical argon gas Gu bubble 30min, again deoxygenation, then reaction system is transferred in the round-bottomed flask of the 100ml that the 0.1124g cuprous bromide is housed, carry out polyreaction 2h at 40 ℃, reaction product is deposited in the methyl alcohol, methyl alcohol is washed and is washed with normal hexane afterwards, and then at room temperature vacuum-drying 24h obtains to constant weight that product is terminal to be the PFEMA of alkynyl.
In the round-bottomed flask of 100ml, add 0.15g 2-isobutyl bromide mono methoxy glycol ester, 1.852g methyl propenoic acid glycidyl ether and 1.125g polyoxyethylene glycol methyl methacrylate, 0.737g 4,4'-dinonyl-2,2'-dipyridyl and 4ml phenylfluoroform, with the reaction system stirring and dissolving, logical argon gas Gu bubble 30min, again deoxygenation, 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, methyl alcohol is washed and is washed with normal hexane afterwards, and then vacuum-drying 24h obtains P(GMA-r-mPEGMA to constant weight under 40 ℃ of conditions)-N
3
Get the 2g end and join in the 10ml phenylfluoroform for the PFEMA of alkynyl, add again 4g sodium azide and 5mlTHF, 60 ℃ of lower reactions 48 hours, concentrated washing with water again 3 times, oven dry obtains pure P(GMA-r-mPEGMA)-N
3
It is terminal for the polymethyl acrylic acid five fluorine ethyl esters of alkynyl (namely end is the PFEMA of alkynyl) add the 3ml phenylfluoroform to get 1.8g, adds 3ml tetrahydrofuran (THF) and P(GMA-r-mPEGMA again)-N
3, add again 0.08gCuBr, add again 0.3ml five methyl diethylentriamine (PMEDTA) with after the reactor deoxygenation, concentrated after reacting 3 days, be deposited in the methyl alcohol, dry again, obtain pure PFEMA-b-P (GMA-r-mPEGMA).
The structure of PFEMA-b-P (GMA-r-mPEGMA) is as follows:
Utilize above-mentioned amphipathic crosslinkable fluoropolymer to prepare super-double-hydrophobic surface, may further comprise the steps:
(1) gets above-mentioned synthetic amphipathic crosslinkable fluoropolymer PFEMA-b-P (GMA-r-mPEGMA) and be dissolved in the N,N-DIMETHYLACETAMIDE, control stirring velocity at 300rpm, continuously stirring 3 hours; The mass ratio 1:50 of fluoropolymer and N,N-DIMETHYLACETAMIDE wherein;
(2) drip water in the amphipathic fluoride polymkeric substance that is stirring in the step (1) with the speed of 5ml/min, stirred 3 days after dropwising, obtain the aqueous solution of fluoropolymer.Wherein the mass ratio of water and N,N-DIMETHYLACETAMIDE is 1:0.001;
(3) cotton with 200mg joins in the middle aqueous solution of step (2), behind the stirring 10min, adds catalyzer again, and wherein the mass ratio of catalyzer and amphipathic fluoride polymkeric substance is 1:0.08;
(4) reaction system in the step (3) is stirred after the 50min, again cotton is taken out, after room temperature is dried, be placed on dry 80min in the vacuum drying oven, namely make super-double-hydrophobic surface at cotton.Wherein oven temperature is controlled at 100 ℃.
Embodiment 4
ATRP polymerization synthesizing amphipathic crosslinkable type fluoropolymer may further comprise the steps:
In the round-bottomed flask of 100ml, add 1.852g perfluoro capryl ethyl-methyl acrylate, 0.203g 2-isobutyl bromide mono methoxy glycol ester, 0.237g 4,4'-dinonyl-2,2'-dipyridyl and 3ml methyl-phenoxide, with the reaction system stirring and dissolving, logical argon gas Gu bubble 30min, again deoxygenation, then reaction system is transferred in the round-bottomed flask of the 50ml that the 0.1124g cuprous bromide is housed, carry out polyreaction 2h at 40 ℃, reaction product is deposited in the methyl alcohol, methyl alcohol is washed and is washed with normal hexane afterwards, and then at room temperature vacuum-drying 24h obtains product P FOEMA-Br to constant weight.
In the round-bottomed flask of 100ml, add the poly-perfluoro capryl ethyl-methyl acrylate (PFOEMA-Br) of above-mentioned synthetic 1.5g, 1.152g methacryloxypropyl triisopropyl TMOS (IPSMA), 1.352g polyoxyethylene glycol methyl propenoic acid glycidyl ether (PEGMA), 0.737g 4,4'-dinonyl-2,2'-dipyridyl and 4ml phenylfluoroform, with the reaction system stirring and dissolving, logical argon gas Gu bubble 30min, again deoxygenation, 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, methyl alcohol is washed and is washed with normal hexane afterwards, and then vacuum-drying 24h obtains PFOEMA-b-P (IPSMA-r-PEGMA) to constant weight under 40 ℃ of conditions.
The structure of PFOEMA-b-P (IPSMA-r-PEGMA) is as follows:
Utilize above-mentioned amphipathic crosslinkable fluoropolymer to prepare super-double-hydrophobic surface, may further comprise the steps:
(1) gets above-mentioned synthetic amphipathic crosslinkable fluoropolymer PFOEMA-b-P (IPSMA-r-PEGMA) 0.1g, be dissolved in the n-formyl sarcolysine base pyrrolidone, control stirring velocity at 400rpm, continuously stirring 4 hours; The mass ratio 1:100 of fluoropolymer and n-formyl sarcolysine base pyrrolidone wherein;
(2) drip water in the amphipathic fluoride polymkeric substance that is stirring in the step (1) with the speed of 20ml/min, stirred 4 days after dropwising, obtain the aqueous solution of fluoropolymer.Wherein the mass ratio of water and n-formyl sarcolysine base pyrrolidone is 1:0.0001;
(3) be that the scraps of paper of 100mg join in the step (2) in the aqueous solution with weight, stir 15min after, add again catalyst ammonia water (concentration is 37%), wherein the mass ratio of ammoniacal liquor and amphipathic fluoride polymkeric substance is 1:0.01;
(4) reaction system in the step (3) is stirred after the 50min, again the scraps of paper are taken out, after room temperature is dried, be placed on dry 130min in the vacuum drying oven, namely make super-double-hydrophobic surface at the scraps of paper.Wherein oven temperature is controlled at 110 ℃.
Embodiment 5
The amphipathic crosslinkable type fluoropolymer of the synthetic following structure of ATRP polymerization:
In the round-bottomed flask of 100ml, add 1.852g methacrylic ester five fluorine ethyl esters, 0.203g 2-isobutyl bromide mono methoxy glycol ester, 0.237g 4,4'-dinonyl-2,2'-dipyridyl and 3ml methyl-phenoxide, with the reaction system stirring and dissolving, logical argon gas Gu bubble 30min, again deoxygenation, then reaction system is transferred in the round-bottomed flask of the 50ml that the 0.1124g cuprous bromide is housed, carry out polyreaction 2h at 40 ℃, reaction product is deposited in the methyl alcohol, methyl alcohol is washed and is washed with normal hexane afterwards, and then at room temperature vacuum-drying 24h obtains product P FEMA-Br to constant weight.
In the round-bottomed flask of 100ml, add the poly-perfluoro capryl ethyl-methyl acrylate (PFEMA-Br) of above-mentioned synthetic 1.5g, 1.152g methacryloxypropyl triisopropyl TMOS (IPSMA), 1.352g polyoxyethylene glycol methyl propenoic acid glycidyl ether (PEGMA), 0.737g 4,4'-dinonyl-2,2'-dipyridyl and 4ml phenylfluoroform, with the reaction system stirring and dissolving, logical argon gas Gu bubble 30min, again deoxygenation, 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, methyl alcohol is washed and is washed with normal hexane afterwards, and then vacuum-drying 24h obtains PFEMA-b-P (IPSMA-r-PEGMA) to constant weight under 40 ℃ of conditions.
The structure of PFEMA-b-P (IPSMA-r-PEGMA) is as follows:
Utilize above-mentioned amphipathic crosslinkable fluoropolymer to prepare super-double-hydrophobic surface, may further comprise the steps:
(1) gets above-mentioned synthetic amphipathic crosslinkable fluoropolymer PFEMA-b-P (IPSMA-r-PEGMA) 0.1g, be dissolved in the dimethyl sulfoxide (DMSO), control stirring velocity at 300rpm, continuously stirring 3 hours; The mass ratio 1:80 of fluoropolymer and dimethyl sulfoxide (DMSO) wherein;
(2) drip water in the amphipathic fluoride polymkeric substance that is stirring in the step (1) with the speed of 10ml/min, stirred 3 days after dropwising, obtain the aqueous solution of fluoropolymer.Wherein the mass ratio of water and dimethyl sulfoxide (DMSO) is 1:0.001;
(3) be that the scraps of paper of 100mg join in the step (2) in the aqueous solution with weight, stir 10min after, add again catalyst of triethylamine, wherein the mass ratio of triethylamine and amphipathic fluoride polymkeric substance is 1:0.1;
(4) reaction system in the step (3) is stirred after the 50min, again the scraps of paper are taken out, after room temperature is dried, be placed on dry 100min in the vacuum drying oven, namely make super-double-hydrophobic surface at the scraps of paper.Wherein oven temperature is controlled at 100 ℃.
The performance of the prepared super-double-hydrophobic surface of each embodiment of table 1
In the table 1, WCA is water contact angle, OCA is oily contact angle, SA is the water roll angle, all according to document (Dean Xiong and Guojun Liu.Diblock-Copolymer-Coated Water-andOil-Repellent Cotton Fabrics.Langmuir 2012,28, the method in 6911-6918) is tested.
Table 1 characterizes the bonding force of super-double-hydrophobic surface on base material by indexs such as resistance to acids and bases, washing fastness, anti-ultrasonic property.
Wherein the testing method of resistance to acids and bases is reference literature: Guang Li, Haiting Zheng, Yanxue Wang, Hu Wang, Qibao Dong, Ruke Bai.A facile strategy for the fabrication of highly stable superhydrophobic cotton fabric using amphiphilic fluorinated triblock azide copolymers.Polymer 51 (2010) 1940e1946) method in, that is: the super-double-hydrophobic surface for preparing is immersed in respectively in the solvent of different pH values, take out afterwards at set intervals sample, water is washed off after the soda acid on surface, test its contact angle with the contact angle instrument again, when the contact angle of water or oil greater than 150 °, represent that the hydrophobic of this material or oleophobic performance do not descend.Until, representing the hydrophobic of its surface or oleophobic performance less than 150 °, its contact angle descending.And record this time, by comparing the length of this time, characterize its resistance to acids and bases.
The testing method of washing fastness is reference literature (Dean Xiong and Guojun Liu.Diblock-Copolymer-Coated Water-and Oil-Repellent Cotton Fabrics.Langmuir2012,28, the method in 6911-6918).
The testing method of anti-ultrasonic property: super-double-hydrophobic surface is immersed among the THF, because THF has good solubility for above-mentioned super-double-hydrophobic surface, then adopt KQ-218 type ultrasonic cleaner (Kunshan Ultrasonic Instruments Co., Ltd.) ultrasonic, measure the contact angle behind the different ultrasonic times, when the contact angle of water or oil greater than 150 °, represent that the hydrophobic of this material or oleophobic performance do not descend.Until, representing the hydrophobic of its surface or oleophobic performance less than 150 °, its contact angle descending.And record this time, by comparing the length of this time, characterize its anti-ultrasonic property.
Can find out from the performance test results of table 1, amphipathic crosslinkable fluoropolymer of the present invention can generate super-double-hydrophobic surface with base material generation crosslinking reaction in water, construction method with respect to traditional super-double-hydrophobic surface, the method and the polymkeric substance that provide in this patent are more cheap, more environmental protection, in addition, adopt the super-double-hydrophobic surface of amphipathic crosslinkable fluoropolymer preparation of the present invention to have excellent super-hydrophobic super oleophobic performance, and its resistance to acids and bases, anti-supersound washing, washable clean smart detergency is all excellent, can satisfy the requirement of industrial application aspect.
Above-described embodiment is the better embodiment 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 (7)
1. amphipathic crosslinkable fluoropolymer is characterized in that: have general formula as follows:
A-b-(B-r-C)
Wherein, the polymerization degree of A segment is 40-1000, and the polymerization degree of B segment is 10-100, and the polymerization degree of C segment is 20-400; The A segment is to be polymerized by monomer a, and the B segment is to be polymerized by monomer b, and the C segment is to be polymerized by monomer c;
The structure of described monomer a, b, c is successively suc as formula shown in I, formula II, the formula III:
In formula I, formula II and formula III, R
1, R
2, R
3Be H or CH
3, R
4Be CH
2, O, COOCH
2Or C
6H
6N, m, z are respectively the integer between the 0-10, and q is the integer between the 4-10; Y is 1; X is epoxide group or TMOS.
2. amphipathic crosslinkable fluoropolymer according to claim 1, it is characterized in that: described monomer a is 3-(perfluor-5-methyl hexyl)-2-hydroxy propyl methacrylate, tetrahydrochysene perfluoro hexyl methacrylic ester, tetrahydrochysene perfluor decyl methacrylic ester, tetrahydrochysene perfluor dodecyl methyl acrylate, hexafluoro isopropylacrylic acid ester, hexafluoro isopropyl methyl acrylate, tetrafluoro propyl methyl acid esters, the perfluoro propyl methacrylic ester, the vinylformic acid trifluoro ethyl ester, methacrylic acid five fluorine ethyl esters, trifluoroethyl methacrylate, perfluoro styrene, the 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 acrylate, perfluor decyl ethyl-methyl acrylate, a kind of in perfluoro capryl ethyl-methyl acrylate or the perfluor heptyl ethyl-methyl acrylate.
3. amphipathic crosslinkable fluoropolymer according to claim 1, it is characterized in that: described monomer b is methacryloxyethyl acid glycidyl ether, propenyl glycidyl ether, 1,2-epoxy group(ing)-5-hexene or methacryloxypropyl triisopropyl TMOS.
4. the application of each described amphipathic crosslinkable fluoropolymer of claim 1-3 in the preparation super-double-hydrophobic surface.
5. the application of amphipathic crosslinkable fluoropolymer according to claim 4 in the preparation super-double-hydrophobic surface is characterized in that may further comprise the steps:
(1) the weighting profit requires each described amphipathic crosslinkable fluoropolymer of 1-3, is dissolved among the solvent E, stirs; The mass ratio 1:(10-100 of amphipathic crosslinkable fluoropolymer and solvent E wherein);
(2) drip water in the stirring in the reaction system of step (1), rate of addition is per minute 1-10ml, obtains the aqueous solution of fluoropolymer after dropwising; Wherein the mass ratio of water and solvent E is 1:(0.0001-0.1);
(3) base material is dipped in the aqueous solution of fluoropolymer, stirs 5-20min, then add catalyzer, restir 30-60min takes out base material, will namely make super-double-hydrophobic surface at base material after the base material oven dry;
The mass ratio of described catalyzer and amphipathic crosslinkable fluoropolymer is 1:(0.01-0.1);
The described solvent E of step (1) is a kind of in tetrahydrofuran (THF), dimethyl sulfoxide (DMSO), dimethyl formamide, n-formyl sarcolysine base pyrrolidone or the N,N-DIMETHYLACETAMIDE;
The described catalyzer of step (3) is a kind of in 2-ethyl-4-methylimidazole, triethylamine, diethylenetriamine, triethylene tetramine, ammoniacal liquor or the hydrochloric acid.
6. the application of amphipathic crosslinkable fluoropolymer according to claim 5 in the preparation super-double-hydrophobic surface, it is characterized in that: the described base material of step (3) is cotton, the scraps of paper or timber.
Each described amphipathic crosslinkable fluoropolymer of claim 1-3 process at preparation water proof anti-corrosive paint, steel surface, the non-resistance coating of the skin protection of the self-cleaning coating of the hydrophobic oleophobic coating of preparation windshield, preparation exterior wall self-cleaning coating, preparation sculpture, military industry equipment, the outer field water-tight corrosion-proof of oil pipeline, preparation oleophobic pipeline lining and prepare application in the yarn fabric of hydrophobic oleophobic type.
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