CN102977292B - 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 preparing super-double-hydrophobic surface thereof.
Background technology
Super-double-hydrophobic surface, due to its unique hydrophobic oleophobic performance, can be applicable to a lot of aspects.Super-double-hydrophobic surface has that self-cleaning function can be used for sun power electroplax or some need to keep clean minute surface, 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 on 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 power-off plant downtime on a large scale, even causes the interruption of the communications and transportation circuits such as railway.
Super-double-hydrophobic surface can be constructed and be formed by a lot of methods, but the most basic condition is to allow surface have very low surface energy, therefore consider fluorochemicals and fluoropolymer, at material surface, plating one deck fluorochemicals film just becomes the most cost-effective method of preparing fluorine 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 chemical bonding mode, thereby gives 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, the fluorine-containing thin layer that surperficial one deck is thicker can be provided, be not vulnerable in actual use the corrosion such as solvent, meanwhile, more difficult damage, but current fluoropolymer used is while forming super-double-hydrophobic surface, between polymkeric substance and substrate, be difficult to really by chemical bonding effect, be bonded together, and be mainly physisorption, therefore, under outer field action, easily lose established super-double-hydrophobic surface.If can develop, not only there is fluoropolymer feature but also can carry out the polymkeric substance of chemical bonding with surface, can form real bonding, thereby make super-double-hydrophobic surface and substrate form one.
For the good super-double-hydrophobic surface material of practicality again 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 with perfluor chain alkyl trichlorosilane or perfluor polymethacrylate, processing and obtaining the surface that surface has super-double-thinning property again after two-step electrochemical processing.There is cohesive strength not in this method or surface holds flimsy problem equally.Patent CN 1379128A has proposed a kind of array structure thin film with chemical gaseous phase depositing process preparation with ultra-amphosphobic energy, but technique is harsher, is not easy to suitability for industrialized production application.
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 is partly unit molecule thin layer, be therefore 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 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 harsh assembling condition simultaneously.
Patent 201110266897.9 has proposed a kind of fluorine-containing silicon-containing copolymer and silicon-dioxide of utilizing and has carried out on the surface of containing active group, assembling film forming after blend, can give well ultra-amphosphobic energy of surface, this method is utilized more fluorine-containing silicon-containing copolymer, and when using, need blend assembling reaction, technique more complicated.
Although in recent years, utilize fluoropolymer to construct the report of super-double-hydrophobic surface more, but most of fluoropolymer and the bonding force between substrate surface of bibliographical information are not strong at present, thereby it is insecure to cause constructed super-double-hydrophobic surface to exist, rub resistance, the shortcoming such as washing fastness is not strong.
On the other hand, it is mainly oil-soluble constructing at present the fluoropolymer that super-double-hydrophobic surface adopts, and this oil soluble fluoropolymer, need to use a large amount of organic solvents, therefore in its application process, has certain environmental issue.
Summary of the invention
Strong and cannot make of the solvent of asepsis environment-protecting the defect of dispersion agent in order to overcome bonding force between existing fluoropolymer and substrate surface, 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 preparing super-double-hydrophobic surface.
Object of the present invention is achieved through the following technical solutions:
An amphipathic crosslinkable fluoropolymer, has general formula as follows:
A-b-(B-r-C)
Wherein, A segment is fluoropolymer, and B segment is crosslinkable polymer, and 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, A segment is to be polymerized by monomer a, and B segment is to be polymerized by monomer b, and C segment is to be polymerized by monomer c.
Described monomer a, b, the structure of c are successively suc as formula shown in I, formula II, formula III:
In formula I, formula II and formula III, R
1, R
2, R
3for H or CH
3, R
4for CH
2, O, COOCH
2or C
6h
6; N, m, z are respectively the integer between 0-10, and q is the integer between 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 described preferred 3-of 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, perfluoro propyl methacrylic ester, vinylformic acid trifluoro ethyl ester, methacrylic acid five fluorine ethyl esters, trifluoroethyl methacrylate, 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 acrylate, perfluor decyl ethyl-methyl acrylate, a kind of in perfluoro capryl ethyl-methyl acrylate or 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, the reaction of reversible addition-fracture chain transfer polymerization, anionic polymerisation, and its synthetic method specifically comprises the following steps:
(1) first monomer a polymerization is obtained to fluoropolymer A;
(2) using 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 comprises the following steps:
(1) get above-mentioned amphipathic crosslinkable fluoropolymer, be dissolved in solvent E, stir; The mass ratio 1:(10-100 of amphipathic crosslinkable fluoropolymer and solvent E wherein);
(2) in stirring, in the reaction system of step (1), drip water, 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, then stir 30-60min, take out base material, after base material is dried, on base material, make super-double-hydrophobic surface;
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, nitrogen methyl-2-pyrrolidone or 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 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 water proof anti-corrosive paint, steel surface and processes, prepares the hydrophobic oleophobic coating of windshield, prepares exterior wall self-cleaning coating, prepares the self-cleaning coating of sculpture, the protection of the skin of military industry equipment, the outer field water-tight corrosion-proof of oil pipeline, prepares the non-resistance coating of oleophobic pipeline lining and prepare the yarn fabric of hydrophobic oleophobic type.
Principle of the present invention is:
Epoxide group is easily open loop under the conditions such as catalyzer, ultraviolet, heat, can occur to be cross-linked with most substrate surfaces, forms a firmly chemical bond.Therefore, epoxide group is referred to as again multi-purpose adhesive, is widely used in the various fields of modern industry as a kind of surface bonding group.Therefore in the present invention, select the monomer that is rich in epoxide group as crosslink part.
The TMOS of selecting in this patent is also a kind ofly can have with surface grafting the group of the base material generation crosslinking reaction of hydroxyl, amino or carboxyl isoreactivity group, is therefore also used as cross-linked polymer, with cotton, and the base material reactions such as the scraps of paper or timber.
Fluoropolymer, as a surperficial base polymer that can be lower in polymkeric substance, is often used to prepare various low surface energies interface.Therefore, also select in this article acrylate containing fluorine material as 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 there is hydrophilic polyethylene glycol acrylate class material as hydrophilic parts, realize the dispersion in water of fluoropolymer in the present invention.
Super-double-hydrophobic surface refers to the surface of the similar lotus leaf in a kind of interface, water droplet cannot flood its surface, can only form the spherical water droplet that contact angle is greater than 150 ° on its surface, and have less roll angle, therefore this surface not only has water-tight corrosion-proof function, has certain self-cleaning function simultaneously.Construct super-double-hydrophobic surface and generally need to possess two two, the first coarse surface, the secondth, low surface energy interface, if therefore material surface itself is coarse, as cotton, timber, paper, only need directly by low surface energy material paving thereon, just can realize hydrophobic oleophobic effect, therefore, in this patent, directly fluoropolymer is layered on the material surface with certain degree of roughness.Utilize centre that epoxide group or TMOS be dispersed in hydrophilic segment as linking agent, utilize fluorine-containing material as low surface energy material, thereby in water, construct super two thin interface.Finally realize the hydrophobic of this material, high adhesion and water-soluble.
The present invention has following advantage and effect with respect to prior art:
(1) in the amphipathic crosslinkable fluoropolymer that prepared by the present invention, contain epoxide group, therefore can utilize epoxide group and most substrate surface to there is bonding force, can be at the super-double-hydrophobic surface of constructing of most substrate surfaces.
(2) TMOS of selecting in this patent is also a kind ofly can have with surface grafting the group of the base material generation crosslinking reaction of hydroxyl, amino or carboxyl isoreactivity group, therefore also can carry out crosslinking reaction with most of base material tables.
(3) in the present invention, by thering is the Racemic glycidol ethers acrylate of crosslinked function and TMOS and hydrophilic polyethylene glycol acrylate, carry out random copolymerization, realize the water-soluble of crosslinked segment, make epoxide group can be in water with substrate surface on active group carry out chemical reaction.
(4) in the present invention, adopt controlled reactive polymer ATRP to realize the synthetic of amphipathic fluoride polymkeric substance, 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 need to adopt the catalysis epoxy additions such as catalyzer or photo-thermal, so be a kind of preparation method of super-double-hydrophobic surface of simple possible.
(6) super-double-hydrophobic surface that utilizes amphipathic crosslinkable fluoropolymer of the present invention to prepare, itself and base material bonding are firm, rub resistance, wash resistant.
Embodiment
Below in conjunction with embodiment, the present invention is described in further detail, but embodiments of the present invention are not limited to this.
Embodiment 1
ATRP method synthesizing amphipathic crosslinkable type fluoropolymer, comprises the following 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, by reaction system stirring and dissolving, logical argon gas Gu bubble 30min, deoxygenation again, then reaction system is transferred in the round-bottomed flask of the 50ml that 0.1124g cuprous bromide is housed, at 40 ℃, carry out polyreaction 2h, reaction product is deposited in methyl alcohol, methyl alcohol is washed and with normal hexane, is washed afterwards, and then at room temperature vacuum-drying 24h, to constant weight, obtains product P TFEMA-Br.
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, by reaction system stirring and dissolving, logical argon gas Gu bubble 30min, deoxygenation again, then reaction system is transferred in the round-bottomed flask of the 100ml that 0.1294g cuprous bromide is housed, at 90 ℃, carry out polyreaction 8h, reaction product is deposited in methyl alcohol, methyl alcohol is washed and with normal hexane, is washed afterwards, then under 40 ℃ of conditions vacuum-drying 24h to constant weight, obtain PTFEMA-b-P (GMA-r-PEGMA).
The structure of PTFEMA-b-P (GMA-r-PEGMA) is as follows:
Utilize above-mentioned amphipathic crosslinkable fluoropolymer to prepare super-double-hydrophobic surface, comprise the following steps: (1) gets above-mentioned synthetic amphipathic crosslinkable fluoropolymer
PTFEMA-b-P (GMA-r-PEGMA) 0.1g, is dissolved in tetrahydrofuran (THF), controls stirring velocity at 100rpm, continuously stirring 2 hours; The mass ratio 1:10 of fluoropolymer and tetrahydrofuran (THF) wherein;
(2) with the speed of 1ml/min, in the amphipathic fluoride polymkeric substance stirring in step (1), drip water, after dropwising, stir 1 day, 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), stir after 5min, then add triethylamine, wherein the mass ratio of triethylamine and amphipathic fluoride polymkeric substance is 1:0.01;
(4) after the reactant in step (3) is stirred to 30min, then filter paper is taken out, after room temperature is dried, be placed on dry 10min in vacuum drying oven, on filter paper, make super-double-hydrophobic surface.Wherein oven temperature is controlled at 80 ℃.
Embodiment 2
Anionic polymerization synthesizing amphipathic crosslinkable type fluoropolymer, comprises the following steps:
At-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.After 25 minutes, add 25.19 milliliters of methacrylic acids, five fluorine ethyl esters, polyreaction carries out adding for 1 hour 21.24 milliliters of vinylformic acid glycidyl ethers (GA) and 25 polyethylene glycol methacrylate-styrene polymers (PEGMA) later simultaneously, and polyreaction continues after 2 hours, to add 1.0 milliliters of anhydrous methanols to stop polyreaction more again.Reaction system is warmed up to after 23 ℃, and distillation and concentration to 100 milliliter is then deposited in polymkeric substance in excessive methyl alcohol, filters and is dried in vacuum drying oven, obtains 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, comprise the following steps:
(1) get above-mentioned synthetic amphipathic crosslinkable fluoropolymer PFEMA-b-P (GA-r-PEGMA) 0.12g, be dissolved in dimethyl formamide, control stirring velocity at 500rpm, continuously stirring 4 hours; The mass ratio 1:100 of fluoropolymer and dimethyl formamide wherein;
(2) with the speed of 10ml/min, in the amphipathic fluoride polymkeric substance stirring in step (1), drip water, after dropwising, stir 4 days, obtain the aqueous solution of fluoropolymer.Wherein the mass ratio of water and dimethyl formamide is 1:0.0001;
(3) the sheet timber of 120mg is joined in the middle aqueous solution of step (2), stir after 20min, then add catalyzer 2-ethyl-4-methylimidazole, wherein the mass ratio between 2-ethyl-4-methylimidazole and amphipathic fluoride polymkeric substance is 1:0.1;
(4) after the reaction solution in step (3) is stirred to 60min, then timber is taken out, after room temperature is dried, be placed on dry 100min in vacuum drying oven, on timber, make super-double-hydrophobic surface.Wherein oven temperature is controlled at 120 ℃.
Embodiment 3
" Click " method of employing synthesizing amphipathic crosslinkable fluoropolymer, comprises the following 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, by reaction system stirring and dissolving, logical argon gas Gu bubble 30min, deoxygenation again, then reaction system is transferred in the round-bottomed flask of the 100ml that 0.1124g cuprous bromide is housed, at 40 ℃, carry out polyreaction 2h, reaction product is deposited in methyl alcohol, methyl alcohol is washed and with normal hexane, is washed afterwards, and then at room temperature vacuum-drying 24h, to constant weight, obtains the PFEMA that product end is 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, by reaction system stirring and dissolving, logical argon gas Gu bubble 30min, deoxygenation again, then reaction system is transferred in the round-bottomed flask of the 100ml that 0.1294g cuprous bromide is housed, at 90 ℃, carry out polyreaction 8h, reaction product is deposited in methyl alcohol, methyl alcohol is washed and with normal hexane, is washed afterwards, then under 40 ℃ of conditions vacuum-drying 24h to constant weight, obtain P(GMA-r-mPEGMA)-N
3.
The PFEMA that gets 2g end and be alkynyl joins in 10ml phenylfluoroform, then adds 4g sodium azide and 5mlTHF, reacts 48 hours at 60 ℃, and concentrated washing with water again 3 times, dries and obtain pure P(GMA-r-mPEGMA)-N
3.
The polymethyl acrylic acid five fluorine ethyl esters (being that end is the PFEMA of alkynyl) of getting 1.8g end and be alkynyl add 3ml phenylfluoroform, then add 3ml tetrahydrofuran (THF) and P(GMA-r-mPEGMA)-N
3, then add 0.08gCuBr, and by after reactor deoxygenation, add again 0.3ml five methyl diethylentriamine (PMEDTA), after reacting 3 days, concentrated, be deposited in methyl alcohol, drier, 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, comprise the following steps:
(1) get above-mentioned synthetic amphipathic crosslinkable fluoropolymer PFEMA-b-P (GMA-r-mPEGMA) and be dissolved in 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) with the speed of 5ml/min, in the amphipathic fluoride polymkeric substance stirring in step (1), drip water, after dropwising, stir 3 days, obtain the aqueous solution of fluoropolymer.Wherein the mass ratio of water and N,N-DIMETHYLACETAMIDE is 1:0.001;
(3) cotton of 200mg is joined in the middle aqueous solution of step (2), stir after 10min, then add catalyzer, wherein the mass ratio of catalyzer and amphipathic fluoride polymkeric substance is 1:0.08;
(4) after the reaction system in step (3) is stirred to 50min, then cotton is taken out, after room temperature is dried, be placed on dry 80min in vacuum drying oven, on cotton, make super-double-hydrophobic surface.Wherein oven temperature is controlled at 100 ℃.
Embodiment 4
ATRP polymerization synthesizing amphipathic crosslinkable type fluoropolymer, comprises the following 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, by reaction system stirring and dissolving, logical argon gas Gu bubble 30min, deoxygenation again, then reaction system is transferred in the round-bottomed flask of the 50ml that 0.1124g cuprous bromide is housed, at 40 ℃, carry out polyreaction 2h, reaction product is deposited in methyl alcohol, methyl alcohol is washed and with normal hexane, is washed afterwards, then at room temperature vacuum-drying 24h to constant weight, obtain product P FOEMA-Br.
In the round-bottomed flask of 100ml, add above-mentioned synthetic 1.5g to gather perfluoro capryl ethyl-methyl acrylate (PFOEMA-Br), 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, by reaction system stirring and dissolving, logical argon gas Gu bubble 30min, deoxygenation again, then reaction system is transferred in the round-bottomed flask of the 100ml that 0.1294g cuprous bromide is housed, at 90 ℃, carry out polyreaction 8h, reaction product is deposited in methyl alcohol, methyl alcohol is washed and with normal hexane, is washed afterwards, then under 40 ℃ of conditions vacuum-drying 24h to constant weight, obtain PFOEMA-b-P (IPSMA-r-PEGMA).
The structure of PFOEMA-b-P (IPSMA-r-PEGMA) is as follows:
Utilize above-mentioned amphipathic crosslinkable fluoropolymer to prepare super-double-hydrophobic surface, comprise the following steps:
(1) get above-mentioned synthetic amphipathic crosslinkable fluoropolymer PFOEMA-b-P (IPSMA-r-PEGMA) 0.1g, be dissolved in nitrogen methyl-2-pyrrolidone, control stirring velocity at 400rpm, continuously stirring 4 hours; The mass ratio 1:100 of fluoropolymer and nitrogen methyl-2-pyrrolidone wherein;
(2) with the speed of 20ml/min, in the amphipathic fluoride polymkeric substance stirring in step (1), drip water, after dropwising, stir 4 days, obtain the aqueous solution of fluoropolymer.Wherein the mass ratio of water and nitrogen methyl-2-pyrrolidone is 1:0.0001;
(3) scraps of paper that are 100mg by weight join in the middle aqueous solution of step (2), stir after 15min, then add catalyst ammonia water (concentration is 37%), and wherein the mass ratio of ammoniacal liquor and amphipathic fluoride polymkeric substance is 1:0.01;
(4) after the reaction system in step (3) is stirred to 50min, then the scraps of paper are taken out, after room temperature is dried, be placed on dry 130min in vacuum drying oven, on the scraps of paper, make super-double-hydrophobic surface.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, by reaction system stirring and dissolving, logical argon gas Gu bubble 30min, deoxygenation again, then reaction system is transferred in the round-bottomed flask of the 50ml that 0.1124g cuprous bromide is housed, at 40 ℃, carry out polyreaction 2h, reaction product is deposited in methyl alcohol, methyl alcohol is washed and with normal hexane, is washed afterwards, and then at room temperature vacuum-drying 24h, to constant weight, obtains product P FEMA-Br.
In the round-bottomed flask of 100ml, add above-mentioned synthetic 1.5g to gather perfluoro capryl ethyl-methyl acrylate (PFEMA-Br), 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, by reaction system stirring and dissolving, logical argon gas Gu bubble 30min, deoxygenation again, then reaction system is transferred in the round-bottomed flask of the 100ml that 0.1294g cuprous bromide is housed, at 90 ℃, carry out polyreaction 8h, reaction product is deposited in methyl alcohol, methyl alcohol is washed and with normal hexane, is washed afterwards, then under 40 ℃ of conditions vacuum-drying 24h to constant weight, obtain PFEMA-b-P (IPSMA-r-PEGMA).
The structure of PFEMA-b-P (IPSMA-r-PEGMA) is as follows:
Utilize above-mentioned amphipathic crosslinkable fluoropolymer to prepare super-double-hydrophobic surface, comprise the following steps:
(1) get above-mentioned synthetic amphipathic crosslinkable fluoropolymer PFEMA-b-P (IPSMA-r-PEGMA) 0.1g, be dissolved in 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) with the speed of 10ml/min, in the amphipathic fluoride polymkeric substance stirring in step (1), drip water, after dropwising, stir 3 days, obtain the aqueous solution of fluoropolymer.Wherein the mass ratio of water and dimethyl sulfoxide (DMSO) is 1:0.001;
(3) scraps of paper that are 100mg by weight join in the middle aqueous solution of step (2), stir after 10min, then add catalyst of triethylamine, and wherein the mass ratio of triethylamine and amphipathic fluoride polymkeric substance is 1:0.1;
(4) after the reaction system in step (3) is stirred to 50min, then the scraps of paper are taken out, after room temperature is dried, be placed on dry 100min in vacuum drying oven, on the scraps of paper, make super-double-hydrophobic surface.Wherein oven temperature is controlled at 100 ℃.
The performance of the prepared super-double-hydrophobic surface of each embodiment of table 1
In table 1, WCA is water contact angle, OCA is oily contact angle, SA is 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, resistance to 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 preparing is immersed in respectively in the solvent of different pH values, take out afterwards at set intervals sample, after water is washed surperficial soda acid off, with contact angle instrument, test its contact angle again, when water or oil contact angle be greater than 150 °, represent that the hydrophobic of this material or oleophobic performance do not decline.Until its contact angle is less than 150 °, represent that the hydrophobic of its surface or oleophobic performance are declining.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 resistance to ultrasonic property: super-double-hydrophobic surface is immersed in 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 after different ultrasonic times, when the contact angle of water or oil is greater than 150 °, represent that the hydrophobic of this material or oleophobic performance do not decline.Until its contact angle is less than 150 °, represent that the hydrophobic of its surface or oleophobic performance are declining.And record this time, by comparing the length of this time, characterize its resistance to ultrasonic property.
From the performance test results of table 1, can find out, 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 in this patent, provide are more cheap, more environmental protection, in addition, the super-double-hydrophobic surface that adopts amphipathic crosslinkable fluoropolymer of the present invention to prepare has excellent super-hydrophobic super oleophobic performance, and its resistance to acids and bases, resistance to supersound washing, washable clean smart detergency is all excellent, can meet the requirement of industrial application aspect.
Above-described embodiment is preferably 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 principle, substitutes, combination, simplify; all should be equivalent substitute mode, within being included in protection scope of the present invention.
Claims (5)
1. an 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; A segment is to be polymerized by monomer a, and B segment is to be polymerized by monomer b, and C segment is to be polymerized by monomer c;
Described monomer a is hexafluoro isopropylacrylic acid ester, hexafluoro isopropyl methyl acrylate, tetrafluoro propyl methyl acid esters, perfluoro propyl methacrylic ester, vinylformic acid trifluoro ethyl ester, methacrylic acid five fluorine ethyl esters, trifluoroethyl methacrylate, 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 decyl ethyl-methyl acrylate, a kind of in perfluoro capryl ethyl-methyl acrylate or perfluor heptyl ethyl-methyl acrylate,
Described monomer b is propenyl glycidyl ether, 1,2-epoxy group(ing)-5-hexene or methacryloxypropyl triisopropyl TMOS;
Described monomer c is polyethylene glycol methacrylate-styrene polymer.
2. the application of amphipathic crosslinkable fluoropolymer claimed in claim 1 in preparing super-double-hydrophobic surface.
3. the application of amphipathic crosslinkable fluoropolymer according to claim 2 in preparing super-double-hydrophobic surface, is characterized in that comprising the following steps:
(1) get the amphipathic crosslinkable fluoropolymer described in claim 1, be dissolved in solvent E, stir; The mass ratio 1:(10-100 of amphipathic crosslinkable fluoropolymer and solvent E wherein);
(2) in stirring, in the reaction system of step (1), drip water, 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, then stir 30-60min, take out base material, after base material is dried, on base material, make super-double-hydrophobic surface;
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, nitrogen methyl-2-pyrrolidone or 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 hydrochloric acid.
4. the application of amphipathic crosslinkable fluoropolymer according to claim 3 in preparing super-double-hydrophobic surface, is characterized in that: the described base material of step (3) is cotton, the scraps of paper or timber.
Amphipathic crosslinkable fluoropolymer claimed in claim 1 preparing water proof anti-corrosive paint, steel surface and process, prepare the hydrophobic oleophobic coating of windshield, prepare exterior wall self-cleaning coating, prepare the self-cleaning coating of sculpture, the protection of the skin of military industry equipment, the outer field water-tight corrosion-proof of oil pipeline and prepare the application in the yarn fabric of hydrophobic oleophobic type.
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| WO2016044880A1 (en) * | 2014-09-25 | 2016-03-31 | Deakin University | Liquid repellent article and process for the preparation of the article |
| CN106280839B (en) * | 2016-07-29 | 2019-05-07 | 徐州佑季化工材料有限公司 | Epoxy group-fluorinated acrylate polymer coating agent preparation method |
| CN107384104A (en) * | 2017-07-12 | 2017-11-24 | 西安理工大学 | A kind of super hydrophobic coating and its preparation method and application |
| CN107384103A (en) * | 2017-07-12 | 2017-11-24 | 西安理工大学 | A kind of preparation method of super-hydrophobic coat |
| CN109265583B (en) * | 2017-07-18 | 2021-05-25 | 北京航天爱锐科技有限责任公司 | Polyethylene fluorine-containing hydrophobic and oleophobic material, coating containing polyethylene fluorine-containing hydrophobic and oleophobic material and preparation method of polyethylene fluorine-containing hydrophobic and oleophobic material |
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