CN106496521A - The preparation method and applications of Cross-linkable Fluoropolyether compound - Google Patents
The preparation method and applications of Cross-linkable Fluoropolyether compound Download PDFInfo
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- C—CHEMISTRY; METALLURGY
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/14—Polycondensates modified by chemical after-treatment
- C08G59/1433—Polycondensates modified by chemical after-treatment with organic low-molecular-weight compounds
- C08G59/1483—Polycondensates modified by chemical after-treatment with organic low-molecular-weight compounds containing sulfur
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- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
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Abstract
The present invention relates to a kind of preparation method and applications of Cross-linkable Fluoropolyether compound, feature be comprising the step of be：Epoxy resin is dissolved in solvent B, Deca dispersibility material, end sulfydryl Fluoropolyether compound and catalyst while stirring at 80 120 DEG C, rate of addition is 1 g/min, 100 g/min, after completion of dropwise addition, after continuing reaction 4 10 hours, after being cooled to room temperature, concentration, Cross-linkable fluorochemical polyether class compound of the reprecipitation in solvent F, needed for being obtained after drying；Then ultra-amphosphobic material is prepared by Cross-linkable fluorochemical polyether class compound again.Its simple production process, not high to reagent and equipment requirements, during fluorine-containing microsphere need not be dispersed in containing fluorous solvent, the cementitious group in surface, cementability are good.
Description
Technical field
The invention belongs to super-amphiphobic material field, and in particular to a kind of preparation method of Cross-linkable Fluoropolyether compound
And its application, its application is the preparation method for being prepared ultra-amphosphobic material by Cross-linkable Fluoropolyether compound.
Background technology
Surface wettability is one of key character of the surface of solids, and wettability can be weighed with the contact angle of water on surface
The surface that water contact angle is more than 150 °, roll angle is less than 10 ° is generally referred to as super hydrophobic surface by amount, and surface has greatly to oil
In 150 ° of contact angle, it is believed that be superoleophobic surface.If both greater than 150 ° of the static contact angle of the water on a certain surface and oil
And its roll angle is both less than 5 °, then the interface can be referred to as super-amphiphobic interface.Super hydrophobic surface and super-double-hydrophobic surface possess necessarily
Self-cleaning function, i.e., the water droplet that surface contaminant such as dust etc. can be tumbled takes away and do not leave any vestige.Automatically cleaning
Coating has the advantages such as water saving, energy-saving and environmental protection, increasingly gets more and more people's extensive concerning, and is the heat of current material subject research
One of point.
Patent 201110131477.X proposes a kind of preparation of fluorine-containing difunctional microsphere and its is applied to construct super-amphiphobic table
Face.Main method is to prepare a kind of nanometer containing multiple functional groups or micro-size particless so as to which surface is not only containing containing fluorination
Compound, also can with substrate reaction and form the group of covalent bond, then this surface grafting is had fluorochemical and can be with
Substrate carries out the nanometer of chemical bonding or micron microsphere is sprayed on substrate surface, and constructs super-amphiphobic interface with this.The invention institute
The coating of preparation has excellent super-amphiphobic characteristic, and coating is bonded with substrate surface by covalent bond, so that super
Double thin performances have preferable durability.But, the accessible base material of the method has certain limitation, it is necessary to containing active group
(such as hydroxyl, carboxyl, amino etc.), does not otherwise possess caking property, and during fluorine-containing microsphere needs to be dispersed in containing fluorous solvent.
Patent 201110266897.9 propose a kind of after being blended using fluorine-containing silicon-containing copolymer and silicon dioxide
Surface containing active group carries out assembling film forming, can give surface good ultra-amphosphobic energy, and this method is using more
Fluorine-containing silicon-containing copolymer, relatively costly, and blending group reaction cartridge is needed, technics comparing is complicated, and base material need to contain active group
Group, does not have universality.
Patent 201110373304.9 is proposed using atom transfer radical polymerization on amino modified inorganic microsphere surface
Grafting crosslinkable monomers and fluorochemical monomer obtain crosslinkable ultra-amphosphobic microsphere, and the fluorine-containing microsphere assembling film forming obtains super-amphiphobic
Surface property is excellent, and there is preferable hydrophobic oleophobic contact angle not only, while having good resistance to acids and bases, also has preferably resistance to
Hou Xing.But the processing procedure of the method is relatively complicated, higher to reagent, equipment requirements, and fluorine-containing microsphere need be dispersed in
Containing in fluorous solvent, also without caking property group, therefore cementability is nor very strong on surface.
Can all use fluoropolymer when super-double-hydrophobic surface is constructed in most of patent at present, but major part contains
Fluoropolymer is 2- (perfluorooctylethyl group) methacrylate (FOEMA), perfluoro caprylic acid (PFOA) and perfluoro octane sulfonate
(PFOS) material such as, this kind of material are all poisonous to environment and human body, are therefore gradually reducing application in a lot of applications.
Content of the invention
In order to overcome the shortcoming of prior art with not enough, the primary and foremost purpose of the present invention is to provide a kind of Cross-linkable fluorine-containing
The preparation method of polyether compound, another object of the present invention is to provide surpassed with the preparation of Cross-linkable Fluoropolyether compound
The preparation method of double thin property materials, simple production process be not high to reagent and equipment requirements, and fluorine-containing microsphere need not be dispersed in and contain
In fluorous solvent, the cementitious group in surface, cementability are good.
In order to reach above-mentioned primary and foremost purpose, the technical scheme is that, which is a kind of Cross-linkable fluorochemical polyether chemical combination
The preparation method of thing, it is characterised in that comprising the step of be：Epoxy resin is dissolved in solvent B, in 80-120 DEG C of following stirring
Side Deca dispersibility material, end sulfydryl Fluoropolyether compound and catalyst, rate of addition are 1 g/min-100 g/min, drip
Plus after terminating, after continuing reaction 4-10 hours, after being cooled to room temperature, concentration, reprecipitation are obtained after drying in solvent F
Required Cross-linkable fluorochemical polyether class compound；Its epoxy resin, solvent B, dispersibility material, end sulfydryl fluorochemical polyether
Mass ratio between compound and catalyst is:1: 10-100: 1-10：1-10:0.00001-0.0001;
The epoxy resin is polyacrylic glycidyl ether material, and its molecular weight is 1000-100000；
The solvent B is：Tetrahydrofuran, Ketohexamethylene, butanone, xylol, dimethylformamide, six alkane of dioxy, dimethyl are sub-
Sulfone, dimethyl acetylamide, N-N ketopyrrolidines, one or more mixture in diphenyl ether and methyl phenyl ethers anisole；
The catalyst is：Triethylamine, tetrabutyl ammonium fluoride, diisopropyl ethyl amine, DMA, octadecyl two
Methyl tertiary amine, oleyl dimethyl tertiary amine, dodeca-tertiary amine, one or more mixture in benzyltriethylammoinium chloride；
Described solvent F is normal hexane, and absolute ether, petroleum ether, ethyl acetate, methanol, ethanol, one or more in water are mixed
Compound.
In the technical program, the synthetic method of the polyacrylic glycidyl ether material is as follows：
Acrylic compounds glycidyl ether monomers are added in solvent B, 60-120 DEG C is increased the temperature to, initiator is added, instead
After continuing reaction 4-10 hours, polymerization inhibitor is added, after being cooled to room temperature, concentration, reprecipitation were obtained institute in solvent F, both
The polyacrylic glycidyl ether material for needing；Wherein acrylic compounds glycidyl ether monomers, solvent B, initiator and polymerization inhibitor
Mass ratio be：1：20-100：0.001-0.005：0.0001-0.0005；
The acrylic compounds glycidyl ether is methyl propenoic acid glycidyl ether, glycidyl ether, adjacent toluene shrink
One or more mixture in glycerin ether, phenyl glycidyl ether；
The initiator be cyclohexanone peroxide, dibenzoyl peroxide, tert-butyl hydroperoxide, azodiisobutyronitrile, azo
One or more mixture in two different heptonitriles；
The polymerization inhibitor is hydroquinone, 1,4-benzoquinone, methylnaphthohydroquinone, MEHQ, 2- tert-butyl hydroquinone, 2,5- bis-
One or more mixture in tert-butyl hydroquinone.
In the technical program, the synthetic method of the end sulfydryl Fluoropolyether compound is as follows：
Fluorochemical polyether is dissolved in tetrahydrofuran after adding lithium aluminium hydride reduction reaction 5-10 hours, obtains end and contain hydroxyl
Fluorochemical polyether, then terminad contains in the fluorochemical polyether solution of hydroxyl and adds thiourea and hydrochloric acid, and concentration of hydrochloric acid is 37%, reaction
2-5 hours, add excessive sodium hydroxide, react 5-10 hours, you can obtain holding sulfydryl Fluoropolyether compound；Wherein contain
The mass ratio of perfluoroalkyl polyether, tetrahydrofuran, lithium aluminium hydride reduction, thiourea, hydrochloric acid and sodium hydroxide is 1：10-20：0.001-0.1：3-6：
0.1-0.5：1-3；The fluorochemical polyether is preferably perfluor -2,5,8- trimethyl -3,6,9- trioxa lauroyl fluorine（CAS is logged in
Number 27639-98-1）.
In order to reach above-mentioned another object, the technical scheme is that, which is a kind of Cross-linkable fluorochemical polyether class
Compound prepares the preparation method of ultra-amphosphobic material, it is characterised in that preparation method is as follows：
Step one
Substrate material surface pretreatment；The base material can be sheet glass, cotton, filter paper, timber, one kind of cement matrix；
The pretreatment of wherein filter paper, timber, cement matrix and cotton is：Successively with ethanol, water washing, then dry；
The pretreatment of sheet glass is：By sheet glass in solution soaking 2-10 hour, then then dried with ethanol, water washing successively；
It is 7 that the solution is volume ratio:3 dense H2SO4And H2O2Mixed liquor；
Step 2
The Cross-linkable Fluoropolyether compound of above-mentioned gained is dissolved in solvent B, inorganic nano-particle and catalysis is added
Agent, is prepared into super-amphiphobic coating after stirring, wherein Cross-linkable Fluoropolyether compound, solvent B, inorganic nano-particle and
The mass ratio of catalyst is 1：1-10:0-0.5：0.0001-0.001；
The inorganic nano-particle is particle diameter for the Nano microsphere of 50-1000nm, and priority protection is silicon dioxide microsphere, titanium dioxide
Titanium microsphere, ferric oxide microsphere, calcium oxide microsphere；
Step 3
The super-amphiphobic coating prepared in step 2 is coated in substrate surface by way of spraying or dip-coating, 20-30 DEG C
Lower film forming, then it is placed on crosslinking 2-24 h in 90-140 DEG C of baking oven, you can obtain a kind of ultra-amphosphobic material.
The present invention compared with prior art, with advantages below and beneficial effect：
1st, such PFPE mercaptan is almost harmless, simple production process to environment, to reagent and equipment requirements
Not high, during fluorine-containing microsphere need not be dispersed in containing fluorous solvent, the cementitious group in surface；
2nd, the present invention is grafted to fluoropolymer in epoxy resin, while remaining part ring using the method for chemical graft
Oxygen group, so that it is guaranteed that fluorine-containing material is securely adhered to substrate surface in polymer form so that constructed super-amphiphobic
Coating has good durability；
3rd, the polymer and inorganic nano-particle have good sympathy, therefore can be by adding inorganic nano-particle come neatly
The roughness at the super-amphiphobic interface that finally constructs is adjusted, so as to obtain more preferable super-double-hydrophobic surface；
4th, the main polymer chain in the present invention may also provide active site graft dispersion polymer, therefore the super-amphiphobic in the patent
Coating is may be dissolved in overwhelming majority dissolving；
5th, this ultra-amphosphobic material can be widely used in electronic touch screen, the automatically cleaning of 3C Product shell, military industry equipment
In terms of the productive lifes such as the windshield such as outer protective, the water-tight corrosion-proof of oil pipeline outer layer, kitchen guarding's apparatus, automobile and aircraft.
Specific embodiment
With reference to embodiment, the present invention is described in further detail, but embodiments of the present invention not limited to this.
Embodiment one
（1）The preparation of end sulfydryl Fluoropolyether compound
Fluorochemical polyether is dissolved in tetrahydrofuran and adds lithium aluminium hydride reduction reaction 5 hours afterwards, obtained end and contain hydroxyl
Fluorochemical polyether, then terminad contains in the fluorochemical polyether solution of hydroxyl and adds thiourea and hydrochloric acid, concentration of hydrochloric acid is 37%, and reaction 2 is little
When, excessive sodium hydroxide is added, is reacted 5 hours, you can obtain holding sulfydryl Fluoropolyether compound；Wherein fluorochemical polyether,
The mass ratio of tetrahydrofuran, lithium aluminium hydride reduction, thiourea, hydrochloric acid and sodium hydroxide is 1：10：0.001：3：0.1：1；Described fluorine-containing poly-
Ether is preferably perfluor -2,5,8- trimethyl -3,6,9- trioxa lauroyl fluorine（CAS accession number 27639-98-1）；
（2）The synthesis of polyacrylic glycidyl ether material
Acrylic compounds glycidyl ether monomers are added in solvent B, 120 DEG C are increased the temperature to, initiator is added, instead after
After continuous reaction 10 hours, polymerization inhibitor is added, after being cooled to room temperature, concentration, reprecipitation were obtained required in solvent F, both
Polyacrylic glycidyl ether material；The matter of wherein acrylic compounds glycidyl ether monomers, solvent B, initiator and polymerization inhibitor
Measuring ratio is：1：100：0.001：0.0001；
The acrylic compounds glycidyl ether is methyl propenoic acid glycidyl ether；The initiator is cyclohexanone peroxide；Institute
Polymerization inhibitor is stated for hydroquinone；The solvent B is tetrahydrofuran；
（3）The preparation of Cross-linkable Fluoropolyether compound
Epoxy resin is dissolved in solvent B, at 80 DEG C while stirring Deca dispersibility material, end sulfydryl fluorochemical polyether chemical combination
Thing and catalyst, rate of addition are 1 g/min, after completion of dropwise addition, after continuing reaction 4 hours, after being cooled to room temperature, concentration, then
It is deposited in solvent F, the Cross-linkable fluorochemical polyether class compound needed for being obtained after drying；Its epoxy resin, solvent
B, dispersibility material, end sulfydryl Fluoropolyether compound and catalyst between mass ratio be:1: 10: 1：1:0.00001；
The epoxy resin is polyacrylic glycidyl ether material, and its molecular weight is 1000；The solvent B is tetrahydrochysene furan
Mutter；The catalyst is triethylamine；The solvent F is normal hexane；
（4）The preparation of ultra-amphosphobic material
Step one
Substrate surface pretreatment；The base material is sheet glass, and the pretreatment of sheet glass is：By sheet glass in piranha solution
Immersion 2 hours, then then dried with ethanol, water washing successively；The volume ratio of piranha solution is 7:3 dense H2SO4And H2O2
Mixed liquor；
Step 2
Above-mentioned obtained Cross-linkable Fluoropolyether compound is dissolved in solvent B, inorganic nano-particle is added and is urged
Agent, is prepared into super-amphiphobic coating, wherein Cross-linkable Fluoropolyether compound, solvent B, inorganic nano-particle after stirring
And the mass ratio of catalyst is 1：1：0：0.0001；
The inorganic nano-particle is the Nano microsphere that particle diameter is 50nm, and priority protection is silicon dioxide microsphere；The solvent B is
Tetrahydrofuran；The catalyst is triethylamine；
Step 3
By the super-amphiphobic coating prepared in step 2 by spraying or dip-coating by way of be coated in substrate surface, at 20 DEG C into
Film, then be placed in 90 DEG C of baking ovens and be crosslinked 2 h, you can obtain a kind of ultra-amphosphobic material.Ultra-amphosphobic material widely can be answered
For electronic touch screen, the automatically cleaning of 3C Product shell, the outer protective of military industry equipment, the water-tight corrosion-proof of oil pipeline outer layer,
In terms of the productive lifes such as the windshield such as kitchen guarding's apparatus, automobile and aircraft.
Embodiment two
（1）The preparation of end sulfydryl Fluoropolyether compound
Fluorochemical polyether is dissolved in tetrahydrofuran and adds lithium aluminium hydride reduction reaction 10 hours afterwards, obtained end and contain hydroxyl
Fluorochemical polyether, then terminad contains in the fluorochemical polyether solution of hydroxyl and adds thiourea and hydrochloric acid, concentration of hydrochloric acid is 37%, and reaction 5 is little
When, excessive sodium hydroxide is added, is reacted 10 hours, you can obtain holding sulfydryl Fluoropolyether compound；Wherein fluorochemical polyether,
The mass ratio of tetrahydrofuran, lithium aluminium hydride reduction, thiourea, hydrochloric acid and sodium hydroxide is 1：20：0.1：6：0.5：3；The fluorochemical polyether
Preferably perfluor -2,5,8- trimethyls -3,6,9- trioxas lauroyl fluorine（CAS accession number 27639-98-1）；
（2）The synthesis of polyacrylic glycidyl ether material
Acrylic compounds glycidyl ether monomers are added in solvent B, 120 DEG C are increased the temperature to, initiator is added, instead after
After continuous reaction 10 hours, polymerization inhibitor is added, after being cooled to room temperature, concentration, reprecipitation were obtained required in solvent F, both
Polyacrylic glycidyl ether material；The matter of wherein acrylic compounds glycidyl ether monomers, solvent B, initiator and polymerization inhibitor
Measuring ratio is：1：100：0.005：0.0005；
The acrylic compounds glycidyl ether is phenyl glycidyl ether；The initiator is 2,2'-Azobis(2,4-dimethylvaleronitrile)；The inhibition
Agent is 2,5- di-tert-butyl hydroquinones；The solvent B is methyl phenyl ethers anisole；
（3）The preparation of Cross-linkable Fluoropolyether compound
Epoxy resin is dissolved in solvent B, Deca dispersibility material while stirring at 120 DEG C holds sulfydryl fluorochemical polyether chemical combination
Thing and catalyst, rate of addition are 100 g/min, after completion of dropwise addition, after continuing reaction 10 hours, after being cooled to room temperature, concentration,
Cross-linkable fluorochemical polyether class compound of the reprecipitation in solvent F, needed for being obtained after drying；Its epoxy resin, molten
Agent B, dispersibility material, end sulfydryl Fluoropolyether compound and catalyst between mass ratio be:1: 100: 10：10:
0.0001;
The epoxy resin is polyacrylic glycidyl ether material, and its molecular weight is 100000；The solvent B is benzene first
Ether；The catalyst is benzyltriethylammoinium chloride；The solvent F is absolute ether；
（4）The preparation of ultra-amphosphobic material
Step one
Substrate surface pretreatment；The base material is cement；The pretreatment of wherein cement matrix is：Ethanol, water washing are used successively, so
After dry；
Step 2
Above-mentioned obtained Cross-linkable Fluoropolyether compound is dissolved in solvent B, inorganic nano-particle is added and is urged
Agent, is prepared into super-amphiphobic coating, wherein Cross-linkable Fluoropolyether compound, solvent B, inorganic nano-particle after stirring
Mass ratio with catalyst is 1：10：0.5：0.001；
The inorganic nano-particle G is the Nano microsphere that particle diameter is 1000nm, and priority protection is calcium oxide microsphere；The solvent B
For methyl phenyl ethers anisole；The catalyst is benzyltriethylammoinium chloride；
Step 3
By the super-amphiphobic coating prepared in step 2 by spraying or dip-coating by way of be coated in substrate surface, at 30 DEG C into
Film, then it is placed on crosslinking 24 hours in 140 DEG C of baking ovens, you can obtain a kind of super-double-hydrophobic surface.Ultra-amphosphobic material can be extensive
Electronic touch screen is applied to, the automatically cleaning of 3C Product shell, the outer protective of military industry equipment, the waterproof of oil pipeline outer layer are prevented
In terms of the productive lifes such as the windshield such as corruption, kitchen guarding's apparatus, automobile and aircraft.
Embodiment three
（1）The preparation of end sulfydryl Fluoropolyether compound
Fluorochemical polyether is dissolved in tetrahydrofuran and adds lithium aluminium hydride reduction reaction 7 hours afterwards, obtained end and contain hydroxyl
Fluorochemical polyether, then terminad contains in the fluorochemical polyether solution of hydroxyl and adds thiourea and hydrochloric acid, concentration of hydrochloric acid is 37%, and reaction 3 is little
When, excessive sodium hydroxide is added, is reacted 6 hours, you can obtain holding sulfydryl Fluoropolyether compound；Wherein fluorochemical polyether,
The mass ratio of tetrahydrofuran, lithium aluminium hydride reduction, thiourea, hydrochloric acid and sodium hydroxide is 1：15：0.01：4：0.4：2；The fluorochemical polyether
Preferably perfluor -2,5,8- trimethyls -3,6,9- trioxas lauroyl fluorine（CAS accession number 27639-98-1）；
（2）The synthesis of polyacrylic glycidyl ether material
Acrylic compounds glycidyl ether monomers are added in solvent B, 110 DEG C are increased the temperature to, initiator is added, instead after
After continuous reaction 6 hours, polymerization inhibitor is added, after being cooled to room temperature, concentration, reprecipitation were obtained required gathering in solvent F, both
Acrylic compounds glycidyl ether material；The quality of wherein acrylic compounds glycidyl ether monomers, solvent B, initiator and polymerization inhibitor
Than for：1：40：0.0035：0.0004；
The acrylic compounds glycidyl ether is glycidyl ether；The initiator is tert-butyl hydroperoxide；Described
Polymerization inhibitor is MEHQ；The solvent B is dimethyl acetylamide；
（3）The preparation of Cross-linkable Fluoropolyether compound
Epoxy resin is dissolved in solvent B, Deca dispersibility material while stirring at 100 DEG C holds sulfydryl fluorochemical polyether chemical combination
Thing and catalyst, rate of addition are 80 g/min, after completion of dropwise addition, after continuing reaction 80 hours, after being cooled to room temperature, concentration,
Cross-linkable fluorochemical polyether class compound of the reprecipitation in solvent F, needed for being obtained after drying；Its epoxy resin, molten
Agent B, dispersibility material, end sulfydryl Fluoropolyether compound and catalyst E between mass ratio be:1: 80: 8：6：
0.00009；
The epoxy resin is polyacrylic glycidyl ether material, and its molecular weight is:80000；The solvent B is dimethyl
Acetamide；Described catalyst is oleyl dimethyl tertiary amine；The solvent F is ethanol；
（4）The preparation of ultra-amphosphobic material
Step one
Substrate surface pretreatment；The base material is cotton；The pretreatment of wherein cotton is：Ethanol, water washing, Ran Hougan are used successively
Dry；
Step 2
Above-mentioned obtained Cross-linkable Fluoropolyether compound is dissolved in solvent B, inorganic nano-particle is added and is urged
Agent, is prepared into super-amphiphobic coating, wherein Cross-linkable Fluoropolyether compound, solvent B, inorganic nano-particle after stirring
Mass ratio with catalyst is 1：6：0.2：0.0005；
The inorganic nano-particle is the Nano microsphere that particle diameter is 800nm, and priority protection is ferric oxide microsphere；The solvent B
For dimethyl acetylamide；Described catalyst is oleyl dimethyl tertiary amine；
Step 3
The super-amphiphobic coating prepared in step 2 is coated in substrate surface by way of spraying, film forming at 25 DEG C, then
It is placed in 120 DEG C of baking ovens and is crosslinked 14 h, you can obtains a kind of ultra-amphosphobic material.Ultra-amphosphobic material can be widely used in
Electronic touch screen, the automatically cleaning of 3C Product shell, the outer protective of military industry equipment, the water-tight corrosion-proof of oil pipeline outer layer, kitchen guarding
In terms of the productive lifes such as the windshield such as apparatus, automobile and aircraft.
Example IV
（1）The preparation of end sulfydryl Fluoropolyether compound
Fluorochemical polyether is dissolved in tetrahydrofuran and adds lithium aluminium hydride reduction reaction 6 hours afterwards, obtained end and contain hydroxyl
Fluorochemical polyether.Thiourea and hydrochloric acid are added again in fluorochemical polyether solution to this end for hydroxyl, concentration of hydrochloric acid is 37%, reaction 4
Hour, excessive sodium hydroxide is added, is reacted 7 hours, you can obtain holding sulfydryl Fluoropolyether compound；Wherein fluorine-containing poly-
The mass ratio of ether, tetrahydrofuran, lithium aluminium hydride reduction, thiourea, hydrochloric acid and sodium hydroxide is 1：11：0.02：4：0.3：2；Described fluorine-containing
Polyethers is preferably perfluor -2,5,8- trimethyl -3,6,9- trioxa lauroyl fluorine（CAS accession number 27639-98-1）；
（2）The synthesis of polyacrylic glycidyl ether material
Acrylic compounds glycidyl ether monomers are added in solvent B, 100 DEG C are increased the temperature to, initiator is added, instead after
After continuous reaction 7 hours, polymerization inhibitor is added, after being cooled to room temperature, concentration, reprecipitation were obtained required gathering in solvent F, both
Acrylic compounds glycidyl ether material；The quality of wherein acrylic compounds glycidyl ether monomers, solvent B, initiator and polymerization inhibitor
Than for：1：70：0.0025：0.0003；
The acrylic compounds glycidyl ether is adjacent toluene glycidyl ether；The initiator is dibenzoyl peroxide；Described
Polymerization inhibitor is MEHQ；The solvent B is six alkane of dioxy；
（3）The preparation of Cross-linkable Fluoropolyether compound
Epoxy resin is dissolved in solvent B, Deca dispersibility material while stirring at 90 DEG C holds sulfydryl fluorochemical polyether chemical combination
Thing and catalyst, rate of addition are 70 g/min, after completion of dropwise addition, after continuing reaction 5 hours, after being cooled to room temperature, concentration, then
It is deposited in solvent F, the Cross-linkable fluorochemical polyether class compound needed for being obtained after drying；Its epoxy resin, solvent
B, dispersibility material, end sulfydryl Fluoropolyether compound and catalyst between mass ratio be:1：30：5：6：0.00008;
The epoxy resin is polyacrylic glycidyl ether material, and its molecular weight is 80000；The solvent B is dioxy six
Alkane；The catalyst is oleyl dimethyl tertiary amine；The solvent F is ethyl acetate；
（4）The preparation of ultra-amphosphobic material
Step one
Substrate surface pretreatment；Base material is filter paper；The pretreatment of wherein filter paper is：Successively with ethanol, water washing, then dry；
Step 2
Above-mentioned obtained Cross-linkable Fluoropolyether compound is dissolved in solvent B, inorganic nano-particle is added and is urged
Agent, is prepared into super-amphiphobic coating, wherein Cross-linkable Fluoropolyether compound, solvent B, inorganic nano-particle after stirring
Mass ratio with catalyst is 1：7：0.1：0.0008；
Described inorganic nano-particle G is the Nano microsphere that particle diameter is 600nm, and priority protection is titanium dioxide microballoon sphere；Described molten
Agent B is six alkane of dioxy；The catalyst is oleyl dimethyl tertiary amine；
Step 3
By the super-amphiphobic coating prepared in step 2 by spraying or dip-coating by way of be coated in substrate surface, at 25 DEG C into
Film, then it is little to be placed in 100 DEG C of baking ovens crosslinking 10, you can obtain a kind of ultra-amphosphobic material.There is the material on ultra-amphosphobic surface
Material can be widely used in electronic touch screen, the automatically cleaning of 3C Product shell, the outer protective of military industry equipment, oil pipeline outer layer
Water-tight corrosion-proof, kitchen guarding's apparatus, in terms of the productive life such as the windshield such as automobile and aircraft.
Embodiment five
（1）The preparation of end sulfydryl Fluoropolyether compound
Fluorochemical polyether is dissolved in tetrahydrofuran and adds lithium aluminium hydride reduction reaction 6 hours afterwards, obtained end and contain hydroxyl
Fluorochemical polyether.Thiourea and hydrochloric acid are added again in fluorochemical polyether solution to this end for hydroxyl（Concentration is 37%）, reaction 2.5
Hour, excessive sodium hydroxide is added, is reacted 6 hours, you can obtain holding sulfydryl Fluoropolyether compound；Wherein fluorine-containing poly-
The mass ratio of ether, tetrahydrofuran, lithium aluminium hydride reduction, thiourea, hydrochloric acid and sodium hydroxide is 1：12：0.1： 6： 0.5：3；Described fluorine-containing
Polyethers is preferably perfluor -2,5,8- trimethyl -3,6,9- trioxa lauroyl fluorine（CAS accession number 27639-98-1）；
（2）The synthesis of polyacrylic glycidyl ether material
Acrylic compounds glycidyl ether monomers are added in solvent B, 100 DEG C are increased the temperature to, initiator is added, instead after
After continuous reaction 5 hours, polymerization inhibitor is added, after being cooled to room temperature, concentration, reprecipitation were obtained required gathering in solvent F, both
Acrylic compounds glycidyl ether material；The quality of wherein acrylic compounds glycidyl ether monomers, solvent B, initiator and polymerization inhibitor
Than for：1：40：0.004：0.0002；
The acrylic compounds glycidyl ether is glycidyl ether；The initiator is cyclohexanone peroxide；The resistance
Poly- agent is 2- tert-butyl hydroquinone；The solvent B is dimethyl acetylamide；
（3）The preparation of Cross-linkable Fluoropolyether compound
Epoxy resin is dissolved in solvent B, Deca dispersibility material while stirring at 90 DEG C holds sulfydryl fluorochemical polyether chemical combination
Thing and catalyst, rate of addition are 50 g/min, after completion of dropwise addition, after continuing reaction 9 hours, after being cooled to room temperature, concentration, then
It is deposited in solvent F, the Cross-linkable fluorochemical polyether class compound needed for being obtained after drying；Its epoxy resin, solvent
B, dispersibility material, end sulfydryl Fluoropolyether compound and catalyst between mass ratio be:1: 50: 6：7:0.0007；
The epoxy resin is polyacrylic glycidyl ether material, and its molecular weight is 90000；The solvent B is dimethyl
Acetamide；The catalyst E is oleyl dimethyl tertiary amine；The solvent F is petroleum ether；
（4）The preparation of ultra-amphosphobic material
Step one
Substrate surface pretreatment；The base material is sheet glass, and the pretreatment of sheet glass is：By sheet glass in piranha solution
Immersion 10 hours, it is 7 that piranha solution is volume ratio:3 dense H2SO4And H2O2Mixed liquor, then use ethanol, water washing successively,
Then dry；
Step 2
Above-mentioned obtained Cross-linkable Fluoropolyether compound is dissolved in solvent B, inorganic nano-particle is added and is urged
Agent, is prepared into super-amphiphobic coating, wherein Cross-linkable Fluoropolyether compound, solvent B, inorganic nano-particle after stirring
Mass ratio with catalyst is 1：4： 0.35：0.0005；
The inorganic nano-particle is the Nano microsphere that particle diameter is 100nm, and priority protection is silicon dioxide microsphere；The solvent B
For dimethyl acetylamide；The catalyst E is oleyl dimethyl tertiary amine；
Step 3
By the super-amphiphobic coating prepared in step 2 by spraying or dip-coating by way of be coated in substrate surface, at 20 DEG C into
Film, then it is placed on crosslinking 14 hours in 110 DEG C of baking ovens, you can obtain a kind of ultra-amphosphobic material.
The performance parameter of double thin property material prepared by 1 embodiment one of table to embodiment five
In table 1, WCA is water contact angle, and OCA is oily contact angle, and WSA is water roll angle, (Dean Xiong and Guojun
Liu. Diblock-copolymer-coated Water-and Oil-Repellent Cotton Fabrics.
Langmuir 2012,28,6911-6918) in the method mentioned tested.
Table 1 characterizes bonding of the super-double-hydrophobic surface on base material by indexs such as resistance to acids and bases, washing fastness, resistance to ultrasounds
Power.
The method of testing of wherein resistance to acids and bases be 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 2010,51,1940-1946) in the method mentioned, i.e.,：By the super-amphiphobic for preparing
Surface is separately immersed in the solvent of different pH values, then at set intervals take out sample, wash with water surface soda acid it
Afterwards, then with its contact angle of contact angle instrument test, when the contact angle of water or oil is more than 150 °, the hydrophobic or oleophobic of the material is represented
Performance does not decline.Until its contact angle is less than 150 °, represent that the hydrophobic or oleophobic performance on its surface have dropped.Record
The time, by comparing the length of this time, characterize its resistance to acids and bases.
The method of testing of washing fastness is reference literature (Dean Xiong and Guojun Liu. Diblock-
copolymer-coated Water-and Oil-Repellent Cotton Fabrics. Langmuir 2012,28,
The method that mentions in 6911-6918).
The method of testing of resistance to ultrasound：Super-double-hydrophobic surface is immersed in THF, because THF is for above-mentioned super-amphiphobic
Surface all has good dissolubility, then adopts KQ-218 type ultrasonic cleaners（Kunshan Ultrasonic Instruments Co., Ltd.）
Ultrasound, the contact angle after the different ultrasonic times of measurement, when the contact angle of water or oil is more than 150 °, represent the hydrophobic or thin of the material
Oiliness can not decline.Until its contact angle is less than 150 °, represent that the hydrophobic or oleophobic performance on its surface have dropped.Note
The time is recorded, by comparing the length of this time, its resistance to ultrasound is characterized.
Can be seen that by table 1：That the double thin property material of embodiment one to embodiment five is bonded with base material is firm, cohesive force strong,
Rub resistance, wash resistant.5. the material with ultra-amphosphobic surface described in can be widely used in electronic touch screen, outside 3C Product
The automatically cleaning of shell, the outer protective of military industry equipment, the water-tight corrosion-proof of oil pipeline outer layer, kitchen guarding's apparatus, automobile and aircraft etc. keep off
In terms of the productive lifes such as wind glass.
Above-described embodiment is the present invention preferably embodiment, but embodiments of the present invention are not by above-described embodiment
Limit, other any spirit without departing from the present invention and the change, modification, replacement that is made under principle, combine, simplification,
Equivalent substitute mode is should be, is included within protection scope of the present invention.
Claims (4)
1. a kind of preparation method of Cross-linkable Fluoropolyether compound, it is characterised in that comprising the step of be：By epoxy resin
It is dissolved in solvent B, Deca dispersibility material, end sulfydryl Fluoropolyether compound and catalyst while stirring at 80-120 DEG C,
Rate of addition is 1 g/min-100 g/min, after completion of dropwise addition, after continuing reaction 4-10 hours, after being cooled to room temperature, concentration,
Cross-linkable fluorochemical polyether class compound of the reprecipitation in solvent F, needed for being obtained after drying；Its epoxy resin, molten
Agent B, dispersibility material, end sulfydryl Fluoropolyether compound and catalyst between mass ratio be:1: 10-100: 1-10：1-
10:0.00001-0.0001;
The epoxy resin is polyacrylic glycidyl ether material, and its molecular weight is 1000-100000；
The solvent B is：Tetrahydrofuran, Ketohexamethylene, butanone, xylol, dimethylformamide, six alkane of dioxy, dimethyl are sub-
Sulfone, dimethyl acetylamide, N-N ketopyrrolidines, one or more mixture in diphenyl ether and methyl phenyl ethers anisole；
The catalyst is：Triethylamine, tetrabutyl ammonium fluoride, diisopropyl ethyl amine, DMA, octadecyl two
Methyl tertiary amine, oleyl dimethyl tertiary amine, dodeca-tertiary amine, one or more mixture in benzyltriethylammoinium chloride；
Described solvent F is normal hexane, and absolute ether, petroleum ether, ethyl acetate, methanol, ethanol, one or more in water are mixed
Compound.
2. the preparation method of Cross-linkable Fluoropolyether compound according to claim 1, it is characterised in that described poly- third
The synthetic method of olefin(e) acid class glycidyl ether material is as follows：
Acrylic compounds glycidyl ether monomers are added in solvent B, 60-120 DEG C is increased the temperature to, initiator is added, instead
After continuing reaction 4-10 hours, polymerization inhibitor is added, after being cooled to room temperature, concentration, reprecipitation were obtained institute in solvent F, both
The polyacrylic glycidyl ether material for needing；Wherein acrylic compounds glycidyl ether monomers, solvent B, initiator and polymerization inhibitor
Mass ratio be：1：20-100：0.001-0.005：0.0001-0.0005；
The acrylic compounds glycidyl ether is methyl propenoic acid glycidyl ether, glycidyl ether, adjacent toluene shrink
One or more mixture in glycerin ether, phenyl glycidyl ether；
The initiator be cyclohexanone peroxide, dibenzoyl peroxide, tert-butyl hydroperoxide, azodiisobutyronitrile, azo
One or more mixture in two different heptonitriles；
The polymerization inhibitor is hydroquinone, 1,4-benzoquinone, methylnaphthohydroquinone, MEHQ, 2- tert-butyl hydroquinone, 2,5- bis-
One or more mixture in tert-butyl hydroquinone.
3. the preparation method of Cross-linkable Fluoropolyether compound according to claim 1, it is characterised in that the end mercapto
The synthetic method of base Fluoropolyether compound is as follows：
Fluorochemical polyether is dissolved in tetrahydrofuran after adding lithium aluminium hydride reduction reaction 5-10 hours, obtains end and contain hydroxyl
Fluorochemical polyether, then terminad contains in the fluorochemical polyether solution of hydroxyl and adds thiourea and hydrochloric acid, and concentration of hydrochloric acid is 37%, reaction
2-5 hours, add excessive sodium hydroxide, react 5-10 hours, you can obtain holding sulfydryl Fluoropolyether compound；Wherein contain
The mass ratio of perfluoroalkyl polyether, tetrahydrofuran, lithium aluminium hydride reduction, thiourea, hydrochloric acid and sodium hydroxide is 1：10-20：0.001-0.1：3-6：
0.1-0.5：1-3；The fluorochemical polyether is preferably perfluor -2,5,8- trimethyl -3,6,9- trioxa lauroyl fluorine（CAS is logged in
Number 27639-98-1）.
4. a kind of application of Cross-linkable fluorochemical polyether class compound, it is characterised in that by Cross-linkable fluorochemical polyether class compound
Ultra-amphosphobic material is prepared, preparation method is as follows：
Step one
Substrate material surface pretreatment；The base material can be sheet glass, cotton, filter paper, timber, one kind of cement matrix；
The pretreatment of wherein filter paper, timber, cement matrix and cotton is：Successively with ethanol, water washing, then dry；
The pretreatment of sheet glass is：By sheet glass in solution soaking 2-10 hour, then then dried with ethanol, water washing successively；
It is 7 that the solution is volume ratio:3 dense H2SO4And H2O2Mixed liquor；
Step 2
The Cross-linkable Fluoropolyether compound of above-mentioned gained is dissolved in solvent B, inorganic nano-particle and catalysis is added
Agent, is prepared into super-amphiphobic coating after stirring, wherein Cross-linkable Fluoropolyether compound, solvent B, inorganic nano-particle and
The mass ratio of catalyst is 1：1-10:0-0.5：0.0001-0.001；
The inorganic nano-particle is particle diameter for the Nano microsphere of 50-1000nm, and priority protection is silicon dioxide microsphere, titanium dioxide
Titanium microsphere, ferric oxide microsphere, calcium oxide microsphere；
Step 3
The super-amphiphobic coating prepared in step 2 is coated in substrate surface by way of spraying or dip-coating, 20-30 DEG C
Lower film forming, then it is placed on crosslinking 2-24 h in 90-140 DEG C of baking oven, you can obtain a kind of ultra-amphosphobic material.
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