CN106496521B - 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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- 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 is the step of including are as follows: epoxy resin is dissolved in solvent B, dispersed substance, end sulfydryl Fluoropolyether compound and catalyst is added dropwise while stirring at 80-120 DEG C, rate of addition is 1 g/min-100 g/min, after completion of dropwise addition, after the reaction was continued 4-10 hours, after being cooled to room temperature, required Cross-linkable fluorochemical polyether class compound can be obtained after dry into solvent F in concentration, reprecipitation；Then ultra-amphosphobic material is prepared by Cross-linkable fluorochemical polyether class compound again.Its simple production process, not high to reagent and equipment requirement, fluorine-containing microballoon does not need to be dispersed in fluoride solvent, the cementitious group in surface, and cementability is good.
Description
Technical field
The invention belongs to super-amphiphobic material fields, and in particular to a kind of preparation method of Cross-linkable Fluoropolyether compound
And its application, application are that the preparation method of ultra-amphosphobic material is prepared by Cross-linkable Fluoropolyether compound.
Background technique
Surface wettability is one of important feature of the surface of solids, and wetability can be weighed with the contact angle of water on surface
Amount, is usually known as super hydrophobic surface on 150 ° or more, surface of the roll angle less than 10 ° for water contact angle, surface possesses greatly oil
In 150 ° of contact angle, it is believed that be superoleophobic surface.If the static contact angle of water and oil on a certain surface is both greater than 150 °
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 have centainly
Self-cleaning function, i.e., the water droplet that surface contaminant such as dust etc. can be tumbled takes away without leaving any trace.Automatically cleaning
Coating has the advantages such as water-saving, energy-saving and environmental protection, gets more and more extensive concerning of people, and is the heat of current material subject research
One of point.
Patent 201110131477.X proposes a kind of preparation of fluorine-containing difunctional microballoon and its applied to constructing super-amphiphobic table
Face.Main method be prepare it is a kind of containing there are many nanometer of functional group or micro-size particles, making its surface not only contain fluorination
Close object, also can with substrate reaction and form the group of covalent bond, then this surface grafting is had into fluorochemical and can be with
The nanometer or micron microballoon that matrix is chemically bonded are sprayed on substrate surface, and construct super-amphiphobic interface with this.The invention institute
The coating of preparation has excellent super-amphiphobic characteristic, and coating is bonded by covalent bond with substrate surface, so that super
Double thin performances have preferable durability.But the accessible substrate of the method has certain limitation, it is necessary to contain active group
(such as hydroxyl, carboxyl, amino) does not otherwise have caking property, and fluorine-containing microballoon needs to be dispersed in fluoride solvent.
Patent 201110266897.9 propose it is a kind of after being blended using fluorine-containing silicon-containing copolymer and silica
Surface containing active group carries out assembling film forming, can assign surface good ultra-amphosphobic energy, and this method utilizes more
Fluorine-containing silicon-containing copolymer, higher cost, and need to be blended a group reaction cartridge, technics comparing is complicated, and substrate 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 microballoon, which obtains super-amphiphobic
Surface property is excellent, not only has preferable hydrophobic oleophobic contact angle, while having good resistance to acid and alkali, also has preferable resistance to
Hou Xing.But the treatment process of this method is relatively complicated, and it is higher to reagent, equipment requirement, and fluorine-containing microballoon needs are dispersed in
In fluoride solvent, surface does not have caking property group yet, therefore cementability is also not very strong.
Fluoropolymer can be all used when constructing super-double-hydrophobic surface 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) etc. substances, this substance is all toxic to environment and human body, therefore gradually applies reducing in many application fields.
Summary of the invention
In order to overcome the disadvantages and deficiencies of the prior art, the primary purpose of the present invention is that provide a kind of Cross-linkable fluorine-containing
The preparation method of polyether compound, another object of the present invention is to provide super with the preparation of Cross-linkable Fluoropolyether compound
The preparation method of double thin property materials, simple production process is not high to reagent and equipment requirement, and fluorine-containing microballoon, which does not need to be dispersed in, to be contained
In fluorous solvent, the cementitious group in surface, cementability is good.
In order to reach above-mentioned primary and foremost purpose, the technical scheme is that, it is a kind of Cross-linkable fluorochemical polyether chemical combination
The preparation method of object, it is characterised in that the step of including are as follows: epoxy resin is dissolved in solvent B, in 80-120 DEG C of following stirring
Dispersed substance, end sulfydryl Fluoropolyether compound and catalyst is added dropwise in side, and rate of addition is 1 g/min-100 g/min, drop
After adding, after the reaction was continued 4-10 hours, after being cooled to room temperature, concentration, reprecipitation can be obtained after dry into solvent F
Required Cross-linkable fluorochemical polyether class compound；Wherein epoxy resin, solvent B, dispersed substance, end sulfydryl fluorochemical polyether
Close the mass ratio between object and catalyst are as follows: 1:10-100:1-10:1-10:0.00001-0.0001;
The epoxy resin is polyacrylic glycidol ether substance, molecular weight 1000-100000；
The solvent B are as follows: tetrahydrofuran, cyclohexanone, butanone, paraxylene, dimethylformamide, six alkane of dioxy, diformazan
Base sulfoxide, dimethyl acetamide, N-N pyrrolidones, one or more of diphenyl ether and methyl phenyl ethers anisole mixture；
The catalyst are as follows: triethylamine, tetrabutyl ammonium fluoride, diisopropyl ethyl amine, n,N-Dimethylaniline, octadecane
Base dimethyl tertiary amine, oleyl dimethyl tertiary amine, dodeca-tertiary amine, one or more of benzyltriethylammoinium chloride mixture；
The solvent F is n-hexane, anhydrous ether, petroleum ether, ethyl acetate, methanol, ethyl alcohol, one of water or several
Kind mixture.
In the technical scheme, the synthetic method of the polyacrylic glycidol ether substance is as follows:
Acrylic compounds glycidyl ether monomers are added in solvent B, increase the temperature to 60-120 DEG C, add initiation
Agent adds polymerization inhibitor after instead the reaction was continued 4-10 hours, and after being cooled to room temperature, concentration, reprecipitation can both be obtained into solvent F
To required polyacrylic glycidol ether substance；Wherein acrylic compounds glycidyl ether monomers, solvent B, initiator and resistance
The mass ratio of poly- agent are as follows: 1:20-100:0.001-0.005:0.0001-0.0005；
The acrylic compounds glycidol ether is methyl propenoic acid glycidyl ether, glycidyl ether, adjacent toluene
One or more of glycidol ether, phenyl glycidyl ether mixture；
The initiator be cyclohexanone peroxide, dibenzoyl peroxide, tert-butyl hydroperoxide, azodiisobutyronitrile,
One or more of azobisisoheptonitrile mixture；
The polymerization inhibitor be hydroquinone, 1,4-benzoquinone, methylnaphthohydroquinone, p-hydroxyanisole, 2- tert-butyl hydroquinone, 2,
One or more of 5- di-tert-butyl hydroquinone mixture.
In the technical scheme, 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
The fluorochemical polyether of hydroxyl, then terminad contain thiocarbamide and hydrochloric acid are added in the fluorochemical polyether solution of hydroxyl, concentration of hydrochloric acid 37%,
Reaction 2-5 hours adds excessive sodium hydroxide, reacts 5-10 hours, and end sulfydryl Fluoropolyether compound can be obtained；Its
Middle fluorochemical polyether, tetrahydrofuran, lithium aluminium hydride reduction, thiocarbamide, hydrochloric acid and sodium hydroxide mass ratio be 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
Accession number 27639-98-1).
In order to reach above-mentioned another object, the technical scheme is that, it is a kind of Cross-linkable fluorochemical polyether class
Close the preparation method that object prepares ultra-amphosphobic material, it is characterised in that the preparation method is as follows:
Step 1
Substrate material surface pretreatment；The base material can for sheet glass, cotton, filter paper, timber, cement matrix one
Kind；
The wherein pretreatment of filter paper, timber, cement matrix and cotton is: successively using ethyl alcohol, water washing, then dries；
The pretreatment of sheet glass is: sheet glass being impregnated 2-10 hours in solution, then successively uses ethyl alcohol, water washing, then
It is dry；The solution is the dense H that volume ratio is 7:32SO4And H2O2Mixed liquor；
Step 2
Above-mentioned resulting Cross-linkable Fluoropolyether compound is dissolved in solvent B, add inorganic nano-particle and
Catalyst is prepared into super-amphiphobic coating after mixing evenly, wherein Cross-linkable Fluoropolyether compound, solvent B, inorganic nano-particle
The mass ratio of son and catalyst is 1:1-10:0-0.5:0.0001-0.001；
The inorganic nano-particle is the nanosphere that partial size is 50-1000nm, and priority protection is silicon dioxide microsphere, two
Titania microsphere, ferric oxide microballoon, calcium oxide microballoon；
Step 3
The super-amphiphobic coating being prepared in step 2 is coated in substrate surface, 20- by way of spraying or dip-coating
It forms a film at 30 DEG C, then is placed on crosslinking 2-24 h in 90-140 DEG C of baking oven, a kind of ultra-amphosphobic material can be obtained.
Compared with prior art, the present invention have the following advantages that and the utility model has the advantages that
1, such perfluoropolyether mercaptan is almost harmless, simple production process to environment, to reagent and equipment
Of less demanding, fluorine-containing microballoon does not need to be dispersed in fluoride solvent, the cementitious group in surface；
2, the present invention uses chemical grafting method, fluoropolymer is grafted in epoxy resin, while remaining portion
Divide epoxy group, so that it is guaranteed that fluorine-containing material is securely adhered to substrate surface in polymer form, so that constructed is super
Double open coats have good durability；
3, the polymer and inorganic nano-particle have good sympathy, therefore can be by addition inorganic nano-particle come clever
The roughness at the super-amphiphobic interface finally constructed is adjusted livingly, to obtain better super-double-hydrophobic surface；
4, active site graft dispersion polymer can also be provided in the main polymer chain in the present invention, therefore super in the patent
Double thin coating may be dissolved in overwhelming majority dissolution；
5, this ultra-amphosphobic material can be widely used in electronic touch screen, the automatically cleaning of 3C Product shell, and military project is set
The production and living sides such as the windshield such as standby waterproof and anticorrosion, kitchen and bath's apparatus, automobile and the aircraft of outer protective, oil pipeline outer layer
Face.
Specific embodiment
Below with reference to embodiment, the present invention is described in further detail, and embodiments of the present invention are not limited thereto.
Embodiment one
(1) preparation of sulfydryl Fluoropolyether compound is held
Fluorochemical polyether is dissolved in tetrahydrofuran after adding lithium aluminium hydride reduction reaction 5 hours, obtains end and contain hydroxyl
The fluorochemical polyether of base, then terminad contain thiocarbamide and hydrochloric acid are added in the fluorochemical polyether solution of hydroxyl, concentration of hydrochloric acid 37%, instead
It answers 2 hours, adds excessive sodium hydroxide, react 5 hours, end sulfydryl Fluoropolyether compound can be obtained；It is wherein fluorine-containing
Polyethers, tetrahydrofuran, lithium aluminium hydride reduction, thiocarbamide, hydrochloric acid and sodium hydroxide mass ratio be 1:10:0.001:3:0.1:1；It is described to contain
Perfluoroalkyl polyether is preferably perfluor -2,5,8- trimethyl -3,6,9- trioxa lauroyl fluorine (CAS accession number 27639-98-1)；
(2) synthesis of polyacrylic glycidol ether substance
Acrylic compounds glycidyl ether monomers are added in solvent B, 120 DEG C is increased the temperature to, adds initiator,
After instead the reaction was continued 10 hours, polymerization inhibitor is added, after being cooled to room temperature, institute is both can be obtained into solvent F in concentration, reprecipitation
The polyacrylic glycidol ether substance needed；Wherein acrylic compounds glycidyl ether monomers, solvent B, initiator and polymerization inhibitor
Mass ratio are as follows: 1:100:0.001:0.0001；
The acrylic compounds glycidol ether is methyl propenoic acid glycidyl ether；The initiator is peroxidating hexamethylene
Ketone；The polymerization inhibitor is hydroquinone；The solvent B is tetrahydrofuran；
(3) preparation of Cross-linkable Fluoropolyether compound
Epoxy resin is dissolved in solvent B, dispersed substance, end sulfydryl fluorochemical polyether is added dropwise while stirring at 80 DEG C
Compound and catalyst, rate of addition is 1 g/min, dense after being cooled to room temperature after the reaction was continued 4 hours after completion of dropwise addition
Required Cross-linkable fluorochemical polyether class compound can be obtained after dry into solvent F in contracting, reprecipitation；Wherein epoxy resin,
Mass ratio between solvent B, dispersed substance, end sulfydryl Fluoropolyether compound and catalyst are as follows: 1:10:1:1:
0.00001；
The epoxy resin is polyacrylic glycidol ether substance, molecular weight 1000；The solvent B is tetrahydro
Furans；The catalyst is triethylamine；The solvent F is n-hexane；
(4) preparation of ultra-amphosphobic material
Step 1
Substrate surface pretreatment；The substrate is sheet glass, and the pretreatment of sheet glass is: sheet glass is molten in piranha
It is impregnated 2 hours in liquid, then successively uses ethyl alcohol, water washing, then dried；The volume ratio of piranha solution is the dense H of 7:32SO4With
H2O2Mixed liquor；
Step 2
Above-mentioned obtained Cross-linkable Fluoropolyether compound is dissolved in solvent B, inorganic nano-particle is added
And catalyst, it is prepared into super-amphiphobic coating after mixing evenly, wherein Cross-linkable Fluoropolyether compound, solvent B, inorganic nano
The mass ratio of particle and catalyst is 1:1:0:0.0001；
The inorganic nano-particle is the nanosphere that partial size is 50nm, and priority protection is silicon dioxide microsphere；It is described molten
Agent B is tetrahydrofuran；The catalyst is triethylamine；
Step 3
By the super-amphiphobic coating being prepared in step 2 spraying or dip-coating by way of be coated in substrate surface, 20 DEG C
Lower film forming, then be placed in 90 DEG C of baking ovens and be crosslinked 2 h, a kind of ultra-amphosphobic material can be obtained.Ultra-amphosphobic material can be extensive
Be applied to electronic touch screen, the automatically cleaning of 3C Product shell, the outer protective of military industry equipment, the waterproof of oil pipeline outer layer are anti-
In terms of the production and living such as the windshield such as corruption, kitchen and bath's apparatus, automobile and aircraft.
Embodiment two
(1) preparation of sulfydryl Fluoropolyether compound is held
Fluorochemical polyether is dissolved in tetrahydrofuran after adding lithium aluminium hydride reduction reaction 10 hours, obtains end and contain hydroxyl
The fluorochemical polyether of base, then terminad contain thiocarbamide and hydrochloric acid are added in the fluorochemical polyether solution of hydroxyl, concentration of hydrochloric acid 37%, instead
It answers 5 hours, adds excessive sodium hydroxide, react 10 hours, end sulfydryl Fluoropolyether compound can be obtained；It is wherein fluorine-containing
Polyethers, tetrahydrofuran, lithium aluminium hydride reduction, thiocarbamide, hydrochloric acid and sodium hydroxide mass ratio be 1:20:0.1:6:0.5:3；It is described fluorine-containing
Polyethers is preferably perfluor -2,5,8- trimethyl -3,6,9- trioxa lauroyl fluorine (CAS accession number 27639-98-1)；
(2) synthesis of polyacrylic glycidol ether substance
Acrylic compounds glycidyl ether monomers are added in solvent B, 120 DEG C is increased the temperature to, adds initiator,
After instead the reaction was continued 10 hours, polymerization inhibitor is added, after being cooled to room temperature, institute is both can be obtained into solvent F in concentration, reprecipitation
The polyacrylic glycidol ether substance needed；Wherein acrylic compounds glycidyl ether monomers, solvent B, initiator and polymerization inhibitor
Mass ratio are as follows: 1:100:0.005:0.0005；
The acrylic compounds glycidol ether is phenyl glycidyl ether；The initiator is azobisisoheptonitrile；It is described
Polymerization inhibitor is 2,5- di-tert-butyl hydroquinone；The solvent B is methyl phenyl ethers anisole；
(3) preparation of Cross-linkable Fluoropolyether compound
Epoxy resin is dissolved in solvent B, dispersed substance is added dropwise while stirring at 120 DEG C, holds sulfydryl fluorochemical polyether
Compound and catalyst, rate of addition is 100 g/min, after completion of dropwise addition, after the reaction was continued 10 hours, and after being cooled to room temperature,
Required Cross-linkable fluorochemical polyether class compound can be obtained after dry into solvent F in concentration, reprecipitation；Wherein asphalt mixtures modified by epoxy resin
Mass ratio between rouge, solvent B, dispersed substance, end sulfydryl Fluoropolyether compound and catalyst are as follows: 1:100:10:10:
0.0001;
The epoxy resin is polyacrylic glycidol ether substance, molecular weight 100000；The solvent B is benzene
Methyl ether；The catalyst is benzyltriethylammoinium chloride；The solvent F is anhydrous ether；
(4) preparation of ultra-amphosphobic material
Step 1
Substrate surface pretreatment；The substrate is cement；The wherein pretreatment of cement matrix is: successively with ethyl alcohol, washing
It washs, then dries；
Step 2
Above-mentioned obtained Cross-linkable Fluoropolyether compound is dissolved in solvent B, inorganic nano-particle is added
And catalyst, it is prepared into super-amphiphobic coating after mixing evenly, wherein Cross-linkable Fluoropolyether compound, solvent B, inorganic nano
The mass ratio of particle and catalyst is 1:10:0.5:0.001；
The inorganic nano-particle G is the nanosphere that partial size is 1000nm, and priority protection is calcium oxide microballoon；It is described molten
Agent B is methyl phenyl ethers anisole；The catalyst is benzyltriethylammoinium chloride；
Step 3
By the super-amphiphobic coating being prepared in step 2 spraying or dip-coating by way of be coated in substrate surface, 30 DEG C
Lower film forming, then be placed in 140 DEG C of baking ovens and be crosslinked 24 hours, a kind of super-double-hydrophobic surface can be obtained.Ultra-amphosphobic material can be wide
It is general to be applied to electronic touch screen, the automatically cleaning of 3C Product shell, the waterproof of the outer protective of military industry equipment, oil pipeline outer layer
In terms of the production and living such as the windshield such as anti-corrosion, kitchen and bath's apparatus, automobile and aircraft.
Embodiment three
(1) preparation of sulfydryl Fluoropolyether compound is held
Fluorochemical polyether is dissolved in tetrahydrofuran after adding lithium aluminium hydride reduction reaction 7 hours, obtains end and contain hydroxyl
The fluorochemical polyether of base, then terminad contain thiocarbamide and hydrochloric acid are added in the fluorochemical polyether solution of hydroxyl, concentration of hydrochloric acid 37%, instead
It answers 3 hours, adds excessive sodium hydroxide, react 6 hours, end sulfydryl Fluoropolyether compound can be obtained；It is wherein fluorine-containing
Polyethers, tetrahydrofuran, lithium aluminium hydride reduction, thiocarbamide, hydrochloric acid and sodium hydroxide mass ratio be 1:15:0.01:4:0.4:2；It is described to contain
Perfluoroalkyl polyether is preferably perfluor -2,5,8- trimethyl -3,6,9- trioxa lauroyl fluorine (CAS accession number 27639-98-1)；
(2) synthesis of polyacrylic glycidol ether substance
Acrylic compounds glycidyl ether monomers are added in solvent B, 110 DEG C is increased the temperature to, adds initiator,
After instead the reaction was continued 6 hours, polymerization inhibitor is added, after being cooled to room temperature, concentration, reprecipitation both can be obtained required into solvent F
Polyacrylic glycidol ether substance；Wherein acrylic compounds glycidyl ether monomers, solvent B, initiator and polymerization inhibitor
Mass ratio are as follows: 1:40:0.0035:0.0004；
The acrylic compounds glycidol ether is glycidyl ether；The initiator is tert-butyl hydroperoxide；
The polymerization inhibitor is p-hydroxyanisole；The solvent B is dimethyl acetamide；
(3) preparation of Cross-linkable Fluoropolyether compound
Epoxy resin is dissolved in solvent B, dispersed substance is added dropwise while stirring at 100 DEG C, holds sulfydryl fluorochemical polyether
Compound and catalyst, rate of addition is 80 g/min, dense after being cooled to room temperature after the reaction was continued 80 hours after completion of dropwise addition
Required Cross-linkable fluorochemical polyether class compound can be obtained after dry into solvent F in contracting, reprecipitation；Wherein epoxy resin,
Mass ratio between solvent B, dispersed substance, end sulfydryl Fluoropolyether compound and catalyst E are as follows: 1:80:8:6:
0.00009；
The epoxy resin is polyacrylic glycidol ether substance, molecular weight are as follows: 80000；The solvent B is two
Methylacetamide；The catalyst is oleyl dimethyl tertiary amine；The solvent F is ethyl alcohol；
(4) preparation of ultra-amphosphobic material
Step 1
Substrate surface pretreatment；The substrate is cotton；The wherein pretreatment of cotton is: successively using ethyl alcohol, water washing, so
After dry；
Step 2
Above-mentioned obtained Cross-linkable Fluoropolyether compound is dissolved in solvent B, inorganic nano-particle is added
And catalyst, it is prepared into super-amphiphobic coating after mixing evenly, wherein Cross-linkable Fluoropolyether compound, solvent B, inorganic nano
The mass ratio of particle and catalyst is 1:6:0.2:0.0005；
The inorganic nano-particle is the nanosphere that partial size is 800nm, and priority protection is ferric oxide microballoon；It is described molten
Agent B is dimethyl acetamide；The catalyst is oleyl dimethyl tertiary amine；
Step 3
The super-amphiphobic coating being prepared in step 2 is coated in substrate surface by way of spraying, at 25 DEG C at
Film, then be placed in 120 DEG C of baking ovens and be crosslinked 14 h, a kind of ultra-amphosphobic material can be obtained.Ultra-amphosphobic material can be extensive
Applied to electronic touch screen, the automatically cleaning of 3C Product shell, the outer protective of military industry equipment, the waterproof of oil pipeline outer layer are anti-
In terms of the production and living such as the windshield such as corruption, kitchen and bath's apparatus, automobile and aircraft.
Example IV
(1) preparation of sulfydryl Fluoropolyether compound is held
Fluorochemical polyether is dissolved in tetrahydrofuran after adding lithium aluminium hydride reduction reaction 6 hours, obtains end and contain hydroxyl
The fluorochemical polyether of base.Addition thiocarbamide and hydrochloric acid into the fluorochemical polyether solution that this end is hydroxyl again, concentration of hydrochloric acid 37%,
Reaction 4 hours adds excessive sodium hydroxide, reacts 7 hours, and end sulfydryl Fluoropolyether compound can be obtained；Wherein contain
Perfluoroalkyl polyether, tetrahydrofuran, lithium aluminium hydride reduction, thiocarbamide, hydrochloric acid and sodium hydroxide mass ratio be 1:11:0.02:4:0.3:2；It is described
Fluorochemical polyether is preferably perfluor -2,5,8- trimethyl -3,6,9- trioxa lauroyl fluorine (CAS accession number 27639-98-1)；
(2) synthesis of polyacrylic glycidol ether substance
Acrylic compounds glycidyl ether monomers are added in solvent B, 100 DEG C is increased the temperature to, adds initiator,
After instead the reaction was continued 7 hours, polymerization inhibitor is added, after being cooled to room temperature, concentration, reprecipitation both can be obtained required into solvent F
Polyacrylic glycidol ether substance；Wherein acrylic compounds glycidyl ether monomers, solvent B, initiator and polymerization inhibitor
Mass ratio are as follows: 1:70:0.0025:0.0003；
The acrylic compounds glycidol ether is adjacent toluene glycidol ether；The initiator is dibenzoyl peroxide；
The polymerization inhibitor is p-hydroxyanisole；The solvent B is six alkane of dioxy；
(3) preparation of Cross-linkable Fluoropolyether compound
Epoxy resin is dissolved in solvent B, dispersed substance is added dropwise while stirring at 90 DEG C, holds sulfydryl fluorochemical polyether
Compound and catalyst, rate of addition is 70 g/min, dense after being cooled to room temperature after the reaction was continued 5 hours after completion of dropwise addition
Required Cross-linkable fluorochemical polyether class compound can be obtained after dry into solvent F in contracting, reprecipitation；Wherein epoxy resin,
Mass ratio between solvent B, dispersed substance, end sulfydryl Fluoropolyether compound and catalyst are as follows: 1:30:5:6:0.00008;
The epoxy resin is polyacrylic glycidol ether substance, molecular weight 80000；The solvent B is two
Six alkane of oxygen；The catalyst is oleyl dimethyl tertiary amine；The solvent F is ethyl acetate；
(4) preparation of ultra-amphosphobic material
Step 1
Substrate surface pretreatment；Substrate is filter paper；The wherein pretreatment of filter paper is: successively using ethyl alcohol, water washing, then does
It is dry；
Step 2
Above-mentioned obtained Cross-linkable Fluoropolyether compound is dissolved in solvent B, inorganic nano-particle is added
And catalyst, it is prepared into super-amphiphobic coating after mixing evenly, wherein Cross-linkable Fluoropolyether compound, solvent B, inorganic nano
The mass ratio of particle and catalyst is 1:7:0.1:0.0008；
The inorganic nano-particle G is the nanosphere that partial size is 600nm, and priority protection is titanium dioxide microballoon sphere；Institute
Stating solvent B is six alkane of dioxy；The catalyst is oleyl dimethyl tertiary amine；
Step 3
By the super-amphiphobic coating being prepared in step 2 spraying or dip-coating by way of be coated in substrate surface, 25 DEG C
Lower film forming, then to be placed in 100 DEG C of baking ovens crosslinking 10 small, and a kind of ultra-amphosphobic material can be obtained.With ultra-amphosphobic surface
Material can be widely used in electronic touch screen, the automatically cleaning of 3C Product shell, outer protective, the oil pipeline of military industry equipment
In terms of the production and living such as the windshield such as waterproof and anticorrosion, kitchen and bath's apparatus, automobile and the aircraft of outer layer.
Embodiment five
(1) preparation of sulfydryl Fluoropolyether compound is held
Fluorochemical polyether is dissolved in tetrahydrofuran after adding lithium aluminium hydride reduction reaction 6 hours, obtains end and contain hydroxyl
The fluorochemical polyether of base.Thiocarbamide and hydrochloric acid (concentration 37%), reaction is added into the fluorochemical polyether solution that this end is hydroxyl again
2.5 hours, excessive sodium hydroxide is added, is reacted 6 hours, end sulfydryl Fluoropolyether compound can be obtained；It is wherein fluorine-containing
Polyethers, tetrahydrofuran, lithium aluminium hydride reduction, thiocarbamide, hydrochloric acid and sodium hydroxide mass ratio be 1:12:0.1:6:0.5:3；It is described to contain
Perfluoroalkyl polyether is preferably perfluor -2,5,8- trimethyl -3,6,9- trioxa lauroyl fluorine (CAS accession number 27639-98-1)；
(2) synthesis of polyacrylic glycidol ether substance
Acrylic compounds glycidyl ether monomers are added in solvent B, 100 DEG C is increased the temperature to, adds initiator,
After instead the reaction was continued 5 hours, polymerization inhibitor is added, after being cooled to room temperature, concentration, reprecipitation both can be obtained required into solvent F
Polyacrylic glycidol ether substance；Wherein acrylic compounds glycidyl ether monomers, solvent B, initiator and polymerization inhibitor
Mass ratio are as follows: 1:40:0.004:0.0002；
The acrylic compounds glycidol ether is glycidyl ether；The initiator is cyclohexanone peroxide；Institute
Stating polymerization inhibitor is 2- tert-butyl hydroquinone；The solvent B is dimethyl acetamide；
(3) preparation of Cross-linkable Fluoropolyether compound
Epoxy resin is dissolved in solvent B, dispersed substance is added dropwise while stirring at 90 DEG C, holds sulfydryl fluorochemical polyether
Compound and catalyst, rate of addition is 50 g/min, dense after being cooled to room temperature after the reaction was continued 9 hours after completion of dropwise addition
Required Cross-linkable fluorochemical polyether class compound can be obtained after dry into solvent F in contracting, reprecipitation；Wherein epoxy resin,
Mass ratio between solvent B, dispersed substance, end sulfydryl Fluoropolyether compound and catalyst are as follows: 1:50:6:7:
0.0007；
The epoxy resin is polyacrylic glycidol ether substance, molecular weight 90000；The solvent B is two
Methylacetamide；The catalyst E is oleyl dimethyl tertiary amine；The solvent F is petroleum ether；
(4) preparation of ultra-amphosphobic material
Step 1
Substrate surface pretreatment；The substrate is sheet glass, and the pretreatment of sheet glass is: sheet glass is molten in piranha
It is impregnated 10 hours in liquid, piranha solution is the dense H that volume ratio is 7:32SO4And H2O2Mixed liquor, then successively with ethyl alcohol, washing
It washs, then dries；
Step 2
Above-mentioned obtained Cross-linkable Fluoropolyether compound is dissolved in solvent B, inorganic nano-particle is added
And catalyst, it is prepared into super-amphiphobic coating after mixing evenly, wherein Cross-linkable Fluoropolyether compound, solvent B, inorganic nano
The mass ratio of particle and catalyst is 1:4:0.35:0.0005；
The inorganic nano-particle is the nanosphere that partial size is 100nm, and priority protection is silicon dioxide microsphere；It is described molten
Agent B is dimethyl acetamide；The catalyst E is oleyl dimethyl tertiary amine；
Step 3
By the super-amphiphobic coating being prepared in step 2 spraying or dip-coating by way of be coated in substrate surface, 20 DEG C
Lower film forming, then be placed in 110 DEG C of baking ovens and be crosslinked 14 hours, a kind of ultra-amphosphobic material can be obtained.
The performance parameter of double thin property materials 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 super-double-hydrophobic surface bonding on base material by indexs such as resistance to acid and alkali, washing fastness, resistance to ultrasounds
Power.
Wherein the test method of resistance to acid and alkali 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, it may be assumed that the super-amphiphobic that will be prepared
Surface is separately immersed in the solvent of different pH values, then takes out sample at regular intervals, be washed off 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 greater than 150 °, the hydrophobic or oleophobic of the material is indicated
Performance does not decline.Until its contact angle is less than 150 °, indicate that the hydrophobic or oleophobic performance on its surface is having dropped.Record
The time, by comparing the length of this time, to characterize its resistance to acid and alkali.
The test method 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 mentioned in 6911-6918).
The test method 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 uses KQ-218 type ultrasonic cleaner (Kunshan Ultrasonic Instruments Co., Ltd.)
Ultrasound, the contact angle after measuring different ultrasonic times, when water or oil contact angle be greater than 150 °, indicate the hydrophobic or thin of the material
Oiliness can not decline.Until its contact angle is less than 150 °, indicate that the hydrophobic or oleophobic performance on its surface is having dropped.Note
The time is recorded, by comparing the length of this time, to characterize its resistance to ultrasound.
By table 1 it can be seen that double thin property materials of embodiment one to embodiment five be bonded with substrate firm, cohesive force by force,
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 gear such as the outer protective of military industry equipment, the waterproof and anticorrosion of oil pipeline outer layer, kitchen and bath's apparatus, automobile and aircraft
In terms of the production and living such as wind glass.
The above embodiment is a preferred embodiment of the present invention, but embodiments of the present invention are not by above-described embodiment
Limitation, other any changes, modifications, substitutions, combinations, simplifications made without departing from the spirit and principles of the present invention,
It should be equivalent substitute mode, be included within the scope of the present invention.
Claims (2)
1. a kind of preparation method of Cross-linkable Fluoropolyether compound, it is characterised in that the step of including are as follows:
The synthesis of step 1 polyacrylic glycidol ether substance
Acrylic compounds glycidyl ether monomers are added in solvent B, increase the temperature to 60-120 DEG C, add initiator, instead
After the reaction was continued 4-10 hours, polymerization inhibitor is added, after being cooled to room temperature, institute is can be obtained into solvent F in concentration, reprecipitation
The polyacrylic glycidol ether substance needed；Wherein acrylic compounds glycidyl ether monomers, solvent B, initiator and polymerization inhibitor
Mass ratio are as follows: 1:20-100:0.001-0.005:0.0001-0.0005；
The synthesis of step 2 end sulfydryl Fluoropolyether compound
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 thiocarbamide and hydrochloric acid is added in the fluorochemical polyether solution of hydroxyl, concentration of hydrochloric acid 37%, reaction
2-5 hours, excessive sodium hydroxide is added, is reacted 5-10 hours, end sulfydryl Fluoropolyether compound can be obtained；Wherein contain
Perfluoroalkyl polyether, tetrahydrofuran, lithium aluminium hydride reduction, thiocarbamide, hydrochloric acid and sodium hydroxide mass ratio be 1:10-20:0.001-0.1:3-6:
0.1-0.5:1-3；The fluorochemical polyether is perfluor -2,5, and 8- trimethyl -3,6, (CAS is logged in 9- trioxa lauroyl fluorine
Number 27639-98-1)；
The synthesis of step 3 Cross-linkable Fluoropolyether compound
Epoxy resin is dissolved in solvent B, the end mercapto of dispersed substance, step 2 synthesis is added dropwise while stirring at 80-120 DEG C
Base Fluoropolyether compound and catalyst, rate of addition is 1 g/min-100 g/min, after completion of dropwise addition, the reaction was continued 4-10
After hour, after being cooled to room temperature, required Cross-linkable fluorochemical polyether is can be obtained after dry into solvent F in concentration, reprecipitation
Class compound；The wherein quality between epoxy resin, solvent B, dispersed substance, end sulfydryl Fluoropolyether compound and catalyst
Than for 1:10-100:1-10:1-10:0.00001-0.0001；The epoxy resin is the polyacrylic contracting of step 1 synthesis
Water glycerin ether substance, molecular weight 1000-100000；
The acrylic compounds glycidol ether be one of methyl propenoic acid glycidyl ether and glycidyl ether or
Two kinds of mixtures；
The solvent B is tetrahydrofuran, cyclohexanone, butanone, paraxylene, dimethylformamide, six alkane of dioxy, dimethyl Asia
Sulfone, dimethyl acetamide, one or more of diphenyl ether and methyl phenyl ethers anisole mixture；
The initiator is cyclohexanone peroxide, dibenzoyl peroxide, tert-butyl hydroperoxide, azodiisobutyronitrile, azo
One or more of two different heptonitriles mixture；
The polymerization inhibitor is hydroquinone, 1,4-benzoquinone, methylnaphthohydroquinone, p-hydroxyanisole, 2- tert-butyl hydroquinone, 2,5- bis-
One or more of tert-butyl hydroquinone mixture；
The solvent F is n-hexane, anhydrous ether, petroleum ether, ethyl acetate, methanol, ethyl alcohol, and one or more of water is mixed
Close object；
The catalyst is triethylamine, tetrabutyl ammonium fluoride, diisopropyl ethyl amine, N, accelerine, octadecyl two
Methyl tertiary amine, oleyl dimethyl tertiary amine, dodeca-tertiary amine, one or more of benzyltriethylammoinium chloride mixture.
2. 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, the preparation method is as follows:
Step 1
Substrate material surface pretreatment；The base material is one kind of sheet glass, cotton, filter paper, timber, cement matrix；Its
The pretreatment of middle filter paper, timber, cement matrix and cotton is: successively using ethyl alcohol, water washing, then dries；
The pretreatment of sheet glass is: sheet glass being impregnated 2-10 hours in solution, then successively uses ethyl alcohol, water washing, is then dried；
The solution is the dense H that volume ratio is 7:32SO4And H2O2Mixed liquor；
Step 2
The Cross-linkable Fluoropolyether compound that claim 1 synthesizes is dissolved in solvent B, add inorganic nano-particle and
Catalyst is prepared into super-amphiphobic coating after mixing evenly, wherein Cross-linkable Fluoropolyether compound, solvent B, inorganic nano-particle
The mass ratio of son and catalyst is 1:1-10:0-0.5:0.0001-0.001；
The inorganic nano-particle is the nanosphere that partial size is 50-1000nm, and nanosphere is silicon dioxide microsphere, titanium dioxide
Titanium microballoon, ferric oxide microballoon and calcium oxide microballoon；
The solvent B is tetrahydrofuran, cyclohexanone, butanone, paraxylene, dimethylformamide, six alkane of dioxy, dimethyl Asia
Sulfone, dimethyl acetamide, one or more of diphenyl ether and methyl phenyl ethers anisole mixture；
Step 3
By the super-amphiphobic coating being prepared in step 2 spraying or dip-coating by way of be coated in substrate surface, 20-30 DEG C
Lower film forming, then it is placed on crosslinking 2-24 h in 90-140 DEG C of baking oven, a kind of ultra-amphosphobic material can be obtained.
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