CN107384103A - A kind of preparation method of super-hydrophobic coat - Google Patents
A kind of preparation method of super-hydrophobic coat Download PDFInfo
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Abstract
The invention discloses a kind of preparation method of super-hydrophobic coat：Dodecafluoroheptyl methacrylate, methyl propenoic acid glycidyl, azodiisobutyronitrile and sodium hydrogensulfite are mixed, add tetrahydrofuran, reaction in a heated state forms reactant, and super hydrophobic coating is obtained after standing；Ultrasonic disperse forms turbid solution after nano silicon, ethanol are mixed with water；The pH value of turbid solution is adjusted to alkalescence, coupling agent and the condensing reflux under heating stirring are added into turbid solution, obtains improved silica, the amino modified silica purified after being filtered with ethanol solution, drying, grinding again, obtain amino modified nano silicon；Super hydrophobic coating is dissolved with tetrahydrofuran, then adds triethylamine, amino modified nano silicon formation modification liquid successively；Substrate is soaked in modification liquid, dried after taking-up.The super-hydrophobic coat prepared using the preparation method of the present invention has stable, lasting ultra-hydrophobicity, and reusable.
Description
Technical field
The present invention is hydrophobic to belong to Hydrophobic coating preparation method and technology field, and in particular to a kind of preparation side of super-hydrophobic coat
Method.
Background technology
Liquid in the wetability of body surface is weighed by the size of surface static contact angle, works as body surface
Static contact angle is higher than 150 °, and such a body surface is referred to as super hydrophobic surface.In recent years, super hydrophobic surface because of its automatically cleaning and is refused
The performances such as water cause the very big concern of all trades and professions.Similar with lotus leaf, water droplet not only easily tumbles in super hydrophobic surface, and is rolling
The dust granule on surface can be taken away during falling, so as to play self-cleaning effect.Super-hydrophobic self-cleaning coating have waterproof,
Many advantages, such as antifog, snow defence, anti-pollution, resist blocking and that, anti-oxidant and anticorrosion, can be widely applied to agricultural, military project, building,
The fields such as traffic, weaving, medical treatment, anti-corrosion and daily life.
The surface wettability of object is mainly what is together decided on by microstructure and chemical composition.Manually prepare super-hydrophobic table
Two kinds of approach in face are respectively：(1) coarse result is constructed in the surface of solids by the method for physics polishing or chemical experiment；
(2) on a solid surface in grafting low chemical energy molecule.At present, the method for preparing super hydrophobic surface mainly has：Electrochemistry is rotten
Erosion method, sol-gal process, phase separation method, electrostatic separation method etc., but the super hydrophobic surface that most methods are prepared is not sufficiently stable,
Easy to aging and acidproof, alkaline-resisting, salt tolerant, washing resistance performance deficiency.
The content of the invention
It is an object of the invention to provide a kind of preparation method of super-hydrophobic coat, the super-hydrophobic coat prepared has steady
Fixed, lasting ultra-hydrophobicity, and it is reusable.
The technical solution adopted in the present invention is a kind of preparation method of super-hydrophobic coat, specifically real according to following steps
Apply：
Step 1, methyl propenoic acid glycidyl is taken, methyl propenoic acid glycidyl is filtered using alumina chromatographic column,
Remove polymerization inhibitor；
Step 2, dodecafluoroheptyl methacrylate, the methyl propenoic acid glycidyl after step 1 processing are weighed respectively
And azodiisobutyronitrile and sodium hydrogensulfite；
Step 3, all materials weighed in step 2 are added in container together, then tetrahydrofuran are added into container,
The container is sealed and is passed through nitrogen, discharges the oxygen in container；
Step 4, after the completion for the treatment of step 3, whole container is positioned in oil bath constant temperature pot and heated, and under the protection of nitrogen
Open magnetic agitation, make dodecafluoroheptyl methacrylate in container, methyl propenoic acid glycidyl, azodiisobutyronitrile and
Sodium hydrogensulfite fully reacts, and question response pours out the reactant formed in container after terminating, and is stood under normal temperature, treats tetrahydrochysene furan
Mutter untill being evaporated completely, obtain super hydrophobic coating PGMA-r-PDFMA, its reaction equation is as follows：
Step 5, after the completion for the treatment of step 4, nano silicon, ethanol and water are mixed, silicon ethanol system is formed, to silicon second
Alcohol system carries out ultrasonic disperse processing, forms turbid solution；
Step 6, first the pH value of the turbid solution obtained through step 5 is adjusted to alkalescence, then coupling is added into the turbid solution
Agent simultaneously carries out condensing reflux under heating stirring, obtains improved silica；Then improved silica is entered with ethanol solution
Row filters, the amino modified silica purified；Finally the amino modified silica to purifying is dried, ground successively
Mill, obtains the amino modified nano silicon of powdery；
Step 7, after the completion for the treatment of step 6, substrate is first cleaned with detergent, soaked in absolute ethyl alcohol, then with clear
Water rinses, and finally dries, and obtains the substrate of cleaning；
Step 8, the super hydrophobic coating PGMA-r-PDFMA obtained through step 4 first dissolved with tetrahydrofuran, then added
0.5mL~1mL triethylamines, it is 9mg/mL transparency liquids to be configured to concentration, adds that the powdery obtained through step 6 is amino modified to be received
Rice silica, and the concentration of the amino modified nano silicon of powdery is 4mg/mL~18mg/mL, forms modification liquid；Will be through
Substrate after step 7 processing is soaked in modification liquid, is dried after taking-up, i.e., forms super-hydrophobic coat in substrate surface.
The features of the present invention also resides in：
In step 2：Dodecafluoroheptyl methacrylate, through step 1 processing after methyl propenoic acid glycidyl and
Mol ratio between azodiisobutyronitrile and sodium hydrogensulfite is 3~9：1：0.04~0.2：0.04~0.2.
In step 4：Temperature in oil bath constant temperature pot is 65 DEG C~75 DEG C, and the magnetic agitation time is 35min~45min.
In steps of 5：The mass fraction of nano silicon is 2.4%, and the mass fraction of ethanol is 90.3%, the matter of water
It is 7.3% to measure fraction, and above constituent content summation is 100%.
In steps of 5：The ultrasonic disperse time is 25min~35min.
Step 6 is specifically implemented according to following steps：
Step 6.1, to obtaining that triethylamine is added dropwise in turbid solution through step 5, untill when pH value is 9, reach alkaline ring
Border；
Step 6.2, the turbid solution obtained through step 6.1 poured into reactor, reactor is placed in 79 DEG C of waters bath with thermostatic control
In pot, the coupling agent KH-550 that 0.008mol~0.01mol is added dropwise after condensing unit is loaded onto, magnetic agitation, condensing reflux 4h~
6h；
Step 6.3, the material obtained through step 6.2 is filtered using being filtered by vacuum pump, obtain improved silica；
Step 6.4, using ethanol solution the improved silica obtained through step 6.3 washed, filtered, repeating 4
Amino modified silica that is secondary, being purified；
Step 6.5, the constant temperature that the amino modified silica of the purifying obtained through step 6.4 is placed in 115 DEG C~125 DEG C
In drying box, drying process 2.5h~3.5h, the amino modified nano silicon of powdery is obtained after ground processing.
In step 6.4：The mass percent concentration of ethanol solution is 95%.
In step 7：The number cleaned with detergent is 3 times~5 times, and the time soaked clearly with ethanol is 4h~6h, is used
The number of the flushing of clear water is 3 times~5 times.
In step 7：Drying temperature is 70 DEG C~90 DEG C.
In step 8：Soak time is 1h~24h, and drying temperature is 110 DEG C~130 DEG C.
The beneficial effects of the present invention are：
The preparation method of the present invention has advantages below：(1) prepared using one-step method high fluorine-containing and containing epoxide group
Polymer, while prepare amino modified nano silicon, both completed into the preparation method with tetrahydrofuran dissolving,
The preparation method is simply efficient, and repeatability is high；(2) preparation method of the invention has universality, available for multiple fiber or
The processing of material, make it that all there is superhydrophobic characteristic.
The super-hydrophobic coat prepared using the preparation method of the present invention has advantages below：(1) it is super-hydrophobic prepared by
The hydrophobic performance of coating is stable, permanent effective, and with well acidproof, alkaline-resisting, salt tolerant and resistance to supersound washing performance；(2) institute
The super-hydrophobic coat of preparation has preferably recycling ability and longer service life.
Embodiment
With reference to embodiment, the present invention is described in detail.
A kind of preparation method of super-hydrophobic coat of the present invention, specifically implements according to following steps：
Step 1, methyl propenoic acid glycidyl (GMA) is taken, methyl propenoic acid glycidyl (GMA) is used into alumina layer
Post filtering is analysed, removes polymerization inhibitor.
Step 2, according to mol ratio be 3~9：1：0.04~0.2：0.04~0.2 weighs the difluoro of methacrylic acid ten respectively
Heptyl ester (DFMA), methyl propenoic acid glycidyl (GMA) and azodiisobutyronitrile and bisulfite after step 1 processing
Sodium；
Wherein, dodecafluoroheptyl methacrylate (DFMA) and methyl propenoic acid glycidyl (GMA) are raw material, azo two
Isobutyronitrile and sodium hydrogensulfite are initiator.
Step 3, all materials weighed in step 2 are added in container together, then tetrahydrofuran are added into container,
The container is sealed and is passed through nitrogen 45min~55min, it is therefore intended that：Discharge the oxygen in container；
Wherein, tetrahydrofuran is solvent, and nitrogen is protection gas, and container can use round-bottomed flask.
Step 4, after the completion for the treatment of step 3, whole container is positioned in oil bath constant temperature pot and heated, and under the protection of nitrogen
Magnetic agitation is opened, makes dodecafluoroheptyl methacrylate (DFMA) in container, methyl propenoic acid glycidyl (GMA), even
Nitrogen bis-isobutyronitrile and sodium hydrogensulfite fully react, and question response pours out the reactant formed in container after terminating, under normal temperature
Stand, untill treating that tetrahydrofuran is evaporated completely, (being usually 1h~3h) obtains super hydrophobic coating PGMA-r-PDFMA；
Wherein, the temperature in oil bath constant temperature pot is 65 DEG C~75 DEG C, and the magnetic agitation time is 35min~45min；
Its reaction equation is as follows：
Step 5, after the completion for the treatment of step 4, nano silicon, ethanol and water are mixed, silicon ethanol system is formed, to silicon second
Alcohol system carries out ultrasonic disperse processing, forms turbid solution；
Wherein, the mass fraction of nano silicon is 2.4%, and the mass fraction of ethanol is 90.3%, the quality point of water
Number is 7.3%, and above constituent content summation is 100%；
The particle diameter of nano silicon is 15 ± 5nm；
The ultrasonic disperse time is 25min~35min.
Step 6, first the pH value of the turbid solution obtained through step 5 is adjusted to alkalescence, then coupling is added into the turbid solution
Agent simultaneously carries out condensing reflux under heating stirring, obtains improved silica；Then improved silica is entered with ethanol solution
Row filters, the amino modified silica purified；Finally the amino modified silica to purifying is dried, ground successively
Mill, obtains the amino modified nano silicon of powdery, specifically implements according to following steps：
Step 6.1, to obtaining that triethylamine is added dropwise in turbid solution through step 5, untill when pH value is 9, reach alkaline ring
Border；
Step 6.2, the turbid solution obtained through step 6.1 poured into reactor, reactor is placed in 79 DEG C of waters bath with thermostatic control
In pot, the coupling agent KH-550 that 0.008mol~0.01mol is added dropwise after condensing unit is loaded onto, magnetic agitation, condensing reflux 4h~
6h；
Step 6.3, the material obtained through step 6.2 is filtered using being filtered by vacuum pump, obtain improved silica；
Step 6.4, using the ethanol solution that mass percent concentration is 95% to the modification titanium dioxide that is obtained through step 6.3
Silicon is washed, filtered, and is repeated 4 times, the amino modified silica purified；
Step 6.5, the constant temperature that the amino modified silica of the purifying obtained through step 6.4 is placed in 115 DEG C~125 DEG C
In drying box, drying process 2.5h~3.5h, the amino modified silica of powdery is obtained after ground processing.
Step 7, after the completion for the treatment of step 6, substrate is first cleaned with detergent, soaked in absolute ethyl alcohol, then with clear
Water rinses, and finally dries, and obtains the substrate of cleaning；
Wherein, the number cleaned with detergent is 3 times~5 times, and the time soaked clearly with ethanol is 4h~6h, with clear water
The number of flushing is 3 times~5 times, and drying temperature is 70 DEG C~90 DEG C；
Substrate elects cloth, filter paper or filter cloth etc. as.
Step 8, the super hydrophobic coating PGMA-r-PDFMA obtained through step 4 first dissolved with tetrahydrofuran, then added
0.5mL~1mL triethylamines, it is 9mg/mL transparency liquids to be configured to concentration, adds that the powdery obtained through step 6 is amino modified to be received
Rice silica, and the concentration of the amino modified nano silicon of powdery is 4mg/mL~18mg/mL, forms modification liquid；Will be through
Substrate after step 7 processing is soaked in modification liquid, is dried after taking-up, i.e., forms super-hydrophobic coat in substrate surface；
Wherein, soak time is 1h~24h；Drying temperature is 110 DEG C~130 DEG C.
Embodiment 1
Methyl propenoic acid glycidyl (GMA) is taken, methyl propenoic acid glycidyl (GMA) is used into alumina chromatographic column mistake
Filter, remove polymerization inhibitor；It is 9 according to mol ratio：1：0.06：0.1 weighs dodecafluoroheptyl methacrylate (DFMA), processing respectively
Methyl propenoic acid glycidyl (GMA) and azodiisobutyronitrile and sodium hydrogensulfite afterwards；By all materials weighed together
It is added in round-bottomed flask, then tetrahydrofuran is added into round-bottomed flask, the round-bottomed flask is sealed and is passed through nitrogen 45min,
Discharge the oxygen in round-bottomed flask；Whole round-bottomed flask is positioned in the oil bath constant temperature pot that temperature is 65 DEG C and heated, and in nitrogen
Magnetic agitation 35min is opened under the protection of gas, makes dodecafluoroheptyl methacrylate (DFMA), the metering system in round-bottomed flask
Acid glycidyl (GMA), azodiisobutyronitrile and sodium hydrogensulfite are fully reacted, and question response will be formed after terminating in round-bottomed flask
Reactant pour out, stood under normal temperature, untill treating that tetrahydrofuran is evaporated completely, obtain super hydrophobic coating PGMA-r-PDFMA, its
Reaction equation is as follows：
Nano silicon, second alcohol and water are mixed, form silicon ethanol system, to silicon ethanol system ultrasonic disperse 25min,
Form turbid solution；Wherein, the mass fraction of nano silicon is 2.4%, and the particle diameter of nano silicon is 15 ± 5nm, second
The mass fraction of alcohol is 90.3%, and the mass fraction of water is 7.3%, and above constituent content summation is 100%；
To obtaining that triethylamine is added dropwise in turbid solution, untill when pH value is 9, reach alkaline environment, the muddiness that will be obtained
Liquid is poured into reactor, and reactor is placed in 79 DEG C of thermostat water baths, loads onto the coupling of dropwise addition 0.008mol after condensing unit
Agent KH-550, magnetic agitation backflow 4h；By the vacuum filtration pumping filter of obtained matter utilization, improved silica is obtained；Utilize
The ethanol solution that mass percent concentration is 95% is washed to improved silica, filtered, and is repeated 4 times, is purified
Amino modified silica；The amino modified silica of purifying is placed in 115 DEG C of thermostatic drying chamber, drying process
2.5h, the amino modified nano silicon of powdery is obtained after ground processing；
Substrate is first cleaned 3 times with detergent, 4h is soaked in absolute ethyl alcohol, then with clear water rinse 3 times, most after
70 DEG C of drying, obtain the substrate of cleaning；
Super hydrophobic coating PGMA-r-PDFMA is first dissolved with tetrahydrofuran, 1mL triethylamines is then added, is configured to concentration
For 9mg/mL transparency liquids, the amino modified nano silicon of powdery is added, and the amino modified nano silicon of powdery
Concentration is 18mg/mL, forms modification liquid；The substrate of cleaning is soaked in 24h in modification liquid, takes out after 130 DEG C of drying, that is, exists
Substrate surface forms super-hydrophobic coat.
Embodiment 2
Methyl propenoic acid glycidyl (GMA) is taken, methyl propenoic acid glycidyl (GMA) is used into alumina chromatographic column mistake
Filter, remove polymerization inhibitor；It is 8 according to mol ratio：1：0.05：0.15 weighs dodecafluoroheptyl methacrylate (DFMA), place respectively
Methyl propenoic acid glycidyl (GMA) and azodiisobutyronitrile and sodium hydrogensulfite after reason；The all materials one that will be weighed
Rise and be added in round-bottomed flask, then tetrahydrofuran is added into round-bottomed flask, the round-bottomed flask is sealed and is passed through nitrogen
50min, discharge the oxygen in round-bottomed flask；Whole round-bottomed flask is positioned in the oil bath constant temperature pot that temperature is 70 DEG C and heated,
And magnetic agitation 40min is opened under the protection of nitrogen, make dodecafluoroheptyl methacrylate (DFMA) in round-bottomed flask, first
Base glycidyl (GMA), azodiisobutyronitrile and sodium hydrogensulfite fully react, question response terminate after by round-bottomed flask
The reactant of interior formation is poured out, and is stood under normal temperature, untill treating that tetrahydrofuran is evaporated completely, obtains super hydrophobic coating PGMA-r-
PDFMA, its reaction equation are as follows：
Nano silicon, second alcohol and water are mixed, form silicon ethanol system, to silicon ethanol system ultrasonic disperse 30min,
Form turbid solution；Wherein, the mass fraction of nano silicon is 2.4%, and the particle diameter of nano silicon is 15 ± 5nm, second
The mass fraction of alcohol is 90.3%, and the mass fraction of water is 7.3%, and above constituent content summation is 100%；
To obtaining that triethylamine is added dropwise in turbid solution, untill when pH value is 9, reach alkaline environment, the muddiness that will be obtained
Liquid is poured into reactor, and reactor is placed in 79 DEG C of thermostat water baths, loads onto the coupling of dropwise addition 0.0085mol after condensing unit
Agent KH-550, magnetic agitation backflow 5h；By the vacuum filtration pumping filter of obtained matter utilization, improved silica is obtained；Utilize
The ethanol solution that mass percent concentration is 95% is washed to improved silica, filtered, and is repeated 4 times, is purified
Amino modified silica；The amino modified silica of purifying is placed in 120 DEG C of thermostatic drying chamber, drying process 3h,
The amino modified nano silicon of powdery is obtained after ground processing；
Substrate is first cleaned 4 times with detergent, 5h is soaked in absolute ethyl alcohol, then with clear water rinse 4 times, most after
80 DEG C of drying, obtain the substrate of cleaning；
Super hydrophobic coating PGMA-r-PDFMA is first dissolved with tetrahydrofuran, 0.85mL triethylamines is then added, is configured to
Concentration is 9mg/mL transparency liquids, adds the amino modified nano silicon of powdery, and the amino modified nanometer titanium dioxide of powdery
The concentration of silicon is 8mg/mL, forms modification liquid；The substrate of cleaning is soaked in 20h in modification liquid, takes out and is dried after 125 DEG C,
Super-hydrophobic coat is formed in substrate surface.
Embodiment 3
Methyl propenoic acid glycidyl (GMA) is taken, methyl propenoic acid glycidyl (GMA) is used into alumina chromatographic column mistake
Filter, remove polymerization inhibitor；It is 6 according to mol ratio：1：0.07：0.09 weighs dodecafluoroheptyl methacrylate (DFMA), place respectively
Methyl propenoic acid glycidyl (GMA) and azodiisobutyronitrile and sodium hydrogensulfite after reason；The all materials one that will be weighed
Rise and be added in round-bottomed flask, then tetrahydrofuran is added into round-bottomed flask, the round-bottomed flask is sealed and is passed through nitrogen
48min, discharge the oxygen in round-bottomed flask；Whole round-bottomed flask is positioned in the oil bath constant temperature pot that temperature is 68 DEG C and heated,
And magnetic agitation 38min is opened under the protection of nitrogen, make dodecafluoroheptyl methacrylate (DFMA) in round-bottomed flask, first
Base glycidyl (GMA), azodiisobutyronitrile and sodium hydrogensulfite fully react, question response terminate after by round-bottomed flask
The reactant of interior formation is poured out, and is stood under normal temperature, untill treating that tetrahydrofuran is evaporated completely, obtains super hydrophobic coating PGMA-r-
PDFMA, its reaction equation are as follows：
Nano silicon, second alcohol and water are mixed, form silicon ethanol system, to silicon ethanol system ultrasonic disperse 28min,
Form turbid solution；Wherein, the mass fraction of nano silicon is 2.4%, and the particle diameter of nano silicon is 15 ± 5nm, second
The mass fraction of alcohol is 90.3%, and the mass fraction of water is 7.3%, and above constituent content summation is 100%；
To obtaining that triethylamine is added dropwise in turbid solution, untill when pH value is 9, reach alkaline environment, the muddiness that will be obtained
Liquid is poured into reactor, and reactor is placed in 79 DEG C of thermostat water baths, loads onto the coupling of dropwise addition 0.0095mol after condensing unit
Agent KH-550, magnetic agitation backflow 4.5h；Obtained matter utilization vacuum filtration pumping is filtered to obtain improved silica；Utilize
The ethanol solution that mass percent concentration is 95% is washed to improved silica, filtered, and is repeated 4 times, is purified
Amino modified silica；The amino modified silica of purifying is placed in 118 DEG C of thermostatic drying chamber, drying process
2.5h, the amino modified nano silicon of powdery is obtained after ground processing；
Substrate is first cleaned 3 times with detergent, 4h is soaked in absolute ethyl alcohol, then with clear water rinse 3 times, most after
75 DEG C of drying, obtain the substrate of cleaning；
Super hydrophobic coating PGMA-r-PDFMA is first dissolved with tetrahydrofuran, 0.75mL triethylamines is then added, is configured to
Concentration is 9mg/mL transparency liquids, adds the amino modified nano silicon of powdery, and the amino modified nanometer titanium dioxide of powdery
The concentration of silicon is 11mg/mL, forms modification liquid；The substrate of cleaning is soaked in 15h in modification liquid, takes out and is dried after 120 DEG C,
Super-hydrophobic coat is formed in substrate surface.
Embodiment 4
Methyl propenoic acid glycidyl (GMA) is taken, methyl propenoic acid glycidyl (GMA) is used into alumina chromatographic column mistake
Filter, remove polymerization inhibitor；It is 5 according to mol ratio：1：0.04：0.2 weighs dodecafluoroheptyl methacrylate (DFMA), processing respectively
Methyl propenoic acid glycidyl (GMA) and azodiisobutyronitrile and sodium hydrogensulfite afterwards；By all materials weighed together
It is added in round-bottomed flask, then tetrahydrofuran is added into round-bottomed flask, the round-bottomed flask is sealed and is passed through nitrogen 53min,
Discharge the oxygen in round-bottomed flask；Whole round-bottomed flask is positioned in the oil bath constant temperature pot that temperature is 72 DEG C and heated, and in nitrogen
Magnetic agitation 42min is opened under the protection of gas, makes dodecafluoroheptyl methacrylate (DFMA), the metering system in round-bottomed flask
Acid glycidyl (GMA), azodiisobutyronitrile and sodium hydrogensulfite are fully reacted, and question response will be formed after terminating in round-bottomed flask
Reactant pour out, stood under normal temperature, untill treating that tetrahydrofuran is evaporated completely, obtain super hydrophobic coating PGMA-r-PDFMA, its
Reaction equation is as follows：
Nano silicon, second alcohol and water are mixed, form silicon ethanol system, to silicon ethanol system ultrasonic disperse 32min,
Form turbid solution；Wherein, the mass fraction of nano silicon is 2.4%, and the particle diameter of nano silicon is 15 ± 5nm, second
The mass fraction of alcohol is 90.3%, and the mass fraction of water is 7.3%, and above constituent content summation is 100%；
To obtaining that triethylamine is added dropwise in turbid solution, untill when pH value is 9, reach alkaline environment, the muddiness that will be obtained
Liquid is poured into reactor, and reactor is placed in 79 DEG C of thermostat water baths, loads onto the coupling of dropwise addition 0.009mol after condensing unit
Agent KH-550, magnetic agitation backflow 5.5h；By the vacuum filtration pumping filter of obtained matter utilization, improved silica is obtained；Profit
Improved silica is washed with the ethanol solution that mass percent concentration is 95%, filtered, is repeated 4 times, is purified
Amino modified silica；The amino modified silica of purifying is placed in 123 DEG C of thermostatic drying chamber, drying process
3h, the amino modified nano silicon of powdery is obtained after ground processing；
Substrate is first cleaned 5 times with detergent, 5.5h is soaked in absolute ethyl alcohol, then with clear water rinse 5 times, finally
In 85 DEG C of drying, the substrate of cleaning is obtained；
Super hydrophobic coating PGMA-r-PDFMA is first dissolved with tetrahydrofuran, 0.6mL triethylamines is then added, is configured to dense
Spend for 9mg/mL transparency liquids, add the amino modified nano silicon of powdery, and the amino modified nano silicon of powdery
Concentration be 14mg/mL, formed modification liquid；The substrate of cleaning is soaked in 10h in modification liquid, takes out and is dried after 120 DEG C, i.e.,
Super-hydrophobic coat is formed in substrate surface.
Embodiment 5
Methyl propenoic acid glycidyl (GMA) is taken, methyl propenoic acid glycidyl (GMA) is used into alumina chromatographic column mistake
Filter, remove polymerization inhibitor；It is 3 according to mol ratio：1：0.2：0.2 weighs dodecafluoroheptyl methacrylate (DFMA), processing respectively
Methyl propenoic acid glycidyl (GMA) and azodiisobutyronitrile and sodium hydrogensulfite afterwards；By all materials weighed together
It is added in round-bottomed flask, then tetrahydrofuran is added into round-bottomed flask, the round-bottomed flask is sealed and is passed through nitrogen 55min,
Discharge the oxygen in round-bottomed flask；Whole round-bottomed flask is positioned in the oil bath constant temperature pot that temperature is 75 DEG C and heated, and in nitrogen
Magnetic agitation 45min is opened under the protection of gas, makes dodecafluoroheptyl methacrylate (DFMA), the metering system in round-bottomed flask
Acid glycidyl (GMA), azodiisobutyronitrile and sodium hydrogensulfite are fully reacted, and question response will be formed after terminating in round-bottomed flask
Reactant pour out, stood under normal temperature, untill treating that tetrahydrofuran is evaporated completely, obtain super hydrophobic coating PGMA-r-PDFMA, its
Reaction equation is as follows：
Nano silicon, second alcohol and water are mixed, form silicon ethanol system, silicon to ethanol system ultrasonic disperse 35min,
Form turbid solution；Wherein, the mass fraction of nano silicon is 2.4%, and the particle diameter of nano silicon is 15 ± 5nm, second
The mass fraction of alcohol is 90.3%, and the mass fraction of water is 7.3%, and above constituent content summation is 100%；
To obtaining that triethylamine is added dropwise in turbid solution, untill when pH value is 9, reach alkaline environment, the muddiness that will be obtained
Liquid is poured into reactor, and reactor is placed in 79 DEG C of thermostat water baths, loads onto the coupling agent of dropwise addition 0.01mol after condensing unit
KH-550, magnetic agitation backflow 6h；Obtained matter utilization vacuum filtration pumping is filtered to obtain improved silica；Utilize quality
The ethanol solution that percent concentration is 95% is washed to improved silica, filtered, and is repeated 4 times, the amino purified
Improved silica；The amino modified silica of purifying is placed in 125 DEG C of thermostatic drying chamber, drying process 3.5h, passed through
The amino modified nano silicon of powdery is obtained after milled processed；
Substrate is first cleaned 5 times with detergent, 6h is soaked in absolute ethyl alcohol, then with clear water rinse 5 times, most after
90 DEG C of drying, obtain the substrate of cleaning；
Super hydrophobic coating PGMA-r-PDFMA is first dissolved with tetrahydrofuran, 0.5mL triethylamines is then added, is configured to dense
Spend for 9mg/mL transparency liquids, add the amino modified nano silicon of powdery, and the amino modified nano silicon of powdery
Concentration be 4mg/mL, formed modification liquid；The substrate of cleaning is soaked in 1h in modification liquid, takes out after 110 DEG C of drying, that is, exists
Substrate surface forms super-hydrophobic coat.
A kind of preparation method of super-hydrophobic coat of the present invention, preparation technology is simply controllable, the super-hydrophobic coat tool prepared
There are stabilization, lasting ultra-hydrophobicity, and it is reusable, the drawbacks of overcoming in the prior art.
Claims (10)
1. a kind of preparation method of super-hydrophobic coat, it is characterised in that specifically implement according to following steps：
Step 1, methyl propenoic acid glycidyl is taken, methyl propenoic acid glycidyl is filtered using alumina chromatographic column, removed
Polymerization inhibitor；
Step 2, weigh respectively dodecafluoroheptyl methacrylate, through step 1 processing after methyl propenoic acid glycidyl and
Azodiisobutyronitrile and sodium hydrogensulfite；
Step 3, all materials weighed in step 2 are added in container together, then tetrahydrofuran is added into container, by this
Container seals and is passed through nitrogen, discharges the oxygen in container；
Step 4, after the completion for the treatment of step 3, whole container is positioned in oil bath constant temperature pot and heated, and opened under the protection of nitrogen
Magnetic agitation, make dodecafluoroheptyl methacrylate, methyl propenoic acid glycidyl, azodiisobutyronitrile and sulfurous in container
Sour hydrogen sodium fully reacts, and question response pours out the reactant formed in container after terminating, and is stood under normal temperature, treats that tetrahydrofuran is waved
Untill distributing, super hydrophobic coating PGMA-r-PDFMA is obtained, its reaction equation is as follows：
Step 5, after the completion for the treatment of step 4, nano silicon, ethanol and water are mixed, silicon ethanol system is formed, to silicon ethanol body
System carries out ultrasonic disperse processing, forms turbid solution；
Step 6, first the pH value of the turbid solution obtained through step 5 is adjusted to alkalescence, then coupling agent is added simultaneously into the turbid solution
Condensing reflux is carried out under heating stirring, obtains improved silica；Then improved silica is taken out with ethanol solution
Filter, the amino modified silica purified；Finally the amino modified silica to purifying is dried, ground successively,
Obtain the amino modified nano silicon of powdery；
Step 7, after the completion for the treatment of step 6, substrate is first cleaned with detergent, soaks in absolute ethyl alcohol, is then rushed with clear water
Wash, finally dry, obtain the substrate of cleaning；
Step 8, the super hydrophobic coating PGMA-r-PDFMA obtained through step 4 first dissolved with tetrahydrofuran, then add 0.5mL
~1mL triethylamines, it is 9mg/mL transparency liquids to be configured to concentration, adds the amino modified nanometer two of the powdery obtained through step 6
Silica, and the concentration of the amino modified nano silicon of powdery is 4mg/mL~18mg/mL, forms modification liquid；Will be through step 7
Substrate after processing is soaked in modification liquid, is dried after taking-up, i.e., forms super-hydrophobic coat in substrate surface.
2. the preparation method of a kind of super-hydrophobic coat according to claim 1, it is characterised in that in the step 2：First
Base dodecafluorhe-ptylacrylate, methyl propenoic acid glycidyl and azodiisobutyronitrile and sulfurous acid after step 1 processing
Mol ratio between hydrogen sodium is 3~9：1：0.04~0.2：0.04~0.2.
3. the preparation method of a kind of super-hydrophobic coat according to claim 1, it is characterised in that in the step 4：Oil
The temperature bathed in constant temperature pot is 65 DEG C~75 DEG C, and the magnetic agitation time is 35min~45min.
4. the preparation method of a kind of super-hydrophobic coat according to claim 1, it is characterised in that in the step 5：Receive
The mass fraction of rice silica is 2.4%, and the mass fraction of ethanol is 90.3%, and the mass fraction of water is 7.3%, above group
It is 100% to divide content summation.
5. the preparation method of a kind of super-hydrophobic coat according to claim 1, it is characterised in that in the step 5：It is super
Sound jitter time is 25min~35min.
6. the preparation method of a kind of super-hydrophobic coat according to claim 1, it is characterised in that the step 6 is specifically pressed
Implement according to following steps：
Step 6.1, to obtaining that triethylamine is added dropwise in turbid solution through step 5, untill when pH value is 9, reach alkaline environment；
Step 6.2, the turbid solution obtained through step 6.1 poured into reactor, reactor is placed in 79 DEG C of thermostat water baths,
Load onto the coupling agent KH-550, magnetic agitation, condensing reflux 4h~6h that 0.008mol~0.01mol is added dropwise after condensing unit；
Step 6.3, the material obtained through step 6.2 is filtered using being filtered by vacuum pump, obtain improved silica；
Step 6.4, using ethanol solution the improved silica obtained through step 6.3 washed, filtered, be repeated 4 times, obtain
To the amino modified silica of purifying；
Step 6.5, the freeze-day with constant temperature that the amino modified silica of the purifying obtained through step 6.4 is placed in 115 DEG C~125 DEG C
In case, drying process 2.5h~3.5h, the amino modified nano silicon of powdery is obtained after ground processing.
7. the preparation method of a kind of super-hydrophobic coat according to claim 6, it is characterised in that in the step 6.4：
The mass percent concentration of ethanol solution is 95%.
8. the preparation method of a kind of super-hydrophobic coat according to claim 1, it is characterised in that in the step 7：With
The number of detergent cleaning is 3 times~5 times, and the time soaked clearly with ethanol is 4h~6h, and the number with the flushing of clear water is 3 times
~5 times.
9. the preparation method of a kind of super-hydrophobic coat according to claim 1 or 8, it is characterised in that in the step 7
In：The drying temperature is 70 DEG C~90 DEG C.
10. the preparation method of a kind of super-hydrophobic coat according to claim 1, it is characterised in that in the step 8：
Soak time is 1h~24h, and drying temperature is 110 DEG C~130 DEG C.
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| CN109536920A (en) * | 2018-11-27 | 2019-03-29 | 东莞市和域战士纳米科技有限公司 | A kind of antifouling nanometer film of super-hydrophobic automatic cleaning and PECVD preparation method |
| CN109609487A (en) * | 2018-11-23 | 2019-04-12 | 西安理工大学 | A kind of biological enzyme of graft polymers and preparation method thereof and fixing means |
| CN111893766A (en) * | 2020-07-28 | 2020-11-06 | 西安科技大学 | Preparation method of multifunctional pH-responsive super-wetting material and application of multifunctional pH-responsive super-wetting material in oil-water separation |
| CN113292898A (en) * | 2021-05-20 | 2021-08-24 | 东莞理工学院 | Wear-resistant high-adhesion super-hydrophobic coating and preparation method thereof |
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| CN109535902B (en) * | 2018-10-15 | 2021-01-15 | 西安理工大学 | Preparation method of super-amphiphobic coating for surface of wood-plastic composite material |
| CN109609487A (en) * | 2018-11-23 | 2019-04-12 | 西安理工大学 | A kind of biological enzyme of graft polymers and preparation method thereof and fixing means |
| CN109536920A (en) * | 2018-11-27 | 2019-03-29 | 东莞市和域战士纳米科技有限公司 | A kind of antifouling nanometer film of super-hydrophobic automatic cleaning and PECVD preparation method |
| CN109536920B (en) * | 2018-11-27 | 2021-02-09 | 深圳和力纳米科技有限公司 | Super-hydrophobic self-cleaning antifouling nano film and PECVD (plasma enhanced chemical vapor deposition) preparation method |
| CN111893766A (en) * | 2020-07-28 | 2020-11-06 | 西安科技大学 | Preparation method of multifunctional pH-responsive super-wetting material and application of multifunctional pH-responsive super-wetting material in oil-water separation |
| CN113292898A (en) * | 2021-05-20 | 2021-08-24 | 东莞理工学院 | Wear-resistant high-adhesion super-hydrophobic coating and preparation method thereof |
| CN113292898B (en) * | 2021-05-20 | 2022-03-04 | 东莞理工学院 | Wear-resistant high-adhesion super-hydrophobic coating and preparation method thereof |
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