CN110358435A - A kind of self-repairing super hydrophobic coating and preparation method thereof - Google Patents
A kind of self-repairing super hydrophobic coating and preparation method thereof Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- 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
- C09D125/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Coating compositions based on derivatives of such polymers
- C09D125/02—Homopolymers or copolymers of hydrocarbons
- C09D125/04—Homopolymers or copolymers of styrene
- C09D125/06—Polystyrene
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- C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
- C09D175/04—Polyurethanes
- C09D175/08—Polyurethanes from polyethers
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- C09D179/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen, with or without oxygen, or carbon only, not provided for in groups C09D161/00 - C09D177/00
- C09D179/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
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- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
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- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
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Abstract
The present invention provides a kind of self-repairing super hydrophobic coating, and self-repairing super hydrophobic coating includes following component by mass percentage: selfreparing macromolecule 10 ~ 30%；Macromolecule plural gel 5 ~ 50%；Polystyrene powder 5 ~ 30%；Solvent 20 ~ 70%；Auxiliary agent 3 ~ 10%, wherein the selfreparing macromolecule includes the following raw material ingredient: polyether polyol, hydroxyl silicon rubber, isophorone diisocyanate, dibutyl tin dilaurate and 3,3'- dinitro diphenyl disulfide；The macromolecule plural gel includes the following raw material ingredient: nano silica, dopamine and dibutyl tin dilaurate.Self-repairing super hydrophobic coating of the invention, wherein macromolecule plural gel is that dopamine and silica and dibutyl tin dilaurate are carried out compound preparation, has high hydrophobic, high viscosity and catalytic performance；The hydrophobic interfaces of self-repairing super hydrophobic coating are made of polystyrene microsphere and nano silica based high molecular plural gel, have micro-nano double structure, can effectively be carried out to large and small water droplet hydrophobic.
Description
Technical field
Present invention relates particularly to a kind of preparation side with the super hydrophobic coating of self-repair function and the super hydrophobic coating
Method.
Background technique
Super hydrophobic coating be it is a kind of with automatically cleaning, the coating of ice-covering-proof, anticorrosion and the performances such as antifouling, it is with higher
Application value.But the endurance quality of existing super hydrophobic coating is poor, after being scraped by external force, it is easy to lose super-hydrophobic
Performance limits super-hydrophobic long-time service outdoors.Therefore, in recent years, the preparation research in relation to permanent seal cooling super hydrophobic coating
Increasingly by light beam, wherein the surface self-repairing for assigning the micro-nano imitative lotus leaf structure of coating surface is to realize that super-hydrophobic coat is resistance to
The optimal path of long type.
Currently, the preparation about permanent seal cooling super-hydrophobic coat has some patents.Such as, patent disclosure (bulletin) number is
The patent of CN103409028B, CN101962514A, CN101791608A etc., these patents use photocatalytic activity nanoparticle
Or crucial inorganic phase of the hydrophobic nano particle as imitative lotus leaf structure, be added in system thermoplasticity or type thermosetting resin at
Film, then spray mo(u)lding.The self-repair function of this kind of super-hydrophobic coat is limited only to oneself of damaged coating surface chemistries
It repairs, and the surface deeper for scratch, then it cannot achieve self-repair function, for the deeper scratch reparation on essential meaning
Material then has not been reported.Therefore, research and develop it is a kind of with persistence and can depth self-repairability super hydrophobic coating it is significant.
Summary of the invention
In view of this, in order to overcome the drawbacks of the prior art, it is super that the object of the present invention is to provide a kind of improved selfreparings
Hydrophobic coating, the coating formed after the drying by the self-repairing super hydrophobic coating when in use, not only have preferably hydrophobicity
Can, and after being destroyed, surface has excellent self-reparing capability.
In order to achieve the above object, the following technical solution is employed by the present invention:
A kind of self-repairing super hydrophobic coating, the self-repairing super hydrophobic coating includes following component by mass percentage:
The selfreparing macromolecule includes the following raw material ingredient: polyether polyol, hydroxyl silicon rubber, two isocyanide of isophorone
Acid esters, dibutyl tin dilaurate and 3,3'- dinitro diphenyl disulfide；The macromolecule plural gel include the following raw material at
Point: silica, dopamine and dibutyl tin dilaurate.
Some preferred embodiments according to the present invention prepare polyether polyols described in the high molecular raw material of the selfreparing
Pure and mild hydroxyl silicon rubber mass ratio is 1:0.5~1:3；The isophorone diisocyanate and dibutyl tin dilaurate quality
Than for 7.5:1~50:1.
Some preferred embodiments according to the present invention prepare dopamine described in the raw material of the macromolecule plural gel
Mass ratio with silica is 1:25~1:45；The mass ratio of the dopamine powder and dibutyl tin dilaurate is 1:1
~1:4.
Some preferred embodiments according to the present invention, the solvent are ethyl alcohol, n,N-dimethylacetamide, acetic acid second
One or more of ester, butyl acetate composition.
Some preferred embodiments according to the present invention, the auxiliary agent are one of dispersing agent, defoaming agent and levelling agent
Or it is a variety of.In some embodiments, dispersing agent BYK182；Defoaming agent is BYK066N；Levelling agent is BYK335.
The present invention also provides a kind of preparation method of self-repairing super hydrophobic coating as described above, the selfreparing is super thin
Water paint includes following component by mass percentage:
The preparation method of the self-repairing super hydrophobic coating include the following steps: to prepare respectively the selfreparing macromolecule,
Macromolecule plural gel and Polystyrene powder are added to n-hexane and ten difluoro heptyl trimethoxies by macromolecule plural gel
Silane is placed in 6~8h of processing in 95~105 DEG C, is then cleaned with isopropanol, obtain super-hydrophobic mixture；It will be described super-hydrophobic
Mixture, selfreparing macromolecule and solvent and auxiliary agent stir evenly after mixing in proportion, can be obtained self-repairing super hydrophobic painting
Material.
Some preferred embodiments according to the present invention, the selfreparing are high molecular the preparation method is as follows: admixtured polyether
Polyalcohol and hydroxyl silicon rubber, and 2~3h of vacuum dehydration at 110~120 DEG C, obtain alcohol/silastic mixture；By different Fo Er
Ketone diisocyanate and dibutyl tin dilaurate are added drop-wise in the alcohol/silastic mixture, are stirred at 80~90 DEG C
30min；Continue to be warming up to 95~100 DEG C, reacts 3.5~5h, obtain selfreparing performed polymer；By 3,3'- dinitro diphenyl disulfide
Ether is dissolved in tetrahydrofuran solution and is added in the selfreparing performed polymer, obtains selfreparing macromolecule.
Wherein, the pure and mild hydroxyl silicon rubber mass ratio 1:0.5~1:3 of the polyether polyols；The isophorone diisocyanate
Ester and dibutyl tin dilaurate mass ratio 7.5:1~50:1, isophorone diisocyanate and alcohol/silastic mixture quality
Than 1:1~1:6；The tetrahydrofuran solution concentration of 3, the 3'- dinitro diphenyl disulfide is 0.6g/mL, 3,3'- dinitros two
The tetrahydrofuran solution and selfreparing prepolymer mass ratio of diphenyl disulfide ether are 1:10~1:40.
Some preferred embodiments according to the present invention, the macromolecule plural gel the preparation method is as follows: by positive silicon
Acetoacetic ester is dissolved in formic acid solvent, and the ammonium hydroxide of 0.04M concentration is added thereto under agitation, will with the hydrochloric acid of 0.3M concentration
Its pH value is adjusted to 5~6；Then dopamine powder and dibutyl tin dilaurate is added, is stirred 3~5 hours in oxygen atmosphere,
30~120min of ultrasound；Poly-dopamine/bis- can be obtained in 8~12h of placement after the ammonium hydroxide of 25~28% volumetric concentrations is added again
Silica/dibutyl tin dilaurate plural gel.
Wherein, the ethyl orthosilicate and formic acid volume ratio are 1:1~1:5；The ammonium hydroxide being added for the first time and positive silicic acid
The volume ratio of ethyl ester is 1:1~1:5；The mass ratio of the dopamine and ethyl orthosilicate is 1:100~1:150；The DOPA
The mass ratio of amine powder and dibutyl tin dilaurate is 1:1~1:4；The described second ammonium hydroxide volume and positive silicic acid second being added
Ester volume ratio is 1:1~1:5.
Some preferred embodiments according to the present invention, the Polystyrene powder the preparation method is as follows: by polyethylene
Pyrrolidones is dissolved in dehydrated alcohol, and 30~60min is stirred at 60-80 DEG C；Azodiisobutyronitrile is dissolved into monomer styrene
In, and be added drop-wise in the ethanol solution of polyvinylpyrrolidone in 20~50min, and stir 10~14h；After reaction,
Obtained white " milky " liquid is centrifuged, is washed 3 times with water and dehydrated alcohol respectively, white powder ball-type knot can be obtained
The polystyrene microsphere of structure；The polystyrene microsphere of shape ball shape structure is dispersed in the potassium dichromate aqueous solution of 0.2M concentration,
1~5h is stirred at 30~50 DEG C, and the coarse Polystyrene powder of etching rear surface can be obtained.
Wherein, polyvinylpyrrolidone and dehydrated alcohol mass ratio 1:100~1:800, azodiisobutyronitrile are thick with surface
Rough styrene mass ratio 1:5~1:40, styrene and dehydrated alcohol mass ratio 1:10~1:60.
Some preferred embodiments according to the present invention, super-hydrophobic mixture the preparation method is as follows: macromolecule is compound
Gel and Polystyrene powder are added to n-hexane and ten difluoro heptyl trimethoxy silanes, be placed in 95~105 DEG C processing 6~
Then 8h is cleaned with isopropanol and super-hydrophobic poly-dopamine/silica/dibutyl tin dilaurate/polystyrene be can be obtained
Mixture.
Wherein, the macromolecule plural gel and shaggy polystyrene mass ratio 1:1~1:4；The n-hexane
With ten difluoro heptyl trimethoxy silane mass ratio 5:1~40:1, macromolecule plural gel and n-hexane mass ratio 1:10~1:
40。
In some embodiments, the above-mentioned self-repairing super hydrophobic coating being prepared is sprayed into substrate and 40~65
Obtained by drying at DEG C to arrive self-repairing super hydrophobic coating, substrate can be glass, foam, woven fabric, sponge, paper, wood, plastics or gold
Belong to.
Compared with prior art, the invention has the beneficial effects that: self-repairing super hydrophobic coating of the invention, height therein
Molecule plural gel is that dopamine and silica and dibutyl tin dilaurate are carried out compound preparation, which has
High hydrophobic, high viscosity and catalytic performance；The hydrophobic interfaces of self-repairing super hydrophobic coating are by polystyrene microsphere and nanometer titanium dioxide
Silicon substrate macromolecule plural gel is constituted, and has micro-nano double structure, can effectively be carried out to large and small water droplet hydrophobic.
Specific embodiment
In order that those skilled in the art will better understand the technical solution of the present invention, below in the embodiment of the present invention
Technical solution be clearly and completely described, it is clear that the described embodiment is only a part of the embodiment of the present invention,
Instead of all the embodiments.Based on the embodiments of the present invention, those of ordinary skill in the art are not making creative labor
Every other embodiment obtained under the premise of dynamic, should fall within the scope of the present invention.
Reagent used in following embodiment is commercially available.
Embodiment 1
A kind of preparation method of self-repairing super hydrophobic coating is present embodiments provided, specifically includes the following steps:
1) prepared by macromolecule plural gel
15mL ethyl orthosilicate is dissolved in 45mL formic acid solvent, 0.04M concentration is added thereto under agitation
Its pH value is adjusted to 5 with the hydrochloric acid of 0.3M concentration by ammonium hydroxide 5mL.Then 0.15g dopamine powder and 0.15g tin dilaurate is added
Dibutyl tin stirs 3 hours, ultrasonic 30min in oxygen atmosphere；It is put after the ammonium hydroxide 4.28mL of 25% volumetric concentration is added again
Setting 8h can be obtained poly-dopamine/silica/dibutyl tin dilaurate plural gel.
2) preparation of shaggy Polystyrene powder
1g polyvinylpyrrolidone is dissolved in 500mL dehydrated alcohol, stirs 30min at 60 DEG C；By 0.625g azo two
Isobutyronitrile is dissolved into 12.5g monomer styrene, and is added drop-wise in the ethanol solution of polyvinylpyrrolidone in 20min, and
Stir 10h；After reaction, obtained white " milky " liquid is centrifuged, is washed 3 times with water and dehydrated alcohol respectively
Obtain the polystyrene microsphere of white powder ball shape structure；The polystyrene microsphere of shape ball shape structure is dispersed to 0.2M concentration
Potassium dichromate aqueous solution in, stir 3h at 40 DEG C, the coarse Polystyrene powder of etching rear surface can be obtained.
3) decorating hydrophobic substances
0.5g macromolecule plural gel and 0.5g Polystyrene powder are added to ten difluoro heptyl three of 5g n-hexane and 40g
Methoxy silane is placed in 95 DEG C and handles 6h, then cleaned with isopropanol can be obtained super-hydrophobic poly-dopamine/silica/
Dibutyl tin dilaurate/polystyrene blends.
4) prepared by selfreparing high molecular material
The pure and mild 12g hydroxyl silicon rubber of 12g polyether polyols is mixed, and the vacuum dehydration 2h at 110 DEG C, obtain alcohol/
Silastic mixture.8g isophorone diisocyanate and 0.27g dibutyl tin dilaurate are successively added drop-wise to alcohol/silicon rubber
In mixture, the mechanical stirring 30min at 80 DEG C；Continue to be warming up to 95 DEG C, reacts 3.5h, obtain selfreparing performed polymer；It will
1.2g concentration is that the tetrahydrofuran solution of 3, the 3'- dinitro diphenyl disulfide of 0.6g/mL is added in selfreparing performed polymer, i.e.,
Selfreparing macromolecule can be obtained.
5) preparation of self-repairing super hydrophobic coating
Each component is mixed by following mass percentage, 30min is sufficiently stirred, can be obtained self-repairing super hydrophobic painting
Material.Wherein, selfreparing macromolecule 10%；Macromolecule plural gel 10%；Polystyrene 10%；Ethyl alcohol 67%；Dispersing agent 1%；
Defoaming agent 1%；Levelling agent 1%.Dispersing agent is BYK182；Defoaming agent is BYK066N；Levelling agent is BYK335.
Embodiment 2
A kind of preparation method of self-repairing super hydrophobic coating is present embodiments provided, specifically includes the following steps:
1) prepared by macromolecule plural gel
15mL ethyl orthosilicate is dissolved in 15mL formic acid solvent, 0.04M concentration is added thereto under agitation
Its pH value is adjusted to 5 with the hydrochloric acid of 0.3M concentration by ammonium hydroxide 5mL；Then 0.1g dopamine powder and 0.3g tin dilaurate two is added
Butyl tin stirs 4 hours, ultrasonic 45min in oxygen atmosphere；It is placed after the ammonium hydroxide 4.28mL of 25% volumetric concentration is added again
Poly-dopamine/silica/dibutyl tin dilaurate plural gel can be obtained in 10h.
2) preparation of shaggy Polystyrene powder
1g polyvinylpyrrolidone is dissolved in 300mL dehydrated alcohol, stirs 35min at 65 DEG C；By 0.625g azo two
Isobutyronitrile is dissolved into 12.5g monomer styrene, and is added drop-wise in the ethanol solution of polyvinylpyrrolidone in 25min, and
Stir 11h；After reaction, obtained white " milky " liquid is centrifuged, is washed 3 times with water and dehydrated alcohol respectively
Obtain the polystyrene microsphere of white powder ball shape structure；The polystyrene microsphere of shape ball shape structure is dispersed to 0.2M concentration
Potassium dichromate aqueous solution in, stir 4h at 35 DEG C, the coarse Polystyrene powder of etching rear surface can be obtained.
3) decorating hydrophobic substances
0.5g macromolecule plural gel and 0.5g Polystyrene powder are added to ten difluoro heptyl three of 5g n-hexane and 1g
Methoxy silane is placed in 95 DEG C and handles 6h, then cleaned with isopropanol can be obtained super-hydrophobic poly-dopamine/silica/
Dibutyl tin dilaurate/polystyrene blends.
4) prepared by selfreparing high molecular material
The pure and mild 12g hydroxyl silicon rubber of 12g polyether polyols is mixed, and the vacuum dehydration 2.3h at 115 DEG C, is obtained
Alcohol/silastic mixture.5g isophorone diisocyanate and 0.1g dibutyl tin dilaurate are successively added drop-wise to alcohol/silicon rubber
In glue mixture, the mechanical stirring 30min at 85 DEG C；Continue to be warming up to 98 DEG C, reacts 3.7h, obtain selfreparing performed polymer；It will
1.2g concentration is that the tetrahydrofuran solution of 3, the 3'- dinitro diphenyl disulfide of 0.6g/mL is added in selfreparing performed polymer, i.e.,
Selfreparing macromolecule can be obtained.
5) preparation of self-repairing super hydrophobic coating
Each component is mixed by following mass percentage, 80min is sufficiently stirred, can be obtained self-repairing super hydrophobic painting
Material.Wherein, selfreparing macromolecule 13%；Macromolecule plural gel 17%；Polystyrene 8%；Ethyl alcohol 58%；Dispersing agent 2%；Disappear
Infusion 2%；Levelling agent 2%.
Embodiment 3
A kind of preparation method of self-repairing super hydrophobic coating is present embodiments provided, specifically includes the following steps:
1) prepared by macromolecule plural gel
15mL ethyl orthosilicate is dissolved in 45mL formic acid solvent, 0.04M concentration is added thereto under agitation
Its pH value is adjusted to 5 with the hydrochloric acid of 0.3M concentration by ammonium hydroxide 5mL；Then 0.1g dopamine powder and 0.15g tin dilaurate two is added
Butyl tin stirs 3 hours, ultrasonic 30min in oxygen atmosphere；It is placed after the ammonium hydroxide 4.28mL of 25% volumetric concentration is added again
Poly-dopamine/silica/dibutyl tin dilaurate plural gel can be obtained in 8h.
2) preparation of shaggy Polystyrene powder
1g polyvinylpyrrolidone is dissolved in 500mL dehydrated alcohol, stirs 30min at 60 DEG C；By 0.625g azo two
Isobutyronitrile is dissolved into 12.5g monomer styrene, and is added drop-wise in the ethanol solution of polyvinylpyrrolidone in 20min, and
Stir 10h；After reaction, obtained white " milky " liquid is centrifuged, is washed 3 times with water and dehydrated alcohol respectively
Obtain the polystyrene microsphere of white powder ball shape structure；The polystyrene microsphere of shape ball shape structure is dispersed to 0.2M concentration
Potassium dichromate aqueous solution in, stir 3h at 40 DEG C, the coarse Polystyrene powder of etching rear surface can be obtained.
3) decorating hydrophobic substances
1g macromolecule plural gel and 2g Polystyrene powder are added to ten difluoro heptyl front three of 10g n-hexane and 80g
Oxysilane is placed in 95 DEG C and handles 6h, is then cleaned with isopropanol and super-hydrophobic poly-dopamine/silica/bis- can be obtained
Dibutyl tin laurate/polystyrene blends.
4) prepared by selfreparing high molecular material
The pure and mild 12g hydroxyl silicon rubber of 12g polyether polyols is mixed, and the vacuum dehydration 2h at 110 DEG C, obtain alcohol/
Silastic mixture.8g isophorone diisocyanate and 0.27g dibutyl tin dilaurate are successively added drop-wise to alcohol/silicon rubber
In mixture, the mechanical stirring 30min at 80 DEG C；Continue to be warming up to 95 DEG C, reacts 3.5h, obtain selfreparing performed polymer；It will
1.2g concentration is that the tetrahydrofuran solution of 3, the 3'- dinitro diphenyl disulfide of 0.6g/mL is added in selfreparing performed polymer, i.e.,
Selfreparing macromolecule can be obtained.
5) preparation of self-repairing super hydrophobic coating
Each component is mixed by following mass percentage, 100min is sufficiently stirred, can be obtained self-repairing super hydrophobic painting
Material.Wherein, selfreparing macromolecule 15%；Macromolecule plural gel 15%；Polystyrene 20%；Ethyl acetate 42%；Dispersing agent
2%；Defoaming agent 3%；Levelling agent 3%.
Embodiment 4
A kind of preparation method of self-repairing super hydrophobic coating is present embodiments provided, specifically includes the following steps:
1) prepared by macromolecule plural gel
15mL ethyl orthosilicate is dissolved in 75mL formic acid solvent, 0.04M concentration is added thereto under agitation
Its pH value is adjusted to 5.5 with the hydrochloric acid of 0.3M concentration by ammonium hydroxide 5mL；Then 0.05g dopamine powder and 0.2g tin dilaurate is added
Dibutyl tin stirs 4.4 hours, ultrasonic 115min in oxygen atmosphere；The ammonium hydroxide 4.28mL of 25% volumetric concentration is added again
Placing 10h afterwards can be obtained poly-dopamine/silica/dibutyl tin dilaurate plural gel.
2) preparation of shaggy Polystyrene powder
1g polyvinylpyrrolidone is dissolved in 800mL dehydrated alcohol, stirs 52min at 72 DEG C；By 0.625g azo two
Isobutyronitrile is dissolved into 21.875g monomer styrene, and is added drop-wise in the ethanol solution of polyvinylpyrrolidone in 48min,
And stir 11.7h；After reaction, obtained white " milky " liquid is centrifuged, is washed 3 times with water and dehydrated alcohol respectively,
The polystyrene microsphere of white powder ball shape structure can be obtained；The polystyrene microsphere of shape ball shape structure is dispersed to 0.2M
In the potassium dichromate aqueous solution of concentration, 3h is stirred at 40 DEG C, the coarse Polystyrene powder of etching rear surface can be obtained.
3) decorating hydrophobic substances
1g macromolecule plural gel and 4g Polystyrene powder are added to ten difluoro heptyl trimethoxy of 30g n-hexane and 6g
Base silane is placed in 98 DEG C and handles 7.3h, is then cleaned with isopropanol and super-hydrophobic poly-dopamine/silica/bis- can be obtained
Dibutyl tin laurate/polystyrene blends.
4) prepared by selfreparing high molecular material
The pure and mild 24g hydroxyl silicon rubber of 12g polyether polyols is mixed, and the vacuum dehydration 2.3h at 116 DEG C, is obtained
Alcohol/silastic mixture.10g isophorone diisocyanate and 1g dibutyl tin dilaurate are successively added drop-wise to alcohol/silicon rubber
In glue mixture, the mechanical stirring 30min at 80 DEG C；Continue to be warming up to 95 DEG C, reacts 3.5h, obtain selfreparing performed polymer；It will
1.2g concentration is that the tetrahydrofuran solution of 3, the 3'- dinitro diphenyl disulfide of 0.6g/mL is added in selfreparing performed polymer, i.e.,
Selfreparing macromolecule can be obtained.
5) preparation of self-repairing super hydrophobic coating
Each component is mixed by following mass percentage, 150min is sufficiently stirred, can be obtained self-repairing super hydrophobic painting
Material.Wherein, selfreparing macromolecule 15%；Macromolecule plural gel 35%；Polystyrene 8%；Ethyl acetate 35%；Dispersing agent
3%；Defoaming agent 1%；Levelling agent 3%.
Embodiment 5
A kind of preparation method of self-repairing super hydrophobic coating is present embodiments provided, specifically includes the following steps:
1) prepared by macromolecule plural gel
20mL ethyl orthosilicate is dissolved in 60mL formic acid solvent, 0.04M concentration is added thereto under agitation
Its pH value is adjusted to 5 with the hydrochloric acid of 0.3M concentration by ammonium hydroxide 6.7mL；Then 0.2g dopamine powder and 0.3g tin dilaurate is added
Dibutyl tin stirs 3 hours, ultrasonic 30min in oxygen atmosphere；It is put after the ammonium hydroxide 5.7mL of 28% volumetric concentration is added again
Setting 8h can be obtained poly-dopamine/silica/dibutyl tin dilaurate plural gel.
2) preparation of shaggy Polystyrene powder
1g polyvinylpyrrolidone is dissolved in 500mL dehydrated alcohol, stirs 30min at 60 DEG C；By 0.625g azo two
Isobutyronitrile is dissolved into 12.5g monomer styrene, and is added drop-wise in the ethanol solution of polyvinylpyrrolidone in 20min, and
Stir 10h；After reaction, obtained white " milky " liquid is centrifuged, is washed 3 times with water and dehydrated alcohol respectively
Obtain the polystyrene microsphere of white powder ball shape structure；The polystyrene microsphere of shape ball shape structure is dispersed to 0.2M concentration
Potassium dichromate aqueous solution in, stir 3h at 40 DEG C, the coarse Polystyrene powder of etching rear surface can be obtained.
3) decorating hydrophobic substances
1g macromolecule plural gel and 3g Polystyrene powder are added to ten difluoro heptyl front three of 10g n-hexane and 80g
Oxysilane is placed in 95 DEG C and handles 6h, is then cleaned with isopropanol and super-hydrophobic poly-dopamine/silica/bis- can be obtained
Dibutyl tin laurate/polystyrene blends.
4) prepared by selfreparing high molecular material
The pure and mild 12g hydroxyl silicon rubber of 12g polyether polyols is mixed, and the vacuum dehydration 3h at 120 DEG C, obtain alcohol/
Silastic mixture.8g isophorone diisocyanate and 0.27g dibutyl tin dilaurate are successively added drop-wise to alcohol/silicon rubber
In mixture, the mechanical stirring 30min at 80 DEG C；Continue to be warming up to 95 DEG C, reacts 3.5h, obtain selfreparing performed polymer；It will
1.2g concentration is that the tetrahydrofuran solution of 3, the 3'- dinitro diphenyl disulfide of 0.6g/mL is added in selfreparing performed polymer, i.e.,
Selfreparing macromolecule can be obtained.
5) preparation of self-repairing super hydrophobic coating
Each component is mixed by following mass percentage, 200min is sufficiently stirred, can be obtained self-repairing super hydrophobic painting
Material.Wherein, selfreparing macromolecule 10%；Macromolecule plural gel 30%；Polystyrene 10%；Ethyl acetate 41%；Dispersing agent
3%；Defoaming agent 3%；Levelling agent 3%.
Embodiment 6
A kind of preparation method of self-repairing super hydrophobic coating is present embodiments provided, specifically includes the following steps:
1) prepared by macromolecule plural gel
20mL ethyl orthosilicate is dissolved in 100mL formic acid solvent, 0.04M concentration is added thereto under agitation
Its pH value is adjusted to 5.2 with the hydrochloric acid of 0.3M concentration by ammonium hydroxide 6.3mL；Then 0.2g dopamine powder and bis- laurel of 0.8g is added
Sour dibutyl tin stirs 4.9 hours, ultrasonic 116min in oxygen atmosphere；The ammonium hydroxide 5.7mL of 28% volumetric concentration is added again
Placing 11.2h afterwards can be obtained poly-dopamine/silica/dibutyl tin dilaurate plural gel.
2) preparation of shaggy Polystyrene powder
1g polyvinylpyrrolidone is dissolved in 700mL dehydrated alcohol, stirs 54min at 77 DEG C；By 0.625g azo two
Isobutyronitrile is dissolved into 18.75g monomer styrene, and is added drop-wise in the ethanol solution of polyvinylpyrrolidone in 20min, and
Stir 13h；After reaction, obtained white " milky " liquid is centrifuged, is washed 3 times with water and dehydrated alcohol respectively
Obtain the polystyrene microsphere of white powder ball shape structure；The polystyrene microsphere of shape ball shape structure is dispersed to 0.2M concentration
Potassium dichromate aqueous solution in, stir 4.9h at 46 DEG C, the coarse Polystyrene powder of etching rear surface can be obtained.
3) decorating hydrophobic substances
1g macromolecule plural gel and 3.8g Polystyrene powder are added to ten difluoro heptyl front three of 40g n-hexane and 1g
Oxysilane is placed in 102 DEG C and handles 7.1h, then cleaned with isopropanol can be obtained super-hydrophobic poly-dopamine/silica/
Dibutyl tin dilaurate/polystyrene blends.
4) prepared by selfreparing high molecular material
The pure and mild 6g hydroxyl silicon rubber of 12g polyether polyols is mixed, and the vacuum dehydration 2.8h at 106 DEG C, obtain alcohol/
Silastic mixture.8g isophorone diisocyanate and 8g dibutyl tin dilaurate are successively added drop-wise to alcohol/silicon rubber to mix
It closes in object, the mechanical stirring 30min at 83 DEG C；Continue to be warming up to 97 DEG C, reacts 4.8h, obtain selfreparing performed polymer；1g is dense
Degree is that the tetrahydrofuran solution of 3, the 3'- dinitro diphenyl disulfide of 0.6g/mL is added in selfreparing performed polymer, be can be obtained
Selfreparing macromolecule.
5) preparation of self-repairing super hydrophobic coating
Each component is mixed by following mass percentage, 250min is sufficiently stirred, can be obtained self-repairing super hydrophobic painting
Material.Wherein, selfreparing macromolecule 21%；Macromolecule plural gel 19%；Polystyrene 12%；Ethyl acetate 41%；Dispersing agent
3%；Defoaming agent 2%；Levelling agent 2%.
The test of embodiment 7 and interpretation of result
The self-repairing super hydrophobic coating that embodiment 1 is prepared is sprayed into substrate of glass and obtained by drying at 50 DEG C
To self-repairing super hydrophobic coating.The self-repairing super hydrophobic coating that embodiment 2 is prepared is sprayed into woven fabric substrate and 50
It is obtained by drying at DEG C to arrive self-repairing super hydrophobic coating.The self-repairing super hydrophobic coating that embodiment 3 is prepared is sprayed into wood
It is in substrate and obtained by drying to self-repairing super hydrophobic coating at 55 DEG C.The self-repairing super hydrophobic that embodiment 4 is prepared applies
Material is sprayed into paper substrates and obtained by drying to self-repairing super hydrophobic coating at 55 DEG C.It is reviewed one's lessons by oneself what embodiment 5 was prepared
Multiple super hydrophobic coating is sprayed into metallic substrates and obtained by drying to self-repairing super hydrophobic coating at 60 DEG C.Embodiment 6 is made
It is sprayed into sponge substrate for obtained self-repairing super hydrophobic coating and obtained by drying to self-repairing super hydrophobic coating at 60 DEG C.
Self-repairing super hydrophobic coating derived above is subjected to hydrophobic angle test and the test of coating repair rate, wherein hydrophobic
Angle is tested using hydrophobic angle analyzer；Repair rate refers to the ratio of tensile strength of material and the preceding tensile strength of reparation after reparation, adopts
It is tested with material stretch test machine, repairing condition is to stand 5 hours under room temperature environment.Test result is as follows table.
1 test result of table
It is super thin to can be seen that the selfreparing formed by the self-repairing super hydrophobic coating in embodiment 1-6 from the data in table 1
Water coating, has excellent performance, and while obtaining excellent hydrophobic angle, can be realized self-repair function.
A kind of preparation method of self-repairing super hydrophobic coating provided by the invention, prepares macromolecule plural gel and surface
Coarse Polystyrene powder, and further hydrophobic modification is carried out to the two；And prepare the high score with self-repair function
Sub- material；A kind of self-repairing super hydrophobic coating can be obtained in the configuration for carrying out coating according still further to certain proportion, has the advantages that
(1) coating obtained by the present invention is to be answered poly-dopamine and silica and dibutyl tin dilaurate
It closes, is then doped the macromolecule of self-repair function.The plural gel has high hydrophobic, high viscosity and catalytic performance, together
When assign its self-repair function.And hydrophobic inorganic phase material reported at present is silica or silane-modified silica material
Material only has high hydrophobic function, without self-repair function.Macromolecule plural gel obtained by the present invention has superior
Performance.
(2) hydrophobic interfaces that the present invention is constituted are the polystyrene microsphere and nanometer titanium dioxide silicon substrate high score of coarse structure
Sub- plural gel is constituted, and has micro-nano double structure, can effectively be carried out to large and small water droplet hydrophobic.
(3) the self-repairing super hydrophobic coating obtained by the present invention, without using any renovation agent or regeneration in repair process
Agent can reach good selfreparing and hydrophobic effect, and low energy consumption for self-repair procedure, does not need inert gas shielding,
It can be carried out under atmospheric atmosphere, be suitble to open air large-area applications.
The above embodiments merely illustrate the technical concept and features of the present invention, and its object is to allow person skilled in the art
Scholar cans understand the content of the present invention and implement it accordingly, and it is not intended to limit the scope of the present invention, it is all according to the present invention
Equivalent change or modification made by Spirit Essence, should be covered by the protection scope of the present invention.
Claims (10)
1. a kind of self-repairing super hydrophobic coating, it is characterised in that: the self-repairing super hydrophobic coating includes by mass percentage
Following component:
The selfreparing macromolecule includes the following raw material ingredient: polyether polyol, hydroxyl silicon rubber, isophorone diisocyanate
Ester, dibutyl tin dilaurate and 3,3'- dinitro diphenyl disulfide；The macromolecule plural gel include the following raw material at
Point: nano silica, dopamine and dibutyl tin dilaurate.
2. a kind of self-repairing super hydrophobic coating according to claim 1, it is characterised in that: prepare the selfreparing macromolecule
Raw material described in the pure and mild hydroxyl silicon rubber mass ratio of polyether polyols be 1:0.5~1:3；The isophorone diisocyanate and
Dibutyl tin dilaurate mass ratio is 7.5:1~50:1.
3. a kind of self-repairing super hydrophobic coating according to claim 1, it is characterised in that: it is compound solidifying to prepare the macromolecule
Dopamine described in the raw material of glue and the mass ratio of nano silica are 1:25~1:45；The dopamine and tin dilaurate two
The mass ratio of butyl tin is 1:1~1:4.
4. a kind of self-repairing super hydrophobic coating according to claim 1, it is characterised in that: the solvent is ethyl alcohol, N, N-
One or more of dimethyl acetamide, ethyl acetate, butyl acetate composition.
5. a kind of self-repairing super hydrophobic coating according to claim 1, it is characterised in that: the auxiliary agent is dispersing agent, disappears
One of infusion and levelling agent are a variety of.
6. the preparation method of the self-repairing super hydrophobic coating as described in claim 1-5 any one, it is characterised in that: it is described from
Repair super hydrophobic coating includes following component by mass percentage:
The preparation method of the self-repairing super hydrophobic coating includes the following steps: to prepare the selfreparing macromolecule, high score respectively
Macromolecule plural gel and Polystyrene powder are added to n-hexane and ten difluoro heptyl trimethoxy silicon by sub- plural gel
Alkane is placed in 6~8h of processing in 95~105 DEG C, is then cleaned with isopropanol, obtain super-hydrophobic mixture；It will be described super-hydrophobic mixed
Conjunction object, selfreparing macromolecule and solvent and auxiliary agent stir evenly after mixing in proportion, can be obtained self-repairing super hydrophobic coating.
7. a kind of self-repairing super hydrophobic coating according to claim 6, it is characterised in that: the macromolecule plural gel and
Mass ratio 1:1~1:4 of Polystyrene powder；The n-hexane and ten difluoro heptyl trimethoxy silane mass ratio 5:1~40:
1, the macromolecule plural gel and n-hexane mass ratio 1:10~1:40.
8. a kind of self-repairing super hydrophobic coating according to claim 6, it is characterised in that: the high molecular system of selfreparing
Preparation Method is as follows: admixtured polyether polyalcohol and hydroxyl silicon rubber, and 2~3h of vacuum dehydration at 110~120 DEG C obtain alcohol/silicon
Rubber composition；Isophorone diisocyanate and dibutyl tin dilaurate are added drop-wise in the alcohol/silastic mixture,
30min is stirred at 80~90 DEG C；Continue to be warming up to 95~100 DEG C, reacts 3.5~5h, obtain selfreparing performed polymer；By 3,
3'- dinitro diphenyl disulfide is dissolved in tetrahydrofuran solution and is added in the selfreparing performed polymer, obtains selfreparing
Macromolecule.
9. a kind of self-repairing super hydrophobic coating according to claim 6, it is characterised in that: the macromolecule plural gel
The preparation method is as follows: ethyl orthosilicate is dissolved in formic acid solvent, ammonium hydroxide is added thereto under agitation, with hydrochloric acid by pH
Value is adjusted to 5~6；Then dopamine powder and dibutyl tin dilaurate is added, 3~5h, ultrasound 30 are stirred in oxygen atmosphere
~120min；It is added after the ammonium hydroxide of 25~28% volumetric concentrations again and places 8~12h that the macromolecule can be obtained is compound solidifying
Glue.
10. a kind of self-repairing super hydrophobic coating according to claim 6, it is characterised in that: the Polystyrene powder
The preparation method is as follows: polyvinylpyrrolidone is dissolved in dehydrated alcohol, 30~60min is stirred at 60-80 DEG C；Azo two is different
Butyronitrile is dissolved into monomer styrene, and is added drop-wise in the ethanol solution of polyvinylpyrrolidone in 20~50min, and stir
10~14h；After reaction, obtained white " milky " liquid is centrifuged and is cleaned, white powder ball-type knot can be obtained
The polystyrene microsphere of structure；The polystyrene microsphere of shape ball shape structure is dispersed in potassium dichromate aqueous solution, at 30~50 DEG C
1~5h is stirred, the coarse Polystyrene powder of etching rear surface can be obtained.
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