CN106433406A - Strawberry-shaped organic/inorganic hybrid microspheres as well as application thereof - Google Patents
Strawberry-shaped organic/inorganic hybrid microspheres as well as application 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
- C09D163/00—Coating compositions based on epoxy resins; Coating compositions based on derivatives of epoxy resins
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J13/00—Colloid chemistry, e.g. the production of colloidal materials or their solutions, not otherwise provided for; Making microcapsules or microballoons
- B01J13/02—Making microcapsules or microballoons
- B01J13/06—Making microcapsules or microballoons by phase separation
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- 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
- C09D111/00—Coating compositions based on homopolymers or copolymers of chloroprene
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- C09D133/00—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 only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
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- C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
- C09D175/04—Polyurethanes
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- 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
- C09D177/00—Coating compositions based on polyamides obtained by reactions forming a carboxylic amide link in the main chain; Coating compositions based on derivatives of such polymers
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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
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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
- C09D7/65—Additives macromolecular
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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
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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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- C09D7/70—Additives characterised by shape, e.g. fibres, flakes or microspheres
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- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
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- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
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Abstract
The invention relates to strawberry-shaped organic/inorganic hybrid microspheres as well as application thereof. The microspheres are prepared based on the following method: (1) placing polystyrene microspheres into a reactor containing concentrated sulfuric acid and enabling reaction for 10 to 60 minutes, washing the product to neutral and then drying in vacuum to obtain sulfonated polyphenylene microsphere powder; (2) adding the sulfonated polystyrene microspheres, ethanol, ethyl orthosilicate and distilled water into the reactor and enabling reaction at room temperature for 24 hours to obtain strawberry-shaped composite microspheres; (3) adding the strawberry-shaped composite microspheres, a solvent and a silane coupling agent into the reactor and enabling reaction for 10 to 15 hours, and centrifuging the product to obtain strawberry-shaped organic/inorganic hybrid microspheres. The application method of the above-mentioned strawberry-shaped organic/inorganic hybrid microspheres is that when cooperated with a common adhesive, the strawberry-shaped organic/inorganic hybrid microspheres are used as a superhydrophobic coating. The strawberry-shaped organic/inorganic hybrid microspheres can be applied to coat the surfaces of various common materials; the preparation method of the coating is simple, and the superhydrophobic surface obtained is excellent in stability.
Description
Technical field
The present invention relates to the technical field of super-hydrophobic coating material, be specifically related to a kind of super-hydrophobic organic/inorganic of strawberry shape
The preparation of hybrid microspheres and the application constructing wear-resisting super-hydrophobic coat thereof.
Background technology
When material surface to the contact angle of water more than 150 °, roll angle less than 10 ° when, it is super-hydrophobic that we claim this material to have
Property.The fifties in last century rises, and external expert and scholar set about studying super-hydrophobic coat, until Germany scientist in 1997
Barthlott[W.Barthlott,et al.Planta,1997,202:1.] et al. confirming, the super-hydrophobic phenomenon of nature is
Together decided on by the mastoid process of micron-scale and the wax crystalline substance of low-surface-energy.River thunder in 2002 et al. [L.Jiang, et
Al.Adv.Mater., 2002,14,1857.] think that the supramastoid nanostructured of micron is same to the ultra-hydrophobicity of material surface
Sample plays an important role, and proposes the low-surface energy substance that ultra-hydrophobicity is by the double mesostructure of the micro-nano on its surface and its surface
Together decide on.This super hydrophobic coating with special wettability anti-icing covering, anticorrosion [Q.Liu, et
al.J.Electro.chem.Soc.,2016,163:213.], automatically cleaning and water-oil separating [Y.Chen, et
al.Appl.Surf.Sci.,2015,335:107.] etc. aspect has important application.Therefore, super hydrophobic material in recent years
Preparation is increasingly paid close attention to by people.
The surface possessing super-hydrophobic effect is generally of two conditions：One is that surface has certain roughness, i.e. micro-
Micro-nano structure；Another is to modify low-surface energy substance on a rough surface.Conventional method has：Etching method, sol-gal process, mould
Plate method, etc..For example, Huang et al. uses NaOH solution etch aluminum alloy surface, constructs flakey micro nano structure, passes through
Low-surface energy substance modify after, its contact angle to water reached 156 ° [Y.Huang, et al.Appl.Surf.Soc.,
2015,356:1012.]；Lee et al. way of collosol and gel forms the SiO with nanometer projection on silico-aluminum surface2Thin
Film, and modify SiO with low surface mass2Obtain super hydrophobic surface [J.W.Lee, et al.Mater.Lett., 2016,168:
83.]；Zhang et al. cigarette ash does template and prepares ultra-hydrophobic paper [J.H.Zhang, the et al.RSC that contact angle is up to 160 °
Adv.,2016,6:12862.].Scale, low cost can prepare, convenient use, there is the super-hydrophobic painting of crocking resistance simultaneously
Layer is the Main way of current super hydrophobic material development.
But, current techniques is only physical action between the nanostructured of these materials and micrometer structure, therefore receives
Rice grain is easy to come off.
Content of the invention
The present invention is directed to endurance quality difference present in current techniques, use the deficiencies such as limited, provide a kind of strawberry shape to have
Machine/inorganic hybridization microballoon.This material uses PS (polystyrene)@SiO2The strawberry shape microballoon of hydridization builds micro-nano structure, is formed
Nano silicon fusion growth on polystyrene microsphere (mother bulb), the micro-nano structure that has that blend compounds stick will be prepared
Strawberry shape microsphere adhesive is in different base, and the micro-nano structure coating therefore being formed has very strong durability；Simultaneously as it is careless
The exposed polystyrene of certain kind of berries shape microballoon preferably can be combined with adhesive, by the method again spraying solvent can make microballoon with micro-
Polystyrene exposed between ball can mutually glue connection, improves the fastness between microballoon and between microballoon and adhesive.This
Invention good endurance, has wide range of applications, and simultaneously scale, low cost can prepare super hydrophobic material, and its core is to have micro-nano
The complex microsphere of structure.
The technical scheme is that：
A kind of strawberry shape hybrid microballoon, this microballoon is prepared by following methods, comprises the following steps：
(1) polystyrene microsphere is put in the reactor filling the concentrated sulfuric acid, at room temperature soak 10min-30min, so
React the sulfonated polystyrene microballoon that 10～60min obtains surface band sulfonic acid group at latter 40 DEG C, with distilled water, product is washed till
Product vacuum is dried by neutrality, obtains sulfonated polystyrene microsphere powder；Quality of material is than for polystyrene microsphere：The concentrated sulfuric acid
=1：1-100；
(2) sulfonated polystyrene microballoon, ethanol, tetraethyl orthosilicate and distilled water are joined in reactor, anti-under room temperature
Answer 24h, product ethanol is washed, after vacuum drying, obtains strawberry shape complex microsphere；Quality is than sulfonated polystyrene microballoon：
Ethanol：Tetraethyl orthosilicate：Distilled water=1：1-1000：1-100：1-100；
(3) it is proportionally added into strawberry shape complex microsphere, solvent, silane coupler in reactor, at 25 DEG C-100 DEG C
Under conditions of, react 10-15h, product is centrifuged, obtains strawberry shape hybrid microballoon；Quality is more micro-than strawberry shape is combined
Ball：Solvent：Silane coupler=1：10-100：0.1-10.
In described step, polystyrene microsphere includes that the crosslinking that linear polystyrene microballoon or the degree of cross linking are 1%-80% gathers
Phenylethylene micro ball, particle size range is 200nm-20 μm；
Solvent in described step (3) is toluene, dimethylbenzene, hexane, petroleum ether, ether, ethanol, methyl alcohol, acetone, acetic acid
One or more in ethyl ester, methyl acetate and isopropyl formate；
Silane coupler in described step (3) be perfluoro capryl trimethoxy silane, perfluoro capryl triethoxysilane,
Perfluoro decyl trimethoxy silane, hexadecyl trimethoxy silane, octadecyl trimethoxysilane, perfluoro decyl three ethoxy
Base silane, trifluoro propane trimethoxy silane, HMDS or octamethylcy-clotetrasiloxane；
The application process of described strawberry shape hybrid microballoon, with common adhesive with the use of as super thin
Water coating, comprises the following steps：
Described strawberry shape hybrid microballoon is joined in dispersion solvent, obtain dispersion liquid；Adhesive is made
Use spraying process that dispersion liquid is coated on the end of solidification as external coating after substrate material surface, solidification again for primer-layer-coated
On layer coating, treat external coating to disperse solvent volatilization completely, external coating sprays a spraying solvent, solvent to be sprayed again
After volatilization completely, i.e. constitute super-hydrophobic coat；
Described quality of material is than for strawberry shape hybrid microballoon：Dispersion solvent=1：10-1000；
Described dispersion solvent and spraying solvent are identical or different, are toluene, dimethylbenzene, hexane, petroleum ether, ether, second
One or more in alcohol, methyl alcohol, acetone, ethyl acetate, methyl acetate and isopropyl formate；
Described matrix material is timber, metal, cement, fabric, plastics or glass；
Described adhesive is epoxy resin (EP), neoprene (CR), Lauxite (UF), polyurethane (PU), polypropylene
Acid resin or polyvinyl alcohol (PVA).
Beneficial effects of the present invention is：The present invention can be coated on multiple common used material surface, and preparation method for coating is succinct, and
The super hydrophobic surface obtaining has excellent stability, therefore super hydrophobic coating prepared by the present invention has good in many fields
Application prospect：
(1) the super hydrophobic coating applicability of the present invention is strong, timber, metal, building inside and outside wall, fabric, plastics, glass surface
Can apply, there is superpower water proof anti-soil effect, the glass surface of coating super hydrophobic coating is prevented by example one
The glass that dirty test discovery scribbles this material will not be by mud pollution；
(2) super hydrophobic coating of the present invention can be arranged in pairs or groups and be used multiple bottom adhesive, such as epoxy resin (EP), neoprene
(CR), Lauxite (UF), polyurethane (PU), polyacrylic resin or polyvinyl alcohol (PVA), different according to use environmental selection
Bottom adhesive, thus widened its range.Additionally, coating coordinates different bottom adhesive can be coated on different bases
Material, and all can present excellent bonding effect；
(3) present invention is during bonding, and the stability tool to coating for the structure of strawberry type microballoon has contributed much, strawberry
Shape microsphere surface has the projection of nanometer, when drop and Studies On Contacts of Rough Surfaces, owing to the capillary effect of water makes liquid
Drip the micro-nano protuberance contacts of a bottom part and coating surface, the air contact between a part and projection.Liquid or semisolid
When adhesive touches polystyrene exposed on strawberry shape microballoon, polystyrene and adhesive can preferably bond.In coating
A time solvent of upper spraying, can mutually be bondd by polystyrene between microballoon, thus add the fastness of super hydrophobic surface.
The static contact angle of gained coating of the present invention is more than 150 °, and roll angle is less than 5 °, reaches super-hydrophobic effect.As in example one to painting
The glass surface covering super hydrophobic coating has carried out antifouling test, has carried out rub resistance to the super hydrophobic surface on glass baseplate simultaneously
Experiment, after discovery abrasion instrument friction 180 circle, contact angle is 155 °, still has super-hydrophobic effect, and this also demonstrates the present invention's
Strawberry shape microballoon can mutually bond after solvent slightly soluble, it is possible to preferably combines with bottom adhesive so that it is be provided with
Very strong crocking resistance.The maximum static contact angle of slide of coating super hydrophobic coating reaches 166.0 °, and roll angle is less than 3 °,
Illustrate that the strawberry shape material of the present invention can construct micro-nano structure, be relatively suitable for as super hydrophobic material.
(4) present invention meets the Cassie-Baxter model generally acknowledged now, the preparation manipulation of super-hydrophobic microballoon in the present invention
Simply, with low cost, it is not necessary to expensive device and harsh process conditions, it is not necessary to complex operations, it is not necessary to complex device, and have excellent
Different, stable ultra-hydrophobicity, can be with the adhesive of multiple maturations with the use of and obtained super hydrophobic surface is firmly resistance to
With.There is good industrial development application prospect.
Brief description
1) Fig. 1 is the microcosmic SEM photograph of the strawberry shape hybrid microballoon prepared by embodiment one；
2) Fig. 2 is the optical photograph of super-hydrophobic coat constructed by embodiment one, and wherein upper right corner illustration is the quiet of this coating
State contact angle tests photo, and maximum static contact angle reaches 166.0 °；
3) Fig. 3 is substrate of glass coating super-hydrophobic coat (right) constructed by embodiment one and uncoated super-hydrophobic coat
(left) contrast photo after mud contamination；
4) Fig. 4 is that substrate of glass coating super-hydrophobic coat constructed in embodiment one is at the light after abrasion instrument test
Learning photo and static contact angle test photo, static contact angle is 155.0 °；
Detailed description of the invention
Below in conjunction with embodiment and accompanying drawing, the present invention is described further；
Polystyrene microsphere of the present invention includes linear polystyrene microballoon or crosslinked polystyrene microsphere, is known
Product, those of ordinary skill in the art can be prepared by commercially available or known method.
Embodiment one：
(1) preparation of strawberry shape hybrid microballoon
1g linear polystyrene microballoon (500nm) is put into the reactor filling 20mL (36.72g) concentrated sulfuric acid (98%)
In, at room temperature soak 10min, then reaction 30min obtains the sulfonated polystyrene microballoon of surface band sulfonic acid group at 40 DEG C,
With distilled water, product is washed till neutrality, product vacuum is dried, obtain sulfonated polystyrene microsphere powder.Take wherein 1g sulfonation to gather
Styrene (PS-sul) microballoon is put in reactor, adds 100mL (78.93g) ethanol, and stirring to sulfonated polystyrene microballoon divides
Dissipating uniformly, being sequentially added into 20g tetraethyl orthosilicate (TEOS) and 20g distilled water in reactor, under room temperature, reaction 24h, obtains grass
Product ethanol is washed 3 times, after vacuum drying, is obtained the PS/SiO of strawberry shape by certain kind of berries shape complex microsphere dispersion liquid2Complex microsphere powder
End.Take the PS/SiO of 1g strawberry shape2Complex microsphere powder adds in reactor, is subsequently adding the dispersion liquid of 100mL (78.93g)
Ethanol, adds the perfluoro capryl trimethoxy silane modified-reaction of 300 μ L (0.44g) to carry out after system temperature reaches 80 DEG C
12h, obtain strawberry shape hybrid microballoon after centrifuging；
(2) strawberry shape hybrid microballoon and epoxy resin are with the use of as super-hydrophobic coat
The strawberry shape hybrid microballoon preparing 1g above-mentioned steps is dispersed in 50g ethanol, obtains dispersion liquid.
By epoxy resin E51 and polyamide in mass ratio 1：The ratio mixing of 1, is uniformly applied in substrate of glass, treats adhesive 60
After DEG C solidification 1.5h, dispersion liquid is applied on bottom that (inside and outside coating is not necessarily to pro rate, only need to all coat i.e. undercoating
Can), after dispersion liquid volatilization, then spray an xylene solvent, treat dimethylbenzene volatilization completely, build super-hydrophobic coat；
The SEM photograph (FEI Co. NanoSEM 450) that accompanying drawing 1 is strawberry shape hybrid microballoon, mutually piles up
Strawberry shape hybrid microballoon can construct the raised structures of micron, on microballoon to be covered with nano silicon convex
Rise, imparted the ultra-hydrophobicity of coating surface by the micro-nano compound structure that both form.
Accompanying drawing 2 is optical photograph on the sheet glass scribbling super-hydrophobic coat for the water droplet under room temperature (25 DEG C), and water droplet is still protected
Holding shape, shows that this surface has stronger hydrophobic performance, and wherein upper right corner illustration is the static contact angle test photograph of this coating
Piece (isThe DSA30 contact angle tester that company produces, test condition：Drop 5uL), under room temperature (25 DEG C), use pure water
The maximum static contact angle of (prepared by the UPR-11-10T water purification machine of Chengdu Ultra Pure Science ＆ Technology Co., Ltd) test super hydrophobic surface is
166.0 °, roll angle is less than 3 ° (contact angle test condition described in following steps and embodiment and tester are same)；
Testing the antifouling experiment of this super-hydrophobic coat on glass plate base material, this experiment is at room temperature carried out, by glass plate
(area is about 110cm to right half part2) apply this super-hydrophobic coat, the unused super-hydrophobic coat process of glass plate left half.By mud
Water sprinkles on whole glass plate, scribbles the non-clay slurry of right half part of super-hydrophobic coat, and a left side for uncoated super-hydrophobic coat is partly
Glass sheet partial sticks mud, and accompanying drawing 3 is its design sketch, has absolutely proved that super hydrophobic material prepared by the present invention has very strong
Anti-pollution function.
Test the anti-wear performance experiment of this super-hydrophobic coat on glass plate base material, this applying coating is ground in JM-IV type
It on the glass brassboard of consumption instrument, is arranged on the glass plate coating on abrasion instrument, under 500g pressure, uses the rubber of 100 mesh
Emery wheel, with the speed of 20r/min, after friction 180 circle, coating still has super-hydrophobic effect, and contact angle is 155.0 °.Fig. 4 is its effect
Fruit figure, illustrates that this coating has stronger rub resistance and fastness, also demonstrates strawberry shape hybrid microballoon conduct
Super hydrophobic coating has the advantage in structure.
Embodiment two：
(1) preparation of strawberry shape hybrid microballoon
The polystyrene microsphere (600nm) that the 1g degree of cross linking is 10% is put into and fills 20mL (36.72g) concentrated sulfuric acid (98%)
Reactor in, at room temperature soak 10min, then reaction 10min obtains the sulfonated polyphenyl of surface band sulfonic acid group at 40 DEG C
Product is washed till neutrality with distilled water by ethene microballoon, is dried product vacuum, obtains sulfonated polystyrene microsphere powder.Take it
Middle 1g sulfonated polystyrene (PS-sul) microballoon is put in reactor, adds 100mL (78.93g) ethanol, and stirring is to sulfonated polyphenyl
Ethene microballoon is uniformly dispersed, and is sequentially added into 20g tetraethyl orthosilicate (TEOS) and 20g distilled water in reactor, reacts under room temperature
24h, obtains strawberry shape complex microsphere dispersion liquid, washes product ethanol 3 times, after vacuum drying, obtains the PS/SiO of strawberry shape2
Complex microsphere powder.Take the PS/SiO of 1g strawberry shape2Complex microsphere powder adds in reactor, is subsequently adding 100mL
(78.93g) dispersion liquid ethanol, adds the perfluor certain herbaceous plants with big flowers base trimethoxy silicon of 300 μ L (0.46g) after system temperature reaches 80 DEG C
Alkane modified-reaction carries out 12h, obtains strawberry shape hybrid microballoon after centrifuging；
(2) strawberry shape hybrid microballoon and polyurethane formulation use as super-hydrophobic coat
The strawberry shape hybrid microballoon preparing 1g above-mentioned steps is dispersed in 50g ethanol, obtains dispersion liquid.
In this example, priming coat is the polyurethane adhesive purchased, and is uniformly applied in substrate of glass, will divide after 100 DEG C of solidification 10min
Scattered liquid is sprayed at (inside and outside coating is not necessarily to pro rate, only need to all coat undercoating) on bottom, treats that dispersion liquid is waved
After Faing, at a time xylene solvent of spraying, treat dimethylbenzene volatilization completely, build super-hydrophobic coat；
After tested, the maximum static contact angle of this sample is 165.0 °；
Mud contamination experiment effect is with example 1；
It it is 154.0 ° with contact angle after method friction 180 circle of example one
Embodiment three：
(1) preparation of strawberry shape hybrid microballoon
1g linear polystyrene microballoon (500nm) is put into the reactor filling 20mL (36.72g) concentrated sulfuric acid (98%)
In, at room temperature soak 10min, then reaction 10min obtains the sulfonated polystyrene microballoon of surface band sulfonic acid group at 40 DEG C,
With distilled water, product is washed till neutrality, product vacuum is dried, obtain sulfonated polystyrene microsphere powder.Take wherein 1g sulfonation to gather
Styrene (PS-sul) microballoon is put in reactor, adds 100mL (78.93g) ethanol, and stirring to sulfonated polystyrene microballoon divides
Dissipating uniformly, being sequentially added into 20g tetraethyl orthosilicate (TEOS) and 20g distilled water in reactor, under room temperature, reaction 24h, obtains grass
Product ethanol is washed 3 times, after vacuum drying, is obtained the PS/SiO of strawberry shape by certain kind of berries shape complex microsphere dispersion liquid2Complex microsphere powder
End.Take the PS/SiO of 1g strawberry shape2Complex microsphere powder adds in reactor, is subsequently adding the dispersion liquid of 100mL (78.93g)
Ethanol, adds the trifluoro propane trimethoxy silane modified-reaction of 250 μ L (0.27g) to carry out after system temperature reaches 80 DEG C
12h, obtains strawberry shape hybrid microballoon after centrifuging；
(2) strawberry shape hybrid microballoon and polyacrylic resin are with the use of as super-hydrophobic coat
The strawberry shape hybrid microballoon preparing 1g above-mentioned steps is dispersed in 50g ethanol, obtains dispersion liquid.
In this example, priming coat is the polyacrylic resin purchased, and is uniformly applied in substrate of glass, by dispersion liquid after 25 DEG C of solidification 2h
It is sprayed at (inside and outside coating is not necessarily to pro rate, only need to all coat undercoating) on bottom, after dispersion liquid volatilization,
At a time xylene solvent of spraying, treat dimethylbenzene volatilization completely, build super-hydrophobic coat；
After tested, the maximum static contact angle of this sample is 163.0 °；
Mud contamination experiment effect is with example 1；
It it is 154.0 ° with contact angle after method friction 180 circle of example one
Embodiment four：
(1) preparation of strawberry shape hybrid microballoon
The polystyrene microsphere (400nm) that the 1g degree of cross linking is 20% is put into and fills 20mL (36.72g) concentrated sulfuric acid (98%)
Reactor in, at room temperature soak 10min, then reaction 10min obtains the sulfonated polyphenyl of surface band sulfonic acid group at 40 DEG C
Product is washed till neutrality with distilled water by ethene microballoon, is dried product vacuum, obtains sulfonated polystyrene microsphere powder.Take it
Middle 1g sulfonated polystyrene (PS-sul) microballoon is put in reactor, adds 100mL (78.93g) ethanol, and stirring is to sulfonated polyphenyl
Ethene microballoon is uniformly dispersed, and is sequentially added into 10g tetraethyl orthosilicate (TEOS) and 10g distilled water in reactor, reacts under room temperature
24h, obtains strawberry shape complex microsphere dispersion liquid, washes product ethanol 3 times, after vacuum drying, obtains the PS/SiO of strawberry shape2
Complex microsphere powder.Take the PS/SiO of 1g strawberry shape2Complex microsphere powder adds in reactor, is subsequently adding 100mL
(78.93g) dispersion liquid ethanol, adds the hexadecyl trimethoxy silicon of 250 μ L (0.22g) after system temperature reaches 80 DEG C
Alkane modified-reaction carries out 12h, obtains strawberry shape hybrid microballoon after centrifuging；
(2) strawberry shape hybrid microballoon and neoprene are with the use of as super-hydrophobic coat
The strawberry shape hybrid microballoon preparing 1g above-mentioned steps is dispersed in 50g ethanol, obtains dispersion liquid.
In this example, base coat solution is the neoprene adhesive purchased, and is uniformly applied in substrate of glass, after 25 DEG C of solidification 30min
Dispersion liquid is sprayed at (inside and outside coating is not necessarily to pro rate, only need to all coat priming coat) on bottom, waits to disperse
After liquid volatilization, at a time xylene solvent of spraying, treat dimethylbenzene volatilization completely, build super-hydrophobic coat；
After tested, the maximum static contact angle of this sample is 160.0 °；
Mud contamination experiment effect is with example 1；
It it is 153.0 ° with contact angle after method friction 180 circle of example one
Embodiment five：
Enforcement step is with embodiment one, and difference is, by bottom uniform application in iron plate substrate, treats adhesive 60
After DEG C solidification 1.5h, dispersion liquid is sprayed on priming coat, treats dispersion liquid volatilization completely, at a time xylene solvent of spraying, treat
Dimethylbenzene volatilization completely, builds super-hydrophobic coat；
After tested, the maximum static contact angle of this sample is 166.0 °；
Mud contamination experiment effect is with embodiment 1；
Embodiment six：
Enforcement step is with embodiment one, and difference is, by bottom uniform application in cement substrate, treats adhesive 60
After DEG C solidification 1.5h, dispersion liquid is sprayed on priming coat, treats dispersion liquid volatilization completely, at a time xylene solvent of spraying, treat
Dimethylbenzene volatilization completely, builds super-hydrophobic coat；
After tested, the maximum static contact angle of this sample is 165.5 °；
Mud contamination experiment effect is with embodiment 1；
Use different silane coupler modified strawberry shape hybrid microballoon, its super hydrophobic surface being formed
Hydrophobic performance is also different.Fluorine-containing silane coupler hydrophobic effect is preferable, but expensive.Therefore can according to reality apply in right
The different silane coupler of the different choice of hydrophobic performance, this various selectivity can reduce the cost of material.Further, root
According to base material with use the difference of environment can select different bottom adhesive, therefore, this coating have stronger adaptability with
Stability.
Unaccomplished matter of the present invention is known technology.
Claims (9)
1. a strawberry shape hybrid microballoon, is characterized by that this microballoon is prepared by following methods, comprises the following steps：
（1）Polystyrene microsphere is put in the reactor filling the concentrated sulfuric acid, at room temperature soak 10min-30min, then 40
React the sulfonated polystyrene microballoon that 10 ~ 60min obtains surface band sulfonic acid group at DEG C, with distilled water, product be washed till neutrality,
Product vacuum is dried, obtains sulfonated polystyrene microsphere powder；Quality of material is than for polystyrene microsphere：The concentrated sulfuric acid=1：1-
100；
（2）Sulfonated polystyrene microballoon, ethanol, tetraethyl orthosilicate and distilled water are joined in reactor, reacts under room temperature
Product ethanol is washed, after vacuum drying, obtains strawberry shape complex microsphere by 24h；Quality is than sulfonated polystyrene microballoon：Second
Alcohol：Tetraethyl orthosilicate：Distilled water=1：1-1000：1-100：1-100；
（3）It is proportionally added into strawberry shape complex microsphere, solvent, silane coupler in reactor, at the bar of 25 DEG C-100 DEG C
Under part, react 10-15h, product is centrifuged, obtains strawberry shape hybrid microballoon；Quality is than strawberry shape complex microsphere：
Solvent：Silane coupler=1：10-100：0.1-10.
2. strawberry shape hybrid microballoon as claimed in claim 1, is characterized by polystyrene microsphere in described step
Including the crosslinked polystyrene microsphere that linear polystyrene microballoon or the degree of cross linking are 1%-80%, particle size range is 200nm-20 μm.
3. strawberry shape hybrid microballoon as claimed in claim 1, is characterized by described step（3）In solvent be
In toluene, dimethylbenzene, hexane, petroleum ether, ether, ethanol, methyl alcohol, acetone, ethyl acetate, methyl acetate and isopropyl formate
One or more.
4. strawberry shape hybrid microballoon as claimed in claim 1, is characterized by described step（3）In silane even
Connection agent is perfluoro capryl trimethoxy silane, perfluoro capryl triethoxysilane, perfluoro decyl trimethoxy silane, cetyl
Trimethoxy silane, octadecyl trimethoxysilane, perfluoro decyl triethoxysilane, trifluoro propane trimethoxy silane,
HMDS or octamethylcy-clotetrasiloxane.
5. the application process of strawberry shape hybrid microballoon as claimed in claim 1, is characterized by include following step
Suddenly：
Described strawberry shape hybrid microballoon is joined in dispersion solvent, obtain dispersion liquid；Using adhesive the end of as
Coated coating is overlying on substrate material surface, uses spraying process that dispersion liquid is coated on the bottom of solidification as external coating after solidification again
On coating, treating to disperse solvent volatilization in external coating completely, spraying a spraying solvent on external coating again, solvent to be sprayed is waved
After distributing entirely, i.e. constitute super-hydrophobic coat.
6. the application process of strawberry shape hybrid microballoon as claimed in claim 5, is characterized by described material matter
Amount ratio is strawberry shape organic/inorganic microballoon：Dispersion solvent=1：10-1000.
7. the application process of strawberry shape hybrid microballoon as claimed in claim 5, is characterized by that described dispersion is molten
Agent and spraying solvent are identical or different, are toluene, dimethylbenzene, hexane, petroleum ether, ether, ethanol, methyl alcohol, acetone, acetic acid second
One or more in ester, methyl acetate and isopropyl formate.
8. the application process of strawberry shape hybrid microballoon as claimed in claim 5, is characterized by described matrix material
Material is timber, metal, cement, fabric, plastics or glass.
9. the application process of strawberry shape hybrid microballoon as claimed in claim 5, is characterized by that described adhesive is
Epoxy resin（EP）, neoprene（CR）, Lauxite（UF）, polyurethane（PU）, polyacrylic resin or polyvinyl alcohol
（PVA）.
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Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107083180A (en) * | 2017-05-25 | 2017-08-22 | 江南大学 | A kind of automatically cleaning reflectance coating based on strawberry type microballoon and preparation method thereof |
| CN107158753A (en) * | 2017-06-08 | 2017-09-15 | 齐鲁工业大学 | It is firm, it is durable, can volume production the effective oil/water separation in the presence of a harsh environment of fluorine graft grapheme based super hydrophobic coating |
| CN109651948A (en) * | 2018-12-12 | 2019-04-19 | 韶关市合众化工有限公司 | A kind of microsphere modified aqueous polyurethane transparent heat insulating dope of PS |
| CN109913177A (en) * | 2019-03-04 | 2019-06-21 | 河北工业大学 | Double phase-change accumulation energy automatically cleaning materials for walls and its application |
| CN110183911A (en) * | 2019-04-19 | 2019-08-30 | 量镀（上海）新材料科技股份有限公司 | A kind of the transparent hydrophobic crystal coating composition and preparation method of efficient blast |
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| CN114517056A (en) * | 2022-01-26 | 2022-05-20 | 常州大学 | Method for preparing stable super-hydrophobic material from raspberry-shaped composite particles |
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| CN115819013A (en) * | 2022-11-24 | 2023-03-21 | 杨凯 | Concrete waterproof agent, waterproof concrete and preparation method thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103627107A (en) * | 2013-12-03 | 2014-03-12 | 齐鲁工业大学 | Preparation method for polystyrene/silver/polypyrrole composite material |
| CN104098102A (en) * | 2014-08-07 | 2014-10-15 | 齐鲁工业大学 | Preparation method of hollow silicon dioxide spheres with sulfonated polystyrene microspheres as template |
| CN104448089A (en) * | 2014-11-28 | 2015-03-25 | 湖北大学 | Preparation method of strawberry-type polystyrene-silicon dioxide nanocomposite microspheres |
| CN105669922A (en) * | 2016-03-10 | 2016-06-15 | 华侨大学 | Preparation method of strawberry type polymer/silicon dioxide nano-composite particles |
-
2016
- 2016-09-27 CN CN201610857185.7A patent/CN106433406B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103627107A (en) * | 2013-12-03 | 2014-03-12 | 齐鲁工业大学 | Preparation method for polystyrene/silver/polypyrrole composite material |
| CN104098102A (en) * | 2014-08-07 | 2014-10-15 | 齐鲁工业大学 | Preparation method of hollow silicon dioxide spheres with sulfonated polystyrene microspheres as template |
| CN104448089A (en) * | 2014-11-28 | 2015-03-25 | 湖北大学 | Preparation method of strawberry-type polystyrene-silicon dioxide nanocomposite microspheres |
| CN105669922A (en) * | 2016-03-10 | 2016-06-15 | 华侨大学 | Preparation method of strawberry type polymer/silicon dioxide nano-composite particles |
Non-Patent Citations (1)
| Title |
|---|
| 范欣: ""聚合物/SiO2草莓型复合粒子的制备及其在梯度润湿性表面中的应用"", 《中国博士学位论文全文数据库 工程科技I辑》 * |
Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
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| CN107158753A (en) * | 2017-06-08 | 2017-09-15 | 齐鲁工业大学 | It is firm, it is durable, can volume production the effective oil/water separation in the presence of a harsh environment of fluorine graft grapheme based super hydrophobic coating |
| CN107158753B (en) * | 2017-06-08 | 2020-04-17 | 齐鲁工业大学 | Firm, durable and mass-producible fluorine-grafted graphene-based super-hydrophobic coating capable of effectively separating oil from water in severe environment |
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| WO2023109364A1 (en) * | 2021-12-17 | 2023-06-22 | 广东美的白色家电技术创新中心有限公司 | Non-stick coating additive, non-stick coating, and preparation method therefor and use thereof |
| CN114517056A (en) * | 2022-01-26 | 2022-05-20 | 常州大学 | Method for preparing stable super-hydrophobic material from raspberry-shaped composite particles |
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