CN107998997A - One species raspberry shape microballoon, super-hydrophobic coat and preparation method thereof - Google Patents
One species raspberry shape microballoon, super-hydrophobic coat and preparation method thereof Download PDFInfo
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- CN107998997A CN107998997A CN201711436432.7A CN201711436432A CN107998997A CN 107998997 A CN107998997 A CN 107998997A CN 201711436432 A CN201711436432 A CN 201711436432A CN 107998997 A CN107998997 A CN 107998997A
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- B—PERFORMING OPERATIONS; TRANSPORTING
- 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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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F271/00—Macromolecular compounds obtained by polymerising monomers on to polymers of nitrogen-containing monomers as defined in group C08F26/00
- C08F271/02—Macromolecular compounds obtained by polymerising monomers on to polymers of nitrogen-containing monomers as defined in group C08F26/00 on to polymers of monomers containing heterocyclic nitrogen
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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
- C09D183/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Coating compositions based on derivatives of such polymers
- C09D183/04—Polysiloxanes
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Abstract
The invention discloses a species raspberry shape microballoon, super-hydrophobic coat and preparation method thereof, include the following steps：(1) poly (methyl methacrylate) micro-sphere is synthesized with dispersion copolymerization method；(2) above-mentioned poly (methyl methacrylate) micro-sphere is taken, the ethanol solution for adding tetraethyl orthosilicate is silica precursor, is reacted using sol-gal process, is synthesized using polymethyl methacrylate as core, and silica is the class raspberry shape microballoon of shell.Preparation method of the present invention is simple, and the class raspberry shape Microsphere Size of preparation is controllable, and super-hydrophobic coat has good chemical stability, resistance to acid and alkali and hydrophobicity, its surface contact angle is 151 °, available for glass, skin, fabric face, metal surface etc..
Description
Technical field
The present invention relates to organic/inorganic composite superhydrophobic material technical field, more particularly to a poly- methyl of species raspberry shape
The synthetic method of methyl acrylate/silicon dioxide composite material and the application in super-hydrophobic coat.
Background technology
The wetability of the surface of solids is the important performance of material, have ultra-hydrophobicity material can be applied to it is antifouling,
Optical lens is antifog, building automatically cleaning, water-oil separating etc..Surface contact angle is more than 150 ° of surface, that is, super-hydrophobic table
Face.In general preparing super hydrophobic surface needs to meet two conditions：First, material surface has low-surface energy substance modification；Second,
Material surface has micro-nano hierarchy.
At present, organic/inorganic composite material is prepared, is had a wide range of applications in super hydrophobic material field.Chinese patent
CN106749790A discloses a kind of preparation method of titanium dioxide/polystyrene core/capsomeric composite material, has fine
Hydrophobic performance.Chinese patent CN106366907A discloses a kind of by hydrophobic nanoparticles and hydrophobic silicone resin alloy
Super hydrophobic coating.Hua Junli etc. uses colloidal sol-gel method, with ethyl orthosilicate (TEOS) and methyltriethoxysilane (MTES)
It is film forming matter for presoma, organosilicon acrylic resin, is prepared for organic-inorganic hybridization super hydrophobic material.
Since present composite organic-inorganic material is simple organic and inorganic blending, the core/shell structure of preparation is answered
Condensation material is concentrated mainly on using technical field of the inorganic material as core, organic material for shell, and is prepared super-hydrophobic compound micro-
There are size to be difficult to control for grain, it is more difficult to is applied to the surfaces such as glass, yarn fabric, metal, limits composite organic-inorganic material and exist
Application in terms of super-hydrophobic coat.
The content of the invention
It is an object of the present invention to：The organic and inorganic that a kind of high molecular material is blended from submicroscopic scope is provided to answer
Condensation material, including dispersion copolymerization method synthesis single dispersing, the polymethyl methacrylate of narrow ditribution, then with polymethyl methacrylate
Microballoon has micro-nano coarse structure polymethyl methacrylate/silicon dioxide composite material, the composite material for templated synthesis
With size is controllable, good chemical stability, resistance to acid and alkali and hydrophobicity.Its technical solution is as follows：
The preparation method of one species raspberry shape microballoon, includes the following steps：
(1) poly (methyl methacrylate) micro-sphere is synthesized with dispersion copolymerization method；
(2) above-mentioned poly (methyl methacrylate) micro-sphere is taken, adds the ethanol solution of tetraethyl orthosilicate as before silica
Body is driven, is reacted, is synthesized using polymethyl methacrylate as core using sol-gal process, silica is the class raspberry shape of shell
Microballoon.
The synthesis of the poly (methyl methacrylate) micro-sphere：Polyvinylpyrrolidone is dispersed in the mixed solvent and leads to nitrogen
Deoxygenation, 40-60 DEG C of stirring 3h；Then the processed methyl methacrylate of ultrasonic disperse and azodiisobutyronitrile mixture are dripped
It is added in polyvinylpyrrolidone dispersion liquid, slowly increases the temperature to 70 DEG C, mechanical agitation, dispersin polymerization obtains polymethyl
Sour methyl ester emulsions, centrifugation, washing, drying, obtain poly (methyl methacrylate) micro-sphere.
Step (1) described poly (methyl methacrylate) micro-sphere, by weight, polymer raw includes methyl methacrylate
9~12.5 parts, 0.09~0.48 part of azodiisobutyronitrile, 3.18~4.38 parts of polyvinylpyrrolidone, mixed solvent 91-125
Part, 64~87 parts of in the mixed solvent methanol, 27~38 parts of deionized water.
By weight, 5.0~20.0 parts of the poly (methyl methacrylate) micro-sphere, tetraethyl orthosilicate are step (2)
0.001~0.6 part, 40~95 parts of ethanol.
The solvent that step (2) synthesis class raspberry shape microballoon uses adjusts solution ph to 9~12 for ethanol, using ammonium hydroxide；
Tetraethyl orthosilicate is added rapidly in ethanol, reaction time 12h.
The super-hydrophobic coat prepared using above-mentioned class raspberry shape microballoon, its preparation method are included the following steps：
(1) the class raspberry shape microballoon ethanol solution of perfluor silane is modified, the poly-methyl methacrylate of hydrophobization is made
The suspension of ester/silica；
(2) finally using dimethyl silicone polymer as filmogen, suspension obtained above is deposited on glass baseplate table
Face, is made super-hydrophobic coat.
The preparation of the super-hydrophobic coat：
PDMS is first coated in the glass substrate surface that cleaned, cold curing 10min, then by obtained uniform suspension
The PDMS surfaces of semi-solid preparation are applied to, it is cured to 24h at room temperature, that is, obtains super-hydrophobic coat.
The perfluor silane is 1H, 1H, 2H, and 2H- perfluoro capryl triethoxysilanes, perfluor silane is in ethanol solution
Concentration be 0.1~0.9g/ml.
Compared with prior art, beneficial effects of the present invention are：
(1) poly (methyl methacrylate) micro-sphere synthesized by dispersion copolymerization method, has the advantages that single dispersing, narrow ditribution
(Fig. 1,2).
(2) using tetraethyl orthosilicate as silica precursor, class raspberry shape polymethyl methacrylate/dioxy of synthesis
SiClx complex microsphere, has reached composite organic-inorganic material in submicroscopic blending (Fig. 3,4).
(3) preparation method of the present invention is simple, and the class raspberry shape Microsphere Size of preparation is controllable, and super-hydrophobic coat has good
Chemical stability, resistance to acid and alkali and hydrophobicity, its surface contact angle are 151 ° (Fig. 6), available for glass, skin, are knitted
Thing surface, metal surface etc..
Brief description of the drawings
Fig. 1 is the scanning electron microscope (SEM) photograph of poly (methyl methacrylate) micro-sphere prepared by the embodiment of the present invention 1.
Fig. 2 is the scanning electron microscope (SEM) photograph of poly (methyl methacrylate) micro-sphere prepared by the embodiment of the present invention 2.
Fig. 3 is sweeping for class raspberry shape polymethyl methacrylate/silicon dioxide complex microsphere prepared by the embodiment of the present invention 1
Retouch electron microscope.
Fig. 4 is sweeping for class raspberry shape polymethyl methacrylate/silicon dioxide complex microsphere prepared by the embodiment of the present invention 2
Retouch electron microscope.
Fig. 5 is the state diagram on the super-hydrophobic coat surface that water droplet drops in the preparation of the embodiment of the present invention 1.
Fig. 6 is the state diagram on the super-hydrophobic coat surface that water droplet drops in the preparation of the embodiment of the present invention 2.
Embodiment
The content for a better understanding of the present invention, is described further by specific embodiment now, but should not
This is interpreted as the full content of the present invention.
Embodiment 1
A. the synthesis of poly (methyl methacrylate) micro-sphere
3.5g polyvinylpyrrolidones are dispersed in methanol/water (70ml/30ml) solvent, leads to nitrogen 30min deoxygenations, adds
55 DEG C of stirring 3h of heat.9.5g methyl methacrylates and 0.1g azodiisobutyronitrile mixtures are added drop-wise to polyvinylpyrrolidone point
In dispersion liquid.Slowly increase the temperature to 70 DEG C, react 24h, centrifugation, washing, that 60 DEG C of dry 12h obtain polymethyl methacrylate is micro-
Ball.
B. the synthesis of class raspberry shape polymethyl methacrylate/silicon dioxide complex microsphere and silicic acid anhydride
The poly (methyl methacrylate) micro-sphere 7.9g of above-mentioned a synthesis is taken, adds ethanol solution (the positive silicon of tetraethyl orthosilicate
Sour tetra-ethyl ester 0.0018g, ethanol 90ml), add ammonium hydroxide and adjust pH value to 11.3, normal-temperature reaction 12h, synthesize the poly- first of class raspberry shape
Base methyl acrylate/SiO 2 composite microsphere.Meanwhile by the polymethyl methacrylate/silicon dioxide microballoon of above-mentioned synthesis
Silicic acid anhydride in the ethanol solution of 0.4g/ml perfluor silane is added to, is prepared into suspension.
C. the preparation of super-hydrophobic coat
First, PDMS (dimethyl silicone polymer of Ao Sibang companies ambient temperature curable) is coated in the glass base cleaned
Material surface, cold curing 10min, then the uniform suspension of the class raspberry shape complex microsphere of fluorination treatment is applied to semi-solid preparation
It, is cured 24h by PDMS surfaces at room temperature, that is, obtains polymethyl methacrylate/silicon dioxide super-hydrophobic coat.
Embodiment 2
A. the synthesis of poly (methyl methacrylate) micro-sphere
3.5g polyvinylpyrrolidones are dispersed in methanol/water (70ml/30ml) solvent, logical nitrogen 30min deoxygenations, 60
DEG C heating stirring 3h.10g methyl methacrylates and 0.4g azodiisobutyronitrile mixtures are added drop-wise to polyvinylpyrrolidone point
In dispersion liquid.Slowly increase the temperature to 70 DEG C, react 24h, centrifugation, washing, that 60 DEG C of dry 12h obtain polymethyl methacrylate is micro-
Ball.
B. the synthesis of class raspberry shape polymethyl methacrylate/silicon dioxide complex microsphere and silicic acid anhydride
The poly (methyl methacrylate) micro-sphere 8.5g of above-mentioned a synthesis is taken, adds ethanol solution (the positive silicon of tetraethyl orthosilicate
Sour tetra-ethyl ester 0.0018g, ethanol 90ml), add ammonium hydroxide and adjust pH value to 11.3, normal-temperature reaction 12h, synthesize the poly- first of class raspberry shape
Base methyl acrylate/SiO 2 composite microsphere.Meanwhile by the polymethyl methacrylate/silicon dioxide microballoon of above-mentioned synthesis
Silicic acid anhydride in the ethanol solution of 0.4g/ml perfluor silane is added to, is prepared into suspension.
C. the preparation of super-hydrophobic coat
First, PDMS is coated in the glass substrate surface cleaned, cold curing 10min, then the class by fluorination treatment
The uniform suspension of raspberry shape complex microsphere is applied to the PDMS surfaces of semi-solid preparation, it is cured to 24h at room temperature, that is, is gathered
Methyl methacrylate/silica super-hydrophobic coat.
Claims (10)
1. the preparation method of a species raspberry shape microballoon, it is characterised in that include the following steps：
(1) poly (methyl methacrylate) micro-sphere is synthesized with dispersion copolymerization method；
(2) above-mentioned poly (methyl methacrylate) micro-sphere is taken, the ethanol solution for adding tetraethyl orthosilicate is silica precursor,
Reacted, synthesized using polymethyl methacrylate as core using sol-gal process, silica is the class raspberry shape microballoon of shell.
2. the preparation method of class raspberry shape microballoon according to claim 1, it is characterised in that：The polymethyl methacrylate
The synthesis of microballoon：Polyvinylpyrrolidone is dispersed in the mixed solvent and leads to nitrogen deoxygenation, 40-60 DEG C of stirring 3h；Then will be super
The methyl methacrylate and azodiisobutyronitrile mixture that sound decentralized processing is crossed are added drop-wise in polyvinylpyrrolidone dispersion liquid,
70 DEG C are slowly increased the temperature to, mechanical agitation, dispersin polymerization obtains polymethyl methacrylate lotion, and centrifugation, wash, is dry,
Obtain poly (methyl methacrylate) micro-sphere.
3. the preparation method of class raspberry shape microballoon according to claim 2, it is characterised in that：Step (1) the poly- methyl-prop
E pioic acid methyl ester microballoon, by weight, polymer raw include 9~12.5 parts of methyl methacrylate, azodiisobutyronitrile 0.09
~0.48 part, 3.18~4.38 parts of polyvinylpyrrolidone, 91-125 parts of mixed solvent, 64~87 parts of in the mixed solvent methanol,
27~38 parts of deionized water.
4. the preparation method of class raspberry shape microballoon according to claim 3, it is characterised in that：Step (2) by weight, institute
State that poly (methyl methacrylate) micro-sphere is 5.0~20 parts, tetraethyl orthosilicate is 0.001~0.6 part, ethanol is 40~95 parts.
5. the preparation method of class raspberry shape microballoon according to claim 4, it is characterised in that：Step (2) synthesizes class raspberry shape
The solvent that microballoon uses adjusts solution ph to 9~12 for ethanol, using ammonium hydroxide；Tetraethyl orthosilicate is added rapidly to ethanol
In, reaction time 12h.
6. class raspberry shape microballoon prepared by Claims 1 to 5 any one method.
A kind of 7. super-hydrophobic coat prepared using class raspberry shape microballoon described in claim 6.
8. the preparation method of super-hydrophobic coat described in claim 7, it is characterised in that：Include the following steps：
(1) the class raspberry shape microballoon ethanol solution of perfluor silane is modified, polymethyl methacrylate/bis- of hydrophobization is made
The suspension of silica；
(2) finally using dimethyl silicone polymer as filmogen, suspension obtained above is deposited on glass substrate surface, is made
Obtain super-hydrophobic coat.
9. preparation method according to claim 8, it is characterised in that：The preparation of the super-hydrophobic coat：
PDMS is first coated in the glass substrate surface cleaned, cold curing 10min, then obtained uniform suspension is smeared
In the PDMS surfaces of semi-solid preparation, it is cured to 24h at room temperature, that is, obtains super-hydrophobic coat.
10. preparation method according to claim 9, it is characterised in that：The perfluor silane is 1H, 1H, 2H, and 2H- is complete
Fluorine octyltri-ethoxysilane, concentration of the perfluor silane in ethanol solution are 0.1~0.9g/ml.
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| CN201711436432.7A CN107998997B (en) | 2017-12-26 | 2017-12-26 | Raspberry-like microsphere, super-hydrophobic coating and preparation method thereof |
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| CN107998997B CN107998997B (en) | 2020-08-07 |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109836052A (en) * | 2019-03-15 | 2019-06-04 | 长春工业大学 | A kind of construction method of polymer matrix super-hydrophobic coat |
| CN112961522A (en) * | 2021-03-09 | 2021-06-15 | 四川大学 | Preparation and application method of super-hydrophobic antibacterial magnesium oxychloride powder coating |
| CN113004749A (en) * | 2019-12-20 | 2021-06-22 | 广东美的白色家电技术创新中心有限公司 | Super-hydrophobic coating and preparation method and application thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105694715A (en) * | 2016-03-28 | 2016-06-22 | 南昌航空大学 | Preparation method of SiO2/PDMS composite transparent super hydrophobic coating |
| CN106563398A (en) * | 2016-10-28 | 2017-04-19 | 佛山科学技术学院 | Preparation method of organic/inorganic composite microspheres with raspberry-like structures and application thereof |
-
2017
- 2017-12-26 CN CN201711436432.7A patent/CN107998997B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105694715A (en) * | 2016-03-28 | 2016-06-22 | 南昌航空大学 | Preparation method of SiO2/PDMS composite transparent super hydrophobic coating |
| CN106563398A (en) * | 2016-10-28 | 2017-04-19 | 佛山科学技术学院 | Preparation method of organic/inorganic composite microspheres with raspberry-like structures and application thereof |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109836052A (en) * | 2019-03-15 | 2019-06-04 | 长春工业大学 | A kind of construction method of polymer matrix super-hydrophobic coat |
| CN113004749A (en) * | 2019-12-20 | 2021-06-22 | 广东美的白色家电技术创新中心有限公司 | Super-hydrophobic coating and preparation method and application thereof |
| WO2021121422A1 (en) * | 2019-12-20 | 2021-06-24 | 广东美的白色家电技术创新中心有限公司 | Superhydrophobic coating, method for preparing same and use thereof |
| CN112961522A (en) * | 2021-03-09 | 2021-06-15 | 四川大学 | Preparation and application method of super-hydrophobic antibacterial magnesium oxychloride powder coating |
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| CN107998997B (en) | 2020-08-07 |
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