CN108440717A - A kind of graphene oxide cladding poly (glycidyl methacrylate) microballoon composite anticorrosion coating auxiliary agent and preparation method thereof - Google Patents
A kind of graphene oxide cladding poly (glycidyl methacrylate) microballoon composite anticorrosion coating auxiliary agent and preparation method thereof Download PDFInfo
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- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
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Abstract
The present invention relates to a kind of graphene oxides to coat poly (glycidyl methacrylate) microballoon composite anticorrosion coating auxiliary agent and preparation method thereof, is mainly prepared that particle diameter distribution is uniform, poly (glycidyl methacrylate) microballoon of micron order size by monodisperse method；It is adsorbed on microsphere surface using surfactant cetyl trimethylammonium bromide (CTAB), the ammonium ion in CTAB is positively charged, and long alkyl chain has lipophile, so that microsphere surface is positively charged after CTAB is adsorbed in PGMA microsphere surfaces；Graphene oxide (GO) has huge specific surface area, and contain the oxygen-containing functional group of a large amount of such as epoxy groups, hydroxyl and carboxyl electronegativity, it can effectively Liquidity limit by Electrostatic Absorption, graphene oxide is irregularly coated on to the surface of polymer microballoon, obtains a kind of graphene oxide cladding poly (glycidyl methacrylate) microballoon (PGMA@GO) composite anticorrosion coating auxiliary agent.
Description
Technical field
The invention belongs to anticorrosive paint fields, and it is micro- to be related to a kind of graphene oxide cladding poly (glycidyl methacrylate)
Ball composite anticorrosion coating auxiliary agent and preparation method thereof.
Background technology
The corrosion and protection of material is a very important new discipline, and corrosion is the main original of metal material failure
Cause.Metal erosion brings great influence to national economy life, at the same also the moment threaten the safety of all kinds of engineering equipments, gradually at
The economic problems paid much attention to for various countries.Corrosion of metal can consume a large amount of resource, burying major safety risks and causing
While heavy economic losses, a series of pollution of natural environments is also led to.
The main method protected at present metal surface has Development of Novel corrosion resistant material, electrochemical protection and surface to apply
Layer etc., wherein surface-coating technology applicability is wide, becomes most common application method.In recent years, graphene (Graphene) at
For the common research hotspot in each field of scientific circles.Some researches show that graphenes to be formed between metal surface and active medium
Physical barriers, " the labyrinth effect " for being similar to scale are shown excellent to obstruct passing through for the small molecules such as water and oxygen
Permeability resistance, corrosion resistance, thermal stability and chemical stability etc., while the good mechanical performance and tribology having
Energy.For graphene oxide compared with graphene, surface can be modified oxygen-containing organo-functional group (carboxyl, the hydroxyl utilized with more
Base, epoxy group), these oxygen-containing organo-functional groups can have good compatibility between matrix resin, can give full play to oxygen
Effect of the graphite alkene as reinforced phase in continuous phase, therefore graphene is expected to become a kind of ideal anti-corrosive metal coating material
Expect auxiliary agent.In graphene anticorrosive paint field, domestic and international researcher has been a series of research, Chinese patent CN105524499A
Natural flake graphite shearing stripping is obtained into graphene microchip by screw extruder, anticorrosive paint is used for, there is good point
Dissipate property and barrier property.Chinese patent application CN105838187A is that the graphene oxide of freeze-drying is added to anti-corrosion by certain mass ratio
In the diluent of coating, ball mill ball milling is used in combination for a period of time, finely dispersed graphene oxide diluent is finally pressed into quality
Than being added in anticorrosive paint, it is prepared into graphene oxide anticorrosive paint.Although researchers have done a large amount of graphene and have been modified
Dispersion experiment, but dispersibility of the graphene in polymeric system, stability problem are not solved very well yet, and graphene is applying
Dispersion problem is the main reason for graphene anticorrosive paint product can not be mass produced and be applied so far in material.
Invention content
Present invention seek to address that the deficiency that existing graphene disperses in anticorrosive paint, in conjunction with graphene oxide and polymer
The characteristics of microballoon, provide a kind of graphene oxide cladding poly (glycidyl methacrylate) microballoon composite anticorrosion coating auxiliary agent and
Preparation method, the anticorrosive paint auxiliary agent are provided simultaneously with rust inhibition and physical barrier performance.
One of the technical solution adopted by the present invention to solve the technical problems is：
A kind of preparation side of graphene oxide cladding poly (glycidyl methacrylate) microballoon composite anticorrosion coating auxiliary agent
Method includes the following steps：
(1) it is that monomer methacrylic acid shrink is sweet to press ionic surfactant polyvinylpyrrolidone (PVP) dosage
5~the 20wt% of grease (GMA) dosage is counted, and PVP is added in absolute ethyl alcohol, and stirring to PVP is completely dissolved, and reaction is added later
Monomer GMA；Reaction system is passed through inert gas, then heats to 65~75 DEG C；
(2) it is monomer by initiator azodiisobutyronitrile (AIBN) dosage after heating up and stablizing in step (1) reaction system
2.5~5wt% of GMA dosages is counted, and is added at one time the AIBN dissolved with absolute ethyl alcohol ultrasonic disperse, and reaction 12~for 24 hours, it is sharp
Polymer microballoon is obtained with dispersin polymerization；
(3) microballoon obtained in step (2) is centrifuged, removes supernatant, then centrifuged with absolute ethyl alcohol ultrasonic disperse
Washing, at least repeatedly abovementioned steps 3 times wash away the monomer and surfactant for having neither part nor lot in reaction in reaction system, then use
The washing of distilled water ultrasonic disperse, centrifugation several times, then by resulting product are freeze-dried, you can it is 1~2 μm to obtain grain size
Monodisperse poly (glycidyl methacrylate) microballoon (PGMA microballoons), relative molecular weight control 8000~30000.
(4) the monodisperse poly (glycidyl methacrylate) microballoon distilled water ultrasonic disperse that will be obtained in step (3)
0.5~1h, it is 1mg/mL~2mg/mL PGMA aqueous microsphere dispersion liquids to obtain solubility；Simultaneously by graphene oxide (GO) distillation
Water 1~2h of ultrasonic disperse, it is 1mg/mL~2mg/mL GO aqueous dispersions to obtain solubility；
(5) scattered poly (glycidyl methacrylate) aqueous microsphere dispersion liquid in step (4) is waited for, by microspheres quality
2 times are added surfactant cetyl trimethylammonium bromide (CTAB), are further continued for ultrasonic disperse, CTAB is made to be completely dissolved, obtain
To evenly dispersed microspheres solution, and CTAB is allowed all to be adsorbed on the surfaces of PGMA microballoons as possible；
(6) under ultrasound condition, the good graphene oxide aqueous dispersions of step (4) ultrasonic disperse are added to the step of reaction
Suddenly in (5) system, continue ultrasound a period of time, be uniformly mixed；
(7) product in step (6) is subjected to filtering and washing, washing 3~6 times is carried out with distilled water, later by gained
Product is freeze-dried, you can obtaining graphene oxide cladding poly (glycidyl methacrylate) microballoon, (PGMA@GO are micro-
Ball).
In this field, commonly uses "@" and indicate that cladding, " A@B " are indicated using A as kernel, using B as the composite construction of shell.This hair
Bright " PGMA@GO microballoons " refers to using PGMA as kernel, using GO as the composite construction of shell.
The technical solution adopted by the present invention to solve the technical problems second is that：
Graphene oxide prepared by above-mentioned preparation method coats poly (glycidyl methacrylate) microballoon, knot
Structure schematic diagram is as shown in Figure 1, can be used as composite anticorrosion coating auxiliary agent.
The beneficial effects of the invention are as follows：
1, the present invention by monodisperse method be prepared grain size be about 1~2 μm and relatively low relative molecular weight (8000~
30000) poly (glycidyl methacrylate) (PGMA) microballoon, particle size are suitble to the absorption of graphene oxide, with
PGMA microballoons dissolve in paint solvent afterwards forms strand, and relatively low relative molecular weight so that form solution viscosity was unlikely to
Greatly, it also offers convenience for the dispersion subsequently with resin matrix.
2, the present invention can be particularly well adsorbed in polymethylacrylic acid contracting using cetyl trimethylammonium bromide (CTAB)
Water glyceride (PGMA) microsphere surface, and CTAB ammonium ion institute it is electrically charged be positive charge, with graphene oxide institute it is electrically charged
For negative electrical charge, the two forms graphene oxide by electrostatic interaction and coats poly (glycidyl methacrylate) microballoon (PGMA@
GO)。
3, poly (glycidyl methacrylate) (PGMA) microballoon prepared in the present invention can be dissolved in toluene, cyclohexanone
Etc. in a series of paint solvents, the polymer of dissolving carries a large amount of epoxy group, can improve the compatibility with resin matrix, leads to
The PGMA@GO to form clad structure are crossed, the reunion of graphene oxide is improved, improves graphene oxide in resin matrix
Dispersibility.
Description of the drawings
Fig. 1 is the structural schematic diagram that graphene oxide coats poly (glycidyl methacrylate) microballoon.
Fig. 2 schemes for SEM：(a) it is poly (glycidyl methacrylate) (PGMA) microballoon, is (b) that graphene oxide coats
Poly (glycidyl methacrylate) microballoon (PGMA@GO).
Fig. 3 schemes for TEM：(a) it is poly (glycidyl methacrylate) (PGMA) microballoon, is (b) that graphene oxide coats
Poly (glycidyl methacrylate) microballoon (PGMA@GO).
Fig. 4 is that graphene oxide dispersion (left side) is coated with graphene oxide prepared by embodiment 1 after placing a period of time
The optical photograph of poly (glycidyl methacrylate) microballoon dispersion liquid (right side).
Specific implementation mode
Technical scheme of the present invention is further detailed below by specific implementation combination attached drawing.
Embodiment 1：
(1) load weighted 1g polyvinylpyrrolidone (PVP) is sequentially added in the three-necked flask of 250mL, 120mL is anti-
It answers solvent absolute ethyl alcohol, magnetic stir bar to wait for that PVP is completely dissolved, 10g reaction monomers glycidyl methacrylate is added
(GMA), it is passed through inert gas N2, after half an hour, reaction system is warming up to 70 DEG C；
(2) with 5mL syringes that the 0.25g initiators for being dissolved in absolute ethyl alcohol in advance is even after the temperature in (1) is stablized
Nitrogen bis-isobutyronitrile (AIBN) is disposably in injection reaction system, and reaction is for 24 hours；
(3) reaction solution of (2) is subjected to centrifugation 5min with 2600r/min on centrifuge, removes supernatant after centrifugation, adds
Enter absolute ethyl alcohol ultrasonic vibration dispersion 5min, wait for centrifugation to bottom of bottle product it is again scattered, at a same speed with the time into
Row centrifugation, repeats aforementioned operation, repeatedly washed product, at least 3 times, then carry out washed product with distilled water with same condition,
It is equally repeated 3 times, obtained product is lyophilized, and the product of white powder, i.e. poly (glycidyl methacrylate) are obtained
Microballoon；
(4) weigh 100mg poly (glycidyl methacrylate)s (PGMA) microballoon in (3), be added 50mL distilled water into
Row dispersion, ultrasonic disperse 0.5h, while 200mg graphene oxides (GO) are weighed, 100mL distilled water is added and carries out ultrasonic disperse,
Ultrasonic disperse 1h；
(5) good 2mg/mL poly (glycidyl methacrylate)s (PGMA) aqueous microsphere dispersion liquid of ultrasonic disperse into (4)
200mg cetyl trimethylammonium bromides (CTAB) are added, continues ultrasound and is completely dissolved to CTAB, obtain evenly dispersed microballoon
Solution allows CTAB to be all adsorbed on the surface of PGMA microballoons as possible；
(6) under ultrasound condition, with disposable dropper by the good 2mg/mL graphene oxide water solutions of ultrasonic disperse in (4)
It in (5) system of addition, is rocked when being added, the two is allowed to mix well；
(7) (6) reaction solution mixed is filtered, and be washed with distilled water 6 times, last lyophilized products, you can
The polymer microballoon (PGMA@GO) coated to graphene oxide.
The poly (glycidyl methacrylate) microballoon (PGMA) that the present invention is prepared by monodisperse method, by Fig. 2 (a)
SEM and the TEM of Fig. 3 (a) can be seen that：Microspherulite diameter distribution is uniform, and surface is smooth, well dispersed.
The poly (glycidyl methacrylate) microballoon (PGMA@GO) of graphene oxide cladding prepared by the present invention, passes through
Comparison diagram 2 (a), Fig. 3 (a) and Fig. 2 (b), Fig. 3 (b) are as can be seen that the microsphere surface of otherwise smooth is coating graphene oxide
Later, there is apparent fold in microsphere surface, like one layer of tulle is covered on microballoon.
Fig. 4 is that graphene oxide dispersion and graphene oxide manufactured in the present embodiment cladding are poly- after placing a period of time
The optical photograph of glycidyl methacrylate microballoon two kinds of dispersion liquids of dispersion liquid.It can be seen from the figure that ultrasound is divided simultaneously
The different dispersion liquids of scattered two kinds, over time, become, there is apparent precipitation to the graphene oxide dispersion in left side in bottom,
And the graphene oxide cladding poly (glycidyl methacrylate) microballoon on right side also disperses relatively good, does not occur apparent
Precipitation, it is seen that the dispersibility of modified PGMA@GO is better than GO.
Embodiment 2：
(1) load weighted 2g polyvinylpyrrolidone (PVP) is sequentially added in the three-necked flask of 150mL, 50mL is anti-
It answers solvent absolute ethyl alcohol, magnetic stir bar to wait for that PVP is completely dissolved, 10g reaction monomers glycidyl methacrylate is added
(GMA), it is passed through inert gas N2, after half an hour, reaction system is warming up to 65 DEG C；
(2) with 5mL syringes that the 0.3g initiators for being dissolved in absolute ethyl alcohol in advance is even after the temperature in (1) is stablized
Nitrogen bis-isobutyronitrile (AIBN) is disposably in injection reaction system, and reaction is for 24 hours；
(3) reaction solution of (2) is subjected to centrifugation 5min with 2500r/min on centrifuge, removes supernatant after centrifugation, adds
Enter absolute ethyl alcohol ultrasonic vibration dispersion 5min, wait for centrifugation to bottom of bottle product it is again scattered, at a same speed with the time into
Row centrifugation, repeats aforementioned operation, repeatedly washed product, at least 3 times, then carry out washed product with distilled water with same condition,
It is equally repeated 3 times, obtained product is lyophilized, and the product of white powder, i.e. poly (glycidyl methacrylate) are obtained
Microballoon；
(4) weigh 100mg poly (glycidyl methacrylate)s (PGMA) microballoon in (3), be added 100mL distilled water into
Row dispersion, ultrasonic disperse 0.5h, while 200mg graphene oxides (GO) are weighed, 200mL distilled water is added and carries out ultrasonic disperse,
Ultrasonic disperse 1h；
(5) good 1mg/mL poly (glycidyl methacrylate)s (PGMA) aqueous microsphere dispersion liquid of ultrasonic disperse into (4)
200mg cetyl trimethylammonium bromides (CTAB) are added, continues ultrasound and is completely dissolved to CTAB, obtain evenly dispersed microballoon
Solution allows CTAB to be all adsorbed on the surface of PGMA microballoons as possible；
(6) under ultrasound condition, with disposable dropper by the good 1mg/mL graphene oxide water solutions of ultrasonic disperse in (4)
It in (5) system of addition, is rocked when being added, the two is allowed to mix well；
(7) (6) reaction solution mixed is filtered, and be washed with distilled water 6 times, last lyophilized products, you can
The polymer microballoon (PGMA@GO) coated to graphene oxide.
Embodiment 3：
(1) load weighted 0.45g polyvinylpyrrolidone (PVP), 30mL are sequentially added in the three-necked flask of 100mL
Reaction dissolvent absolute ethyl alcohol, magnetic stir bar wait for that PVP is completely dissolved, and 3g reaction monomers glycidyl methacrylate is added
(GMA), it is passed through inert gas N2, after half an hour, reaction system is warming up to 75 DEG C；
(2) after the temperature in (1) is stablized, the 0.126g initiators of absolute ethyl alcohol will be dissolved in advance with 5mL syringes
Azodiisobutyronitrile (AIBN) disposably in injection reaction system, reacts 12h；
(3) reaction solution of (2) is subjected to centrifugation 5min with 2800r/min on centrifuge, removes supernatant after centrifugation, adds
Enter absolute ethyl alcohol ultrasonic vibration dispersion 5min, wait for centrifugation to bottom of bottle product it is again scattered, at a same speed with the time into
Row centrifugation, repeats aforementioned operation, repeatedly washed product, at least 3 times, then carry out washed product with distilled water with same condition,
It is equally repeated 3 times, obtained product is lyophilized, and the product of white powder, i.e. poly (glycidyl methacrylate) are obtained
Microballoon；
(4) weigh 100mg poly (glycidyl methacrylate)s (PGMA) microballoon in (3), be added 50mL distilled water into
Row dispersion, ultrasonic disperse 0.5h, while 200mg graphene oxides (GO) are weighed, 200mL distilled water is added and carries out ultrasonic disperse,
Ultrasonic disperse 1h；
(5) good 2mg/mL poly (glycidyl methacrylate)s (PGMA) aqueous microsphere dispersion liquid of ultrasonic disperse into (4)
200mg cetyl trimethylammonium bromides (CTAB) are added, continues ultrasound and is completely dissolved to CTAB, obtain evenly dispersed microballoon
Solution allows CTAB to be all adsorbed on the surface of PGMA microballoons as possible；
(6) under ultrasound condition, with disposable dropper by the good 1mg/mL graphene oxide water solutions of ultrasonic disperse in (4)
It in (5) system of addition, is rocked when being added, the two is allowed to mix well；
(7) (6) reaction solution mixed is filtered, is used in combination distilled water repeatedly to wash, last lyophilized products, you can
The polymer microballoon (PGMA@GO) coated to graphene oxide.
Embodiment 4：
(1) load weighted 0.5g polyvinylpyrrolidone (PVP), 50mL are sequentially added in the three-necked flask of 150mL
Reaction dissolvent absolute ethyl alcohol, magnetic stir bar wait for that PVP is completely dissolved, and 10g reaction monomers glycidyl methacrylate is added
(GMA), it is passed through inert gas N2, after half an hour, reaction system is warming up to 70 DEG C；
(2) with 5mL syringes that the 0.5g initiators for being dissolved in absolute ethyl alcohol in advance is even after the temperature in (1) is stablized
Nitrogen bis-isobutyronitrile (AIBN) disposably in injection reaction system, reacts 18h；
(3) reaction solution of (2) is subjected to centrifugation 5min with 2700r/min on centrifuge, removes supernatant after centrifugation, adds
Enter absolute ethyl alcohol ultrasonic vibration dispersion 5min, wait for centrifugation to bottom of bottle product it is again scattered, at a same speed with the time into
Row centrifugation, repeats aforementioned operation, repeatedly washed product, at least 3 times, then carry out washed product with distilled water with same condition,
It is equally repeated 3 times, obtained product is lyophilized, and the product of white powder, i.e. poly (glycidyl methacrylate) are obtained
Microballoon；
(4) weigh 150mg poly (glycidyl methacrylate)s (PGMA) microballoon in (3), be added 100mL distilled water into
Row dispersion, ultrasonic disperse 1h, while 300mg graphene oxides (GO) are weighed, 200mL distilled water is added and carries out ultrasonic disperse, surpasses
Sound disperses 2h；
(5) into (4), good 1.5mg/mL poly (glycidyl methacrylate)s (PGMA) aqueous microsphere of ultrasonic disperse dissipates
300mg cetyl trimethylammonium bromides (CTAB) are added in liquid, continue ultrasound and are completely dissolved to CTAB, obtain evenly dispersed micro-
Ball solution allows CTAB to be all adsorbed on the surface of PGMA microballoons as possible；
(6) with disposable dropper that the good 1.5mg/mL graphene oxides of ultrasonic disperse in (4) is water-soluble under ultrasound condition
Liquid is added in (5) system, is rocked when being added, and the two is allowed to mix well；
(7) (6) reaction solution mixed is filtered, and be washed with distilled water 6 times, last lyophilized products, you can
The polymer microballoon (PGMA@GO) coated to graphene oxide.
The above, only present pre-ferred embodiments, therefore cannot limit the scope of implementation of the present invention according to this, i.e., according to
Equivalent changes and modifications made by the scope of the claims of the present invention and description all should still belong in the range of the present invention covers.
Claims (10)
1. a kind of preparation method of graphene oxide cladding poly (glycidyl methacrylate) microballoon composite anticorrosion coating auxiliary agent,
It is characterized in that：Including：
1) based on 5~20wt% that PVP dosages are GMA dosages, PVP is added in absolute ethyl alcohol, GMA is added after PVP dissolvings；
Reaction system is passed through inert gas, then heats to 65~75 DEG C；
2) after temperature in step 1) is stablized, based on 2.5~5wt% that AIBN dosages are GMA dosages, it is dissolved in absolute ethyl alcohol
In AIBN be added reaction system in, reaction 12~for 24 hours；
3) product of step 2) is separated by solid-liquid separation, solid portion washing, drying obtain PGMA microballoons；
4) the PGMA microballoon water 0.5~1h of ultrasonic disperse for obtaining step 3), the PGMA aqueous microspheres for obtaining 1~2mg/mL dissipate
Liquid；By GO water 1~2h of ultrasonic disperse, the GO aqueous dispersions of 1~2mg/mL are obtained；
5) CTAB is added by 1~3 times of PGMA microspheres qualities in the PGMA aqueous microsphere dispersion liquids obtained to step 4), continues ultrasound
Processing makes CTAB dissolve；
6) under ultrasound, the GO aqueous dispersions that step 4) obtains are added in the system of step 5), continuing to be ultrasonically treated makes mixing
Uniformly；
7) product for obtaining step 6) is separated by solid-liquid separation, solid portion washing, drying, and it is poly- to obtain the graphene oxide cladding
Glycidyl methacrylate microballoon.
2. preparation method according to claim 1, it is characterised in that：In the step 3), obtained PGMA microspherulite diameters
It is 1~2 μm.
3. preparation method according to claim 1, it is characterised in that：In the step 3), that obtain is monodisperse PGMA
Microballoon.
4. preparation method according to claim 1, it is characterised in that：In the step 3), the method for separation of solid and liquid be from
The heart.
5. preparation method according to claim 1, it is characterised in that：In the step 3), the method for washing is using nothing
The washing of water-ethanol ultrasonic disperse, centrifugation several times, are then washed with distilled water ultrasonic disperse, are centrifuged several times.
6. preparation method according to claim 1, it is characterised in that：In the step 3), the phase of obtained PGMA microballoons
It is 8000~30000 to molecular weight.
7. preparation method according to claim 1, it is characterised in that：In the step 7), the method for separation of solid and liquid is to take out
Filter.
8. preparation method according to claim 1, it is characterised in that：In the step 7), the method for washing is using steaming
Distilled water is washed several times.
9. preparation method according to claim 1, it is characterised in that：In the step 3) and step 7), dry method
For freeze-drying.
10. the graphene oxide prepared by a kind of preparation method according to any one of claim 1 to 9 coats poly- methyl
Glycidyl acrylate microballoon composite anticorrosion coating auxiliary agent.
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| CN109749500A (en) * | 2018-12-29 | 2019-05-14 | 厦门大学 | A kind of graphene/azobenzene polymer composite anticorrosion coating auxiliary agent and preparation method thereof |
| CN109942732A (en) * | 2019-04-09 | 2019-06-28 | 东莞市道睿石墨烯研究院 | A kind of polymethyl methacrylate and graphene oxide composite material and preparation method thereof |
| CN111117035A (en) * | 2019-12-30 | 2020-05-08 | 郎溪佳联新材料有限公司 | Modified polyethylene alloy plastic and preparation method thereof |
| CN111393942A (en) * | 2020-04-29 | 2020-07-10 | 美盈森集团股份有限公司 | Super-hydrophobic coating agent, transparent super-hydrophobic coating, and preparation method and application thereof |
| CN111978771A (en) * | 2019-05-21 | 2020-11-24 | 中车唐山机车车辆有限公司 | Modified graphene oxide, preparation method thereof, anticorrosive paint containing modified graphene oxide and preparation method |
| CN114307670A (en) * | 2021-12-01 | 2022-04-12 | 佛山市南海区苏科大环境研究院 | PGMA (poly (propylene glycol methacrylate)) copolymer microsphere blending and polyethyleneimine coating grafted modified polymer film and preparation method thereof |
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| US20110224376A1 (en) * | 2010-03-15 | 2011-09-15 | University Of Central Florida Research Foundation, Inc. | Carbon nanotube or graphene-based aerogels |
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| CN111393942A (en) * | 2020-04-29 | 2020-07-10 | 美盈森集团股份有限公司 | Super-hydrophobic coating agent, transparent super-hydrophobic coating, and preparation method and application thereof |
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