CN108440717B - Graphene oxide coated poly glycidyl methacrylate microsphere composite anticorrosive coating additive and preparation method thereof - Google Patents
Graphene oxide coated poly glycidyl methacrylate microsphere composite anticorrosive coating additive and preparation method thereof Download PDFInfo
- Publication number
- CN108440717B CN108440717B CN201810213508.8A CN201810213508A CN108440717B CN 108440717 B CN108440717 B CN 108440717B CN 201810213508 A CN201810213508 A CN 201810213508A CN 108440717 B CN108440717 B CN 108440717B
- Authority
- CN
- China
- Prior art keywords
- pgma
- graphene oxide
- microsphere
- microspheres
- glycidyl methacrylate
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Images
Classifications
-
- 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
- C08F8/00—Chemical modification by after-treatment
- C08F8/30—Introducing nitrogen atoms or nitrogen-containing groups
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/02—Elements
- C08K3/04—Carbon
- C08K3/042—Graphene or derivatives, e.g. graphene oxides
-
- 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
- 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
Abstract
The invention relates to a graphene oxide coated poly glycidyl methacrylate microsphere composite anticorrosive coating additive and a preparation method thereof, which mainly comprises the steps of preparing poly glycidyl methacrylate microspheres with uniform particle size distribution and micron-sized size by a monodisperse method; the surface active agent Cetyl Trimethyl Ammonium Bromide (CTAB) is adsorbed on the surface of the microsphere, ammonium ions in the CTAB are positively charged, the long alkyl chain has lipophilicity, and the surface of the microsphere is positively charged after the CTAB is adsorbed on the surface of the PGMA microsphere; graphene Oxide (GO) has a large specific surface area, contains a large number of electronegative oxygen-containing functional groups such as epoxy groups, hydroxyl groups and carboxyl groups, can effectively adsorb cations through electrostatic adsorption, and is irregularly coated on the surface of a polymer microsphere to obtain the graphene oxide coated poly glycidyl methacrylate microsphere (PGMA @ GO) composite anticorrosive coating additive.
Description
Technical Field
The invention belongs to the field of anticorrosive coatings, and relates to a graphene oxide coated poly glycidyl methacrylate microsphere composite anticorrosive coating additive and a preparation method thereof.
Background
The corrosion and protection of materials are a very important new discipline, and the corrosion is a main reason of the failure of metal materials. The metal corrosion brings important influence to national economic life, and simultaneously threatens the safety of various engineering equipment all the time, and becomes an economic problem which is highly emphasized by various countries. The corrosion of metals consumes a large amount of resources, and causes a series of natural environmental pollution while burying a great potential safety hazard and causing great economic loss.
At present, the main methods for protecting the metal surface include development of novel corrosion-resistant materials, electrochemical protection, surface coatings and the like, wherein the surface coating technology has wide applicability and becomes the most common using method. In recent years, Graphene (Graphene) has become a common research hotspot in various fields of the scientific community. Researches show that the graphene can form a physical barrier layer between the metal surface and an active medium, and is similar to the 'maze effect' of scales, so that the graphene can block the passage of small molecules such as water, oxygen and the like, shows excellent permeability resistance, corrosion resistance, thermal stability, chemical stability and the like, and has good mechanical properties and tribological properties. Compared with graphene, the graphene oxide has more oxygen-containing organic functional groups (carboxyl, hydroxyl and epoxy) on the surface, and the oxygen-containing organic functional groups can be modified and utilized, have good compatibility with matrix resin, and can fully play the role of the graphene oxide as a reinforcing phase in a continuous phase, so that the graphene oxide is expected to become an ideal auxiliary agent for the metal anticorrosive coating material. In the field of graphene anticorrosive coatings, researchers at home and abroad make a series of researches, and Chinese patent CN105524499A obtains graphene nanoplatelets by shearing and stripping natural crystalline flake graphite through a screw extruder, and the graphene nanoplatelets are used for anticorrosive coatings and have good dispersibility and barrier property. The Chinese patent application CN105838187A is that freeze-dried graphene oxide is added into a diluent of an anticorrosive paint according to a certain mass ratio, ball milling is carried out for a period of time by using a ball mill, and finally the uniformly dispersed graphene oxide diluent is added into the anticorrosive paint according to the mass ratio to prepare the graphene oxide anticorrosive paint. Although researchers do a large number of graphene modification and dispersion experiments, the problems of dispersibility and stability of graphene in a polymer system are not well solved, and the problem of dispersibility of graphene in a coating is a main reason why graphene anticorrosive coating products cannot be produced and applied on a large scale.
Disclosure of Invention
The invention aims to solve the problem of insufficient dispersion of graphene in the existing anticorrosive coating, and provides an auxiliary agent of an anticorrosive coating prepared from graphene oxide coated poly glycidyl methacrylate microsphere and a preparation method thereof by combining the characteristics of graphene oxide and polymer microspheres.
One of the technical schemes adopted by the invention for solving the technical problems is as follows:
a preparation method of an auxiliary agent of graphene oxide coated poly glycidyl methacrylate microsphere composite anticorrosive paint comprises the following steps:
(1) adding PVP into absolute ethyl alcohol according to the amount of ionic surfactant polyvinylpyrrolidone (PVP) being 5-20 wt% of the amount of monomer Glycidyl Methacrylate (GMA), stirring until the PVP is completely dissolved, and then adding reaction monomer GMA; introducing inert gas into the reaction system, and then heating to 65-75 ℃;
(2) after the temperature in the reaction system in the step (1) is raised stably, adding AIBN which is ultrasonically dispersed and dissolved by absolute ethyl alcohol at one time according to the dosage of Azodiisobutyronitrile (AIBN) as an initiator accounting for 2.5-5 wt% of the dosage of GMA as a monomer, reacting for 12-24 h, and obtaining polymer microspheres by utilizing dispersion polymerization;
(3) centrifuging the microspheres obtained in the step (2), pouring out supernatant, performing ultrasonic dispersion and centrifugal washing by using absolute ethyl alcohol, repeating the step for at least 3 times, washing off monomers and surfactants which do not participate in the reaction in a reaction system, performing ultrasonic dispersion and washing by using distilled water, centrifuging for a plurality of times, and freeze-drying the obtained product to obtain monodisperse poly glycidyl methacrylate microspheres (PGMA microspheres) with the particle size of 1-2 mu m, wherein the relative molecular weight of the microspheres is controlled at 8000-30000.
(4) Ultrasonically dispersing the monodisperse poly glycidyl methacrylate microspheres obtained in the step (3) for 0.5-1 h by using distilled water to obtain PGMA microsphere water dispersion liquid with the solubility of 1-2 mg/mL; meanwhile, ultrasonically dispersing Graphene Oxide (GO) for 1-2 h by using distilled water to obtain GO water dispersion with the solubility of 1-2 mg/mL;
(5) adding Cetyl Trimethyl Ammonium Bromide (CTAB) serving as a surfactant into the dispersed aqueous dispersion of the polyglycidyl methacrylate microspheres in the step (4) according to 2 times of the mass of the microspheres, continuing ultrasonic dispersion to completely dissolve the CTAB to obtain a uniformly dispersed microsphere solution, and allowing the CTAB to be adsorbed on the surfaces of the PGMA microspheres as much as possible;
(6) under the ultrasonic condition, adding the graphene oxide aqueous dispersion liquid subjected to ultrasonic dispersion in the step (4) into the system obtained in the step (5), continuing to perform ultrasonic treatment for a period of time, and uniformly mixing;
(7) and (3) carrying out suction filtration and washing on the product obtained in the step (6), washing for 3-6 times by using distilled water, and then carrying out freeze drying on the obtained product to obtain the graphene oxide coated poly glycidyl methacrylate microspheres (PGMA @ GO microspheres).
In the art, "@" is commonly used to indicate a cladding, and "a @ B" indicates a composite structure with a as an inner core and B as a shell. The PGMA @ GO microsphere refers to a composite structure with PGMA as an inner core and GO as a shell layer.
The second technical scheme adopted by the invention for solving the technical problems is as follows:
the graphene oxide coated poly glycidyl methacrylate microspheres prepared by the preparation method have a structural schematic diagram shown in figure 1, and can be used as a composite anticorrosive coating additive.
The invention has the beneficial effects that:
1. the method comprises the steps of preparing Poly Glycidyl Methacrylate (PGMA) microspheres with the particle size of about 1-2 mu m and the lower relative molecular weight (8000-30000) by a monodispersion method, wherein the particle size is suitable for adsorption of graphene oxide, the PGMA microspheres are dissolved in a coating solvent to form molecular chains, and the lower relative molecular weight prevents the viscosity of the formed solution from being too high, so that convenience is brought to subsequent dispersion with a resin matrix.
2. According to the invention, Cetyl Trimethyl Ammonium Bromide (CTAB) can be well adsorbed on the surface of the Poly Glycidyl Methacrylate (PGMA) microsphere, the charges of ammonium ions of the CTAB are positive charges, and the charges of ammonium ions and graphene oxide are negative charges, and the two are subjected to electrostatic interaction to form the graphene oxide coated poly glycidyl methacrylate microsphere (PGMA @ GO).
3. The Poly Glycidyl Methacrylate (PGMA) microspheres prepared by the method can be dissolved in a series of coating solvents such as toluene and cyclohexanone, the dissolved polymer has a large number of epoxy groups, the compatibility with a resin matrix can be improved, the agglomeration of graphene oxide is improved by forming PGMA @ GO with a coating structure, and the dispersibility of the graphene oxide in the resin matrix is improved.
Drawings
Fig. 1 is a schematic structural diagram of graphene oxide coated poly glycidyl methacrylate microspheres.
FIG. 2 is a SEM image: (a) the microsphere is a Poly Glycidyl Methacrylate (PGMA) microsphere, and the (b) is a graphene oxide coated poly glycidyl methacrylate microsphere (PGMA @ GO).
FIG. 3 is a TEM image: (a) the microsphere is a Poly Glycidyl Methacrylate (PGMA) microsphere, and the (b) is a graphene oxide coated poly glycidyl methacrylate microsphere (PGMA @ GO).
Fig. 4 is an optical photograph of the graphene oxide dispersion liquid (left) after being left for a period of time and the graphene oxide-coated polyglycidyl methacrylate microsphere dispersion liquid (right) prepared in example 1.
Detailed Description
The technical solution of the present invention will be further described below by referring to the accompanying drawings.
Example 1:
(1) sequentially adding weighed 1g of polyvinylpyrrolidone (PVP), 120mL of reaction solvent absolute ethyl alcohol and a magnetic stirring bar into a 250mL three-neck flask, adding 10g of reaction monomer Glycidyl Methacrylate (GMA) when the PVP is completely dissolved, and introducing inert gas N2After half an hour, heating the reaction system to 70 ℃;
(2) after the temperature in the step (1) is stable, 0.25g of initiator Azobisisobutyronitrile (AIBN) dissolved in absolute ethyl alcohol in advance is injected into the reaction system at one time by using a 5mL injector to react for 24 hours;
(3) centrifuging the reaction solution in the step (2) on a centrifuge at 2600r/min for 5min, pouring out supernatant after centrifugation, adding absolute ethyl alcohol, ultrasonically oscillating and dispersing for 5min, after the product centrifuged to the bottom of the bottle is well dispersed again, centrifuging at the same speed and time, repeating the operation, repeatedly washing the product for at least 3 times, washing the product with distilled water under the same condition, repeating the operation for 3 times, and freeze-drying the obtained product to obtain a white powdery product, namely the polyglycidyl methacrylate microspheres;
(4) weighing 100mg of the polyglycidyl methacrylate (PGMA) microspheres in the step (3), adding 50mL of distilled water for dispersing, and performing ultrasonic dispersion for 0.5h, meanwhile, weighing 200mg of Graphene Oxide (GO), adding 100mL of distilled water for performing ultrasonic dispersion, and performing ultrasonic dispersion for 1 h;
(5) adding 200mg of Cetyl Trimethyl Ammonium Bromide (CTAB) into the ultrasonically dispersed 2mg/mL polyglycidyl methacrylate (PGMA) microsphere aqueous dispersion in the step (4), and continuing to perform ultrasonic treatment until the CTAB is completely dissolved to obtain a uniformly dispersed microsphere solution, so that the CTAB is adsorbed on the surface of the PGMA microsphere as much as possible;
(6) under the ultrasonic condition, adding the 2mg/mL graphene oxide aqueous solution subjected to ultrasonic dispersion in the step (4) into the system (5) by using a disposable dropper, and shaking the two solutions while adding to ensure that the two solutions are fully and uniformly mixed;
(7) and (3) carrying out suction filtration on the mixed reaction solution (6), washing with distilled water for 6 times, and finally freeze-drying the product to obtain the graphene oxide coated polymer microsphere (PGMA @ GO).
The polyglycidyl methacrylate microspheres (PGMA) prepared by the monodisperse method of the present invention can be seen from the SEM of fig. 2(a) and the TEM of fig. 3 (a): the microsphere has uniform particle size distribution, smooth surface and good dispersion.
By comparing fig. 2(a), fig. 3(a), fig. 2(b) and fig. 3(b), it can be seen that the graphene oxide coated poly (glycidyl methacrylate) microsphere (PGMA @ GO) prepared by the present invention has obvious wrinkles on the surface of the microsphere as if a layer of gauze covered on the microsphere after the original smooth microsphere surface is coated with graphene oxide.
Fig. 4 is an optical photograph of two dispersions of the graphene oxide dispersion and the graphene oxide-coated polyglycidyl methacrylate microsphere dispersion prepared in this example after being left for a certain period of time. It can be seen from the figure that, in two different dispersions subjected to ultrasonic dispersion, after a period of time, the graphene oxide dispersion on the left side has obvious precipitation on the bottom, while the graphene oxide coated polyglycidyl methacrylate microspheres on the right side have better dispersion and no obvious precipitation, so that the dispersibility of the modified PGMA @ GO is better than that of GO.
Example 2:
(1) sequentially adding weighed 2g of polyvinylpyrrolidone (PVP), 50mL of reaction solvent absolute ethyl alcohol and a magnetic stirrer into a 150mL three-neck flask, adding 10g of reaction monomer Glycidyl Methacrylate (GMA) when the PVP is completely dissolved, and introducing inert gas N2After half an hour, heating the reaction system to 65 ℃;
(2) after the temperature in the step (1) is stable, 0.3g of initiator Azobisisobutyronitrile (AIBN) dissolved in absolute ethyl alcohol in advance is injected into the reaction system at one time by using a 5mL injector to react for 24 hours;
(3) centrifuging the reaction solution in the step (2) on a centrifuge at 2500r/min for 5min, pouring out supernatant after centrifugation, adding absolute ethyl alcohol, ultrasonically oscillating and dispersing for 5min, centrifuging at the same speed and time after the product centrifuged to the bottom of the bottle is redispersed, repeating the operation, repeatedly washing the product for at least 3 times, washing the product with distilled water under the same condition, repeating the operation for 3 times, and freeze-drying the obtained product to obtain a white powdery product, namely the polyglycidyl methacrylate microspheres;
(4) weighing 100mg of the polyglycidyl methacrylate (PGMA) microspheres in the step (3), adding 100mL of distilled water for dispersing, and performing ultrasonic dispersion for 0.5h, meanwhile, weighing 200mg of Graphene Oxide (GO), adding 200mL of distilled water for performing ultrasonic dispersion, and performing ultrasonic dispersion for 1 h;
(5) adding 200mg of Cetyl Trimethyl Ammonium Bromide (CTAB) into the 1mg/mL aqueous dispersion of the Poly Glycidyl Methacrylate (PGMA) microspheres subjected to ultrasonic dispersion in the step (4), and continuing ultrasonic dispersion until the CTAB is completely dissolved to obtain a uniformly dispersed microsphere solution, so that the CTAB is adsorbed on the surface of the PGMA microspheres as much as possible;
(6) under the ultrasonic condition, adding the 1mg/mL graphene oxide aqueous solution subjected to ultrasonic dispersion in the step (4) into the system (5) by using a disposable dropper, and shaking the system while adding to ensure that the graphene oxide aqueous solution and the graphene oxide aqueous solution are fully and uniformly mixed;
(7) and (3) carrying out suction filtration on the mixed reaction solution (6), washing with distilled water for 6 times, and finally freeze-drying the product to obtain the graphene oxide coated polymer microsphere (PGMA @ GO).
Example 3:
(1) sequentially adding weighed 0.45g of polyvinylpyrrolidone (PVP), 30mL of reaction solvent absolute ethyl alcohol and a magnetic stirring bar into a 100mL three-neck flask, adding 3g of reaction monomer Glycidyl Methacrylate (GMA) when the PVP is completely dissolved, and introducing inert gas N2After half an hour, heating the reaction system to 75 ℃;
(2) after the temperature in the step (1) is stable, 0.126g of initiator Azobisisobutyronitrile (AIBN) dissolved in absolute ethyl alcohol in advance is injected into the reaction system at one time by using a 5mL injector to react for 12 hours;
(3) centrifuging the reaction solution in the step (2) on a centrifuge at 2800r/min for 5min, pouring out supernatant after centrifugation, adding absolute ethyl alcohol, ultrasonically oscillating and dispersing for 5min, centrifuging at the same speed and time after the product centrifuged to the bottom of the bottle is redispersed, repeating the operation, repeatedly washing the product for at least 3 times, washing the product with distilled water under the same condition, repeating the operation for 3 times, and freeze-drying the obtained product to obtain a white powdery product, namely the polyglycidyl methacrylate microspheres;
(4) weighing 100mg of the polyglycidyl methacrylate (PGMA) microspheres in the step (3), adding 50mL of distilled water for dispersing, and performing ultrasonic dispersion for 0.5h, meanwhile, weighing 200mg of Graphene Oxide (GO), adding 200mL of distilled water for performing ultrasonic dispersion, and performing ultrasonic dispersion for 1 h;
(5) adding 200mg of Cetyl Trimethyl Ammonium Bromide (CTAB) into the ultrasonically dispersed 2mg/mL polyglycidyl methacrylate (PGMA) microsphere aqueous dispersion in the step (4), and continuing to perform ultrasonic treatment until the CTAB is completely dissolved to obtain a uniformly dispersed microsphere solution, so that the CTAB is adsorbed on the surface of the PGMA microsphere as much as possible;
(6) under the ultrasonic condition, adding the 1mg/mL graphene oxide aqueous solution subjected to ultrasonic dispersion in the step (4) into the system (5) by using a disposable dropper, and shaking the system while adding to ensure that the graphene oxide aqueous solution and the graphene oxide aqueous solution are fully and uniformly mixed;
(7) and (3) carrying out suction filtration on the mixed reaction liquid (6), washing the reaction liquid for multiple times by using distilled water, and finally freeze-drying the product to obtain the graphene oxide coated polymer microsphere (PGMA @ GO).
Example 4:
(1) sequentially adding weighed 0.5g of polyvinylpyrrolidone (PVP), 50mL of reaction solvent absolute ethyl alcohol and a magnetic stirring bar into a 150mL three-neck flask, adding 10g of reaction monomer Glycidyl Methacrylate (GMA) when the PVP is completely dissolved, and introducing inert gas N2After half an hour, heating the reaction system to 70 ℃;
(2) after the temperature in the step (1) is stable, 0.5g of initiator Azobisisobutyronitrile (AIBN) dissolved in absolute ethyl alcohol in advance is injected into the reaction system at one time by a 5mL injector to react for 18 h;
(3) centrifuging the reaction solution in the step (2) on a centrifuge at 2700r/min for 5min, pouring out supernatant after centrifugation, adding absolute ethyl alcohol, ultrasonically oscillating and dispersing for 5min, centrifuging at the same speed and time after the product centrifuged to the bottom of the bottle is redispersed, repeating the operation, repeatedly washing the product for at least 3 times, washing the product with distilled water under the same condition, repeating the operation for 3 times, and freeze-drying the obtained product to obtain a white powdery product, namely the polyglycidyl methacrylate microspheres;
(4) weighing 150mg of the polyglycidyl methacrylate (PGMA) microspheres in the step (3), adding 100mL of distilled water for dispersing, and performing ultrasonic dispersion for 1h, meanwhile, weighing 300mg of Graphene Oxide (GO), adding 200mL of distilled water for performing ultrasonic dispersion, and performing ultrasonic dispersion for 2 h;
(5) adding 300mg of Cetyl Trimethyl Ammonium Bromide (CTAB) into the ultrasonically dispersed 1.5mg/mL polyglycidyl methacrylate (PGMA) microsphere aqueous dispersion in the step (4), and continuing to perform ultrasonic treatment until the CTAB is completely dissolved to obtain a uniformly dispersed microsphere solution, so that the CTAB is adsorbed on the surface of the PGMA microsphere as much as possible;
(6) under the ultrasonic condition, adding the 1.5mg/mL graphene oxide aqueous solution subjected to ultrasonic dispersion in the step (4) into the system (5) by using a disposable dropper, and shaking the two solutions while adding to ensure that the two solutions are fully mixed;
(7) and (3) carrying out suction filtration on the mixed reaction solution (6), washing with distilled water for 6 times, and finally freeze-drying the product to obtain the graphene oxide coated polymer microsphere (PGMA @ GO).
The above description is only a preferred embodiment of the present invention, and therefore should not be taken as limiting the scope of the invention, which is defined by the appended claims and their equivalents.
Claims (8)
1. A preparation method of graphene oxide coated poly glycidyl methacrylate microsphere composite anticorrosive paint auxiliary agent is characterized by comprising the following steps: the method comprises the following steps:
1) adding PVP into absolute ethyl alcohol according to the amount of 5-20 wt% of the PVP, and adding GMA after the PVP is dissolved; introducing inert gas into the reaction system, and then heating to 65-75 ℃;
2) after the temperature in the step 1) is stable, adding AIBN dissolved in absolute ethyl alcohol into a reaction system according to the dosage of AIBN accounting for 2.5-5 wt% of the dosage of GMA, and reacting for 12-24 h;
3) carrying out solid-liquid separation on the product obtained in the step 2), and washing and drying a solid part to obtain PGMA microspheres; the particle size of the obtained PGMA microspheres is 1-2 mu m; the relative molecular weight of the obtained PGMA microspheres is 8000-30000;
4) ultrasonically dispersing the PGMA microspheres obtained in the step 3) for 0.5-1 h by using water to obtain 1-2 mg/mL PGMA microsphere aqueous dispersion; ultrasonically dispersing GO for 1-2 h by using water to obtain 1-2 mg/mL GO water dispersion;
5) adding CTAB into the PGMA microsphere aqueous dispersion obtained in the step 4) according to 1-3 times of the mass of the PGMA microspheres, and continuing ultrasonic treatment to dissolve the CTAB;
6) under ultrasonic waves, adding the GO water dispersion obtained in the step 4) into the system in the step 5), and continuing ultrasonic treatment to uniformly mix;
7) and (3) carrying out solid-liquid separation on the product obtained in the step 6), washing and drying a solid part to obtain the graphene oxide coated poly glycidyl methacrylate microspheres.
2. The method of claim 1, wherein: in the step 3), the monodisperse PGMA microspheres are obtained.
3. The method of claim 1, wherein: in the step 3), the solid-liquid separation method is centrifugation.
4. The method of claim 1, wherein: in the step 3), the washing method comprises the steps of ultrasonic dispersion washing by adopting absolute ethyl alcohol and centrifuging for a plurality of times, and then ultrasonic dispersion washing by using distilled water and centrifuging for a plurality of times.
5. The method of claim 1, wherein: in the step 7), the solid-liquid separation method is suction filtration.
6. The method of claim 1, wherein: in the step 7), the washing method is to wash with distilled water for several times.
7. The method of claim 1, wherein: in the step 3) and the step 7), the drying method is freeze drying.
8. The graphene oxide coated poly glycidyl methacrylate microsphere composite anticorrosive coating auxiliary agent prepared by the preparation method according to any one of claims 1 to 7.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810213508.8A CN108440717B (en) | 2018-03-15 | 2018-03-15 | Graphene oxide coated poly glycidyl methacrylate microsphere composite anticorrosive coating additive and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810213508.8A CN108440717B (en) | 2018-03-15 | 2018-03-15 | Graphene oxide coated poly glycidyl methacrylate microsphere composite anticorrosive coating additive and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN108440717A CN108440717A (en) | 2018-08-24 |
| CN108440717B true CN108440717B (en) | 2020-04-03 |
Family
ID=63195387
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201810213508.8A Active CN108440717B (en) | 2018-03-15 | 2018-03-15 | Graphene oxide coated poly glycidyl methacrylate microsphere composite anticorrosive coating additive and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN108440717B (en) |
Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109749500B (en) * | 2018-12-29 | 2020-05-12 | 厦门大学 | Graphene/azobenzene polymer composite anticorrosive paint additive and preparation method thereof |
| CN109942732B (en) * | 2019-04-09 | 2021-04-20 | 东莞市道睿石墨烯研究院 | Polymethyl methacrylate and graphene oxide composite material and preparation method thereof |
| CN111978771B (en) * | 2019-05-21 | 2022-03-01 | 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 |
| 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 |
| CN111393942B (en) * | 2020-04-29 | 2022-05-10 | 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 |
| CN114307670B (en) * | 2021-12-01 | 2024-03-15 | 苏州科技大学 | PGMA copolymer microsphere blend combined polyethyleneimine coating grafted modified polymer film and preparation method thereof |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20130129588A (en) * | 2012-05-21 | 2013-11-29 | (주)고딘테크 | Method for producing graphene-copolymer nanocomposite |
| CN105062299A (en) * | 2015-07-15 | 2015-11-18 | 延平区鑫东来新型导电材料加工厂 | Modified graphene conductive coating and preparation method thereof |
| WO2015182829A1 (en) * | 2014-05-26 | 2015-12-03 | 울산대학교 산학협력단 | Graphene-polymer composite and method for preparing same |
| CN105462336A (en) * | 2015-11-25 | 2016-04-06 | 厦门大学 | Preparation method of nanopolyaniline-containing compound anti-corrosion coating auxiliary agent |
| CN107556797A (en) * | 2017-10-13 | 2018-01-09 | 厦门大学 | A kind of preparation method of grapheme/polyaniline composite material anticorrosive paint auxiliary agent |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US8975326B2 (en) * | 2010-03-15 | 2015-03-10 | Lei Zhai | Carbon nanotube or graphene-based aerogels |
-
2018
- 2018-03-15 CN CN201810213508.8A patent/CN108440717B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20130129588A (en) * | 2012-05-21 | 2013-11-29 | (주)고딘테크 | Method for producing graphene-copolymer nanocomposite |
| WO2015182829A1 (en) * | 2014-05-26 | 2015-12-03 | 울산대학교 산학협력단 | Graphene-polymer composite and method for preparing same |
| CN105062299A (en) * | 2015-07-15 | 2015-11-18 | 延平区鑫东来新型导电材料加工厂 | Modified graphene conductive coating and preparation method thereof |
| CN105462336A (en) * | 2015-11-25 | 2016-04-06 | 厦门大学 | Preparation method of nanopolyaniline-containing compound anti-corrosion coating auxiliary agent |
| CN107556797A (en) * | 2017-10-13 | 2018-01-09 | 厦门大学 | A kind of preparation method of grapheme/polyaniline composite material anticorrosive paint auxiliary agent |
Non-Patent Citations (3)
| Title |
|---|
| Graphene oxide porous paper from amine-functionalized poly(glycidyl methacrylate)/graphene oxide core-shell microspheres;Oh, Joonsuk，等;《Journal of materials chemistry》;20101231;第9200-9204页 * |
| 甲基丙烯酸缩水甘油酯功能化石墨烯的;斳飞;《高等学校化学学报》;20150910;第36卷(第09期);第1713-1718页 * |
| 石墨烯的制备与功能化及其在复合材料中的应用研究;范金辰;《中国博士学位论文全文数据库》;20141215(第12期);B015-20页 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN108440717A (en) | 2018-08-24 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN108440717B (en) | Graphene oxide coated poly glycidyl methacrylate microsphere composite anticorrosive coating additive and preparation method thereof | |
| Qi et al. | Preparation of acrylate polymer/silica nanocomposite particles with high silica encapsulation efficiency via miniemulsion polymerization | |
| CN101250313B (en) | Nano-particle compound and preparation method thereof | |
| CN105462336B (en) | A kind of preparation method of the composite anticorrosion coating auxiliary agent containing nano polyaniline | |
| CN100478388C (en) | Method for preparing conductive, high molecular compound particles of polystyrene / polyaniline | |
| CN100484985C (en) | Conductive polyanion/starch shell-core type composite microsphere and its preparation method | |
| CN101220187A (en) | Magnetic composite microsphere with nucleocapsid structure and method for producing the same | |
| CN1718619A (en) | Magnetic composite microglobule possessing inorganic/organic core shell structure and its preparation method | |
| CN100398614C (en) | Solvent-free inorganic nano particle fluid and preparation method thereof | |
| CN102659990A (en) | Method for preparing stable-dispersibility pigment/polymer core-shell structure composite granules by using by polymer-wrapped pigment particles | |
| CN105131309A (en) | Polymer/synthetic Laponite composite colloid dispersing agent and preparation method thereof | |
| CN104277171A (en) | Preparation method of nano calcium carbonate modified styrene-acrylic emulsion | |
| CN1307262C (en) | Nano high-molecular microsphere with conductivity and magnetism and its preparation method | |
| CN111992151A (en) | preparation method of pH stimulation responsive slow-release hybrid microspheres | |
| CN114539855A (en) | Preparation method of super-amphiphobic coating with stable sea-island structure | |
| Ono et al. | Preparation and properties of polymethyl methacrylate latex dispersions having no surfactant | |
| CN110511602A (en) | A kind of composite material, water-based anticorrosive paint and preparation method thereof | |
| CN101353395B (en) | Functional red microsphere and preparation thereof | |
| CN103396505A (en) | Preparation method of pure cationic nanosphere | |
| CN101161697B (en) | Method for preparing grafted nano titanium oxide functional particles | |
| CN111187375B (en) | Method for synthesizing cationic polystyrene microspheres by dispersion polymerization | |
| Hwang et al. | Porous microspheres of polyaniline, poly (o-toluidine), and poly (m-toluidine) prepared from double emulsions stabilized by toluidine isomers as the single surfactant | |
| CN100567345C (en) | A kind of method of preparing polymer nano micelle by water solution polymerization self-emulsification | |
| CN100500700C (en) | Method for preparing grain size monodispersed core-shell structural conductive polymer microspheres | |
| Ji et al. | Revisit to the self-assembled hybrid acrylate/silica core-shell structured particles in the presence of unmodified silica particles |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |