CN113462202A - Method for improving dispersion effect of graphene in acrylic emulsion - Google Patents

Method for improving dispersion effect of graphene in acrylic emulsion Download PDF

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Publication number
CN113462202A
CN113462202A CN202110705595.0A CN202110705595A CN113462202A CN 113462202 A CN113462202 A CN 113462202A CN 202110705595 A CN202110705595 A CN 202110705595A CN 113462202 A CN113462202 A CN 113462202A
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graphene
modifier
mass
modified
powder
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CN202110705595.0A
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张�诚
许林铁
刘军磊
罗俊涛
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Zhejiang University of Technology ZJUT
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Zhejiang University of Technology ZJUT
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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
    • C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK  ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
    • C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
    • C09C1/44—Carbon
    • C09C1/46—Graphite
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK  ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
    • C09C3/00—Treatment in general of inorganic materials, other than fibrous fillers, to enhance their pigmenting or filling properties
    • C09C3/08—Treatment with low-molecular-weight non-polymer organic compounds

Abstract

The invention provides a method for improving the dispersion effect of graphene in acrylic emulsion. The method comprises the steps of adding a certain amount of modifier into powder graphene, adding a proper amount of water, uniformly stirring, performing dispersion modification for a certain time, taking out, and drying to obtain powder. The modifier is added under the condition of external mechanical force, benzene rings on the modifier molecules can form pi-pi conjugation with graphene, so that the modifier is firmly attached to the surface of the graphene, and a large number of hydrophilic groups are contained on the modifier molecules and can form acting forces such as hydrogen bonds and the like with water. The modified graphene has the characteristic of long-time stable dispersion, and has a good application prospect in acrylic resin emulsion.

Description

Method for improving dispersion effect of graphene in acrylic emulsion
(I) technical field
The invention relates to a method for improving the dispersion effect of graphene in acrylic emulsion.
(II) background of the invention
Graphene is a two-dimensional material which is formed by carbon atoms in a planar hybrid orbit into a hexagonal honeycomb structure and has the thickness of only a single carbon atom, and is one of the thinnest and hardest nano materials known in the world.
Graphene has a huge application prospect, so that a method which is high in quality, less in pollution and easy to prepare is urgently needed to be found to meet the application requirement of the currently vigorously developed graphene, the current method for producing the graphene on a large scale at home and abroad mainly adopts a chemical method and a physical method, and the graphene is easy to agglomerate due to the fact that the graphene has a large specific surface area, the dispersion effect is poor, the physical and chemical properties of the graphene are much smaller than the theoretical value, the application of the graphene in practice is limited, and further improvement is needed.
Disclosure of the invention
Aiming at the problem that the graphene is poor in dispersing effect in the process, the invention aims to provide a method for improving the dispersibility of the graphene in acrylic emulsion.
The technical scheme adopted by the invention is as follows:
a method of improving the dispersion effect of graphene in an acrylic emulsion, the method comprising:
(1) dissolving a certain amount of modifier in absolute ethyl alcohol to prepare a modified solution with the mass concentration of 0.05-8%; the modifier is one of the following or a mixture of two or more of the following: (E) -cyclooct-2-en-1-yl (4-nitrophenyl) carbonate, 2-bromobicyclo [2,2,1] heptane, potassium pentyltrichloroborate, n-butyl thiophosphoric triamide, aminotrimethylene phosphonic acid, antioxidant 702, benzyltrimethylsilane, 3' -dithiobis (propan-1-ol), tetraisopropyl methylenediphosphate, cyanomethylene tri-n-butylphosphine;
(2) adding the modified liquid into the graphene powder, adding a proper amount of water, stirring at 300-800 rpm for 3-30 min, then starting a sand mill for sanding, and finally performing spray drying to obtain the modified graphene powder with improved dispersibility in the acrylic emulsion.
In order to improve the agglomeration phenomenon of graphene, the inventor of the present application finds that the dispersion effect of graphene can be effectively improved by mixing graphene with a modifier according to a certain ratio, a certain modification dispersion means and a certain drying means after a large number of experiments and researches.
Specifically, the sanding parameters in the step (2) are as follows: the rotational speed of the sand mill is 800-1500 rpm, the mass of the zirconium coin is 2-3.5 kg, and the sand milling time is 5-30 min.
Preferably, the mass of the modifier in the modifying solution in the step (2) is 1-10% of the mass of the powder graphene.
Preferably, the mass amount of water in the step (2) is 50-80 times of the mass of the powder graphene.
Specifically, the spray drying parameters in the step (2) are as follows: the inlet temperature is 110-200 ℃, and the wind speed is 50-250 m2The peristaltic speed is 200-1000 mL/h.
Preferably, the modifier in the step (1) is an antioxidant 702.
The invention has the following beneficial effects: according to the invention, the modifier is added under the condition of external mechanical force, benzene rings on the modifier molecules can form pi-pi conjugation with graphene, so that the modifier is firmly attached to the surface of the graphene, and a large number of hydrophilic groups are contained on the modifier molecules, so that the modifier molecules can form acting forces such as hydrogen bonds with water. The modified graphene prepared by the method has the characteristic of long-time stable dispersion, and has a good application prospect in acrylic resin emulsion.
(IV) description of the drawings
FIG. 1 is a schematic flow chart of the present invention.
Fig. 2 is an SEM image of graphene of example 2(b) of comparative example 1 (a).
Fig. 3 is an infrared spectrum of graphene before (comparative example 1) and after (example 2) modification.
Fig. 4 is a photograph of graphene resin dispersions of comparative examples 1(a, c) and 2(b, d) under 40-magnification and 100-magnification optical microscopes.
Fig. 5 is a contact angle test chart of graphene of comparative example 1(a) and example 2 (b).
(V) detailed description of the preferred embodiments
The invention will be further described with reference to specific examples, but the scope of the invention is not limited thereto:
example 1:
referring to fig. 1, the process schematic diagram of the invention is as follows:
0.5g of antioxidant 702 is weighed into a 100mL small beaker, 60g of absolute ethyl alcohol is added, and the mixture is stirred and dissolved to obtain a modified solution.
Weighing 50g of graphene raw material into a mixing barrel, adding the prepared modification solution, and adding 3000g of deionized water. Starting the high-speed stirrer, rotating at 650rpm for 5 min.
Turning on and turning on the sand mill, the rotational speed of the sand mill is 1100rpm, the mass of the zirconium coin is 2.1kg, and the sand milling time is 15 min.
And (3) passing the obtained slurry through a spray dryer to obtain modified graphene powder, wherein the spray drying parameters are as follows: the inlet temperature is 140-170 ℃, and the wind speed is 60-200 m2And/h, the peristaltic speed is 300-800 mL/h, and the modified graphene with good dispersion effect and stability is obtained.
Example 2:
1.5g of antioxidant 702 is weighed into a 100mL small beaker, 60g of absolute ethyl alcohol is added, and the mixture is stirred and dissolved to obtain a modified solution.
Weighing 50g of graphene raw material into a mixing barrel, adding the prepared modification solution, and adding 3000g of deionized water. Starting the high-speed stirrer, rotating at 650rpm for 5 min.
Turning on and turning on the sand mill, the rotational speed of the sand mill is 1100rpm, the mass of the zirconium coin is 2.1kg, and the sand milling time is 15 min.
And (3) passing the obtained slurry through a spray dryer to obtain modified graphene powder, wherein the spray drying parameters are as follows: the inlet temperature is 140-170 ℃, and the wind speed is 60-200 m2And/h, the peristaltic speed is 300-800 mL/h, and the modified graphene with good dispersion effect and stability is obtained.
Example 3:
3.5g of antioxidant 702 is weighed into a 100mL small beaker, 60g of absolute ethyl alcohol is added, and the mixture is stirred and dissolved to obtain a modified solution.
Weighing 50g of graphene raw material into a mixing barrel, adding the prepared modification solution, and adding 3000g of deionized water. Starting the high-speed stirrer, rotating at 650rpm for 5 min.
Turning on and turning on the sand mill, the rotational speed of the sand mill is 1100rpm, the mass of the zirconium coin is 2.1kg, and the sand milling time is 15 min.
And (3) passing the obtained slurry through a spray dryer to obtain modified graphene powder, wherein the spray drying parameters are as follows: the inlet temperature is 140-170 ℃, and the wind speed is 60-200 m2And/h, the peristaltic speed is 300-800 mL/h, and the modified graphene with good dispersity and stability is obtained.
SEM images of the modified graphene are seen in fig. 2 and compared with the graphene before modification (comparative example 1). As can be seen, the Graphene (GR) before modification is entirely dark due to poor conductivity, while the resistivity of single-layer graphene is less than that of multi-layer graphene; many very thin wrinkles can be seen in the Modified Graphene (MGR) picture, which is an effect of stacking between single-layer graphene. Under the action of sanding, a large number of modifier molecules are adsorbed on the surface of graphene, pi-pi conjugation occurs between one end of each modifier molecule and a graphene sheet, the surface energy of the graphene is reduced, and agglomeration among the graphene is reduced, so that the modified graphene has fewer layers.
The ir spectrum of the modified graphene is shown in fig. 3, and is compared with that of the graphene before modification (comparative example 1). As can be seen, GR is 3448.9cm-1A wider absorption peak is positioned and is an O-H stretching vibration peak; at 1500cm-1And 1600cm-1The peak is the vibration peak of the skeleton of the benzene ring, 1797.2cm-1The peak at (a) may be a peak of the out-of-plane deformation vibration of the benzene ring. In the infrared spectrogram of MGR, 3419.3cm-1Is the stretching vibration peak of O-H, 1200.7cm-1Is the O-H bending vibration peak of carboxylic acid, 1050.1cm-1The peak of (2) is a stretching vibration absorption peak of C-O bond in carboxylic acid at 1585.7cm-1And 1595.3cm-1The peak may be a characteristic peak of benzene ring conjugation, and the modifier is successfully adsorbed to the surface of graphene.
Pictures of the modified graphene resin dispersed under 40-magnification and 100-magnification optical microscopes are shown in fig. 4 and compared with the graphene before modification (comparative example 1). As can be seen from the figure, the images of the graphene/acrylic resin films before and after modification under 40X and 100X optical microscopes, (a) and (b) are surface morphologies of the two graphene/resin films amplified by 40 times, wherein more black particles appear in (a) and the graphene in (b) is dispersed more uniformly; the particles in (c) are more pronounced at a magnification of 100 times and only a small local amount of particles in (d). Black particles in the picture are generated by agglomeration of graphene in acrylic resin matrix, and the modified graphene promotes dispersion of the modified graphene and the acrylic resin matrix due to hydrophilic functional groups attached to the surface; the modifier is attached to the surface of the graphene, so that the surface energy of the graphene is reduced, and the self-aggregation of the graphene can be effectively reduced.
Contact angle of graphene before modification fig. 5 was tested and compared with graphene before modification (comparative example 1). As can be seen from the figure, the water contact angle before graphene modification is 145 degrees, while the water contact angle after graphene modification is 112 degrees, and the contact angle is reduced by 22.7 percent. The hydrophobicity of the modified graphene is obviously reduced because the modifier is provided with more hydrophilic group functional groups, and the large pi bond on the modifier is interacted with the graphene, so that the modifier with a plurality of hydrophilic groups is attached to the surface of the graphene, and the hydrophobicity of the graphene is reduced.
Comparative example 1:
50g of graphene raw material is weighed in a mixing barrel, 60g of absolute ethyl alcohol is added, and 3000g of deionized water is added. Starting the high-speed stirrer, rotating at 650rpm for 5 min.
Turning on and turning on the sand mill, the rotational speed of the sand mill is 1100rpm, the mass of the zirconium coin is 2.1kg, and the sand milling time is 15 min.
And (3) obtaining graphene powder from the obtained graphene powder by a spray dryer, wherein the spray drying parameters are as follows: the inlet temperature is 140-170 ℃, and the wind speed is 60-200 m2And/h, and the peristaltic speed is 300-800 mL/h, so that the comparative graphene is obtained.
The graphene prepared in the above 4 examples was mixed with acrylic resin (manufacturer: kaidelberg standard: KG-12), and the fineness of the graphene in the acrylic resin was measured. The specific process is as follows: the fineness of the graphene resin is tested by a QXD type scraper fineness meter, 30g of acrylic resin is weighed, 50mg of defoaming agent and leveling agent are added while stirring, 90mg of graphene is added while stirring after 10min of stirring, and the stirring is continued for 20 min. The mixed slurry is dropped into a fineness tester for testing, and the error is reduced by repeating for multiple times.
The test was carried out according to the GB/T1724-93 specification.
The following is a comparison of the fineness of the modified graphene of examples 1 to 3 and comparative example 1 in an acrylic resin:
example 1 Example 2 Example 3 Comparative example 1
Fineness/. mu.m 65 60 75 80
Therefore, the method can effectively improve the dispersibility of the graphene in the acrylic emulsion.
In the above embodiments, any modification, equivalence, replacement improvement, etc. in the material ratio and the process manner related to the present invention should be included in the protection scope of the present invention to verify the effect of the small molecule in improving the graphene.

Claims (6)

1. A method of improving the dispersion effect of graphene in an acrylic emulsion, the method comprising:
(1) dissolving a certain amount of modifier in absolute ethyl alcohol to prepare a modified solution with the mass concentration of 0.05-8%; the modifier is one of the following or a mixture of two or more of the following: (E) -cyclooct-2-en-1-yl (4-nitrophenyl) carbonate, 2-bromobicyclo [2,2,1] heptane, potassium pentyltrichloroborate, n-butyl thiophosphoric triamide, aminotrimethylene phosphonic acid, antioxidant 702, benzyltrimethylsilane, 3' -dithiobis (propan-1-ol), tetraisopropyl methylenediphosphate, cyanomethylene tri-n-butylphosphine;
(2) adding the modified liquid into the graphene powder, adding a proper amount of water, stirring at 300-800 rpm for 3-30 min, then starting a sand mill for sanding, and finally performing spray drying to obtain the modified graphene powder with improved dispersibility in the acrylic emulsion.
2. The method of claim 1, wherein the sanding parameters of step (2) are: the rotational speed of the sand mill is 800-1500 rpm, the mass of the zirconium coin is 2-3.5 kg, and the sand milling time is 5-30 min.
3. The method according to claim 1, wherein the mass of the modifier in the modifying solution in the step (2) is 1-10% of the mass of the powder graphene.
4. The method according to claim 1, wherein the water used in the step (2) is 50-80 times the weight of the graphene powder.
5. The method of claim 1, wherein the spray drying parameters in step (2) are: the inlet temperature is 110-200 ℃, and the wind speed is 50-250 m2The peristaltic speed is 200-1000 mL/h.
6. The method of claim 1, wherein the modifier of step (1) is an antioxidant 702.
CN202110705595.0A 2021-06-24 2021-06-24 Method for improving dispersion effect of graphene in acrylic emulsion Pending CN113462202A (en)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113801539A (en) * 2021-10-12 2021-12-17 浙江鱼童新材料股份有限公司 Preparation method of graphene epoxy resin coating

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Publication number Priority date Publication date Assignee Title
CN102516829A (en) * 2011-12-09 2012-06-27 中国科学院宁波材料技术与工程研究所 Ultrasonic-assisted method for preparing polymer functionalized graphene
CN103788556A (en) * 2014-01-26 2014-05-14 中国科学院长春应用化学研究所 Graphene-based polymer composite material and preparation method thereof
CN104448074A (en) * 2014-12-09 2015-03-25 厦门凯纳石墨烯技术有限公司 Special modified graphene for polymerization of vinyl chloride
CN107880697A (en) * 2017-10-25 2018-04-06 佛山科学技术学院 A kind of graphene oxide modified aqueous acrylic acid functional paint and preparation method thereof
CN111718694A (en) * 2020-06-19 2020-09-29 宝依德精密模切(无锡)有限公司 Heat conducting fin and preparation method thereof
CN112408374A (en) * 2020-11-27 2021-02-26 浙江工业大学 Method for reducing graphene agglomeration

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102516829A (en) * 2011-12-09 2012-06-27 中国科学院宁波材料技术与工程研究所 Ultrasonic-assisted method for preparing polymer functionalized graphene
CN103788556A (en) * 2014-01-26 2014-05-14 中国科学院长春应用化学研究所 Graphene-based polymer composite material and preparation method thereof
CN104448074A (en) * 2014-12-09 2015-03-25 厦门凯纳石墨烯技术有限公司 Special modified graphene for polymerization of vinyl chloride
CN107880697A (en) * 2017-10-25 2018-04-06 佛山科学技术学院 A kind of graphene oxide modified aqueous acrylic acid functional paint and preparation method thereof
CN111718694A (en) * 2020-06-19 2020-09-29 宝依德精密模切(无锡)有限公司 Heat conducting fin and preparation method thereof
CN112408374A (en) * 2020-11-27 2021-02-26 浙江工业大学 Method for reducing graphene agglomeration

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113801539A (en) * 2021-10-12 2021-12-17 浙江鱼童新材料股份有限公司 Preparation method of graphene epoxy resin coating

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