CN109455710A - A method of the functional monomer polymeric modification graphene based on non-covalent bond - Google Patents
A method of the functional monomer polymeric modification graphene based on non-covalent bond Download PDFInfo
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Abstract
A method of the functional monomer polymeric modification graphene based on non-covalent bond, first by graphene oxide ultrasonic disperse Yu Shuizhong；It is separately added into dispersing agent, the monomer for being able to carry out free radical polymerization, persulfuric acid salt initiator again, polymerize 2-8 hours at 60-80 DEG C；It is eventually adding hydrazine hydrate, continues 2-4 hour of agitating and heating at 80-100 DEG C, is cooled to room temperature, washing to neutrality, freeze-drying obtains modified graphene.The method of the present invention does not destroy the structure of graphene, and energy consumption is low, simple process, chemical substance dosage is few, can process and generate in water.
Description
Technical field
The present invention relates to technical field of graphene, and in particular to a kind of functional monomer polymeric modification based on non-covalent bond
The method of graphene.
Background technique
Graphene (graphene) is carbon atom with SP2The monoatomic layer material that hybrid form is formed, shows distinctive
Mechanical property and magnetic properties and nanoscale.Although single-layer graphene is not easy to obtain, can be obtained from graphite more
Layer graphene, and have the advantages that single-layer graphene, in fields such as electro-catalysis, biosensor, biomaterial and drug conveyings
It has broad application prospects.
The pure carbon material of graphene, easily aggregation condensation, the surface-clinging ability of matrix is poor, bad dispersibility.It is general when in use
Will by surface chemical modification with a small amount of small organic molecule of covalent bond keyed or polymer segment, improve graphene in water
In, the dispersibility in solvent or medium.Traditional method of modifying based on covalent bond can destroy the structure of graphene, form table
Planar defect destroys its performance.
Summary of the invention
The method of the purpose of the present invention is to provide a kind of functional monomer polymeric modification graphene based on non-covalent bond,
The structure of graphene is not destroyed, and energy consumption is low, simple process, chemical substance dosage is few, can process and generate in water.
The technical solution that the present invention uses is:
A method of the functional monomer polymeric modification graphene based on non-covalent bond, comprising the following steps:
(1) by graphene oxide ultrasonic disperse Yu Shuizhong；
(2) dispersing agent, the monomer for being able to carry out free radical polymerization, persulfuric acid salt is separately added under stirring to cause
Agent polymerize 2-8 hours at 60-80 DEG C；
(3) hydrazine hydrate is added, continues 2-4 hour of agitating and heating at 80-100 DEG C, be cooled to room temperature, be washed with water to
Property, modified graphene is obtained after dry in freeze drier (pressure 40Kpa, -40 DEG C of temperature).
Further, the mass volume ratio of the graphene oxide and water is 50-100mg:40mL.
Further, the mixing speed of step (2) is 300-600r/min, and temperature is 15-30 DEG C.
Further, the dispersing agent is emulsifier or surfactant agent, is selected from stearic acid, dodecyl benzene sulfonic acid
Sodium, quaternary ammonium compound, sodium soap, lauryl sodium sulfate, sodium alkyl sulfonate, sodium alklyarylsulfonate, pull open powder, rosin soap,
One of polyether surfactant, cetab, it is critical when the concentration of dispersing agent in water is lower than 25 DEG C
Micellar concentration.
Further, the concentration of the dodecyl sodium sulfate and lauryl sodium sulfate in water is 5mmol/L, bromine
Changing the concentration of cetrimonium in water is 0.5mmol/L.
Further, the monomer is the monomer that can carry out free radical polymerization, such as acrylic compounds, esters of acrylic acid list
Body.Monomer is selected from 2-hydroxyethyl methacrylate, acrylonitrile, methyl methacrylate, glycidyl methacrylate, first
Base dimethylaminoethyl acrylate, methyl acrylate, acrylic acid, methacrylic acid, acrylamide, methacrylic acid trifluoro second
One of ester, vinylacetate, vinyl chloride, methyl styrene, styrene；The mass volume ratio of the graphene oxide and monomer is
100mg:0.1-1mL.
Further, the persulfuric acid salt initiator is potassium peroxydisulfate or ammonium persulfate, the quality of initiator and monomer
Volume ratio is 0.015-0.1g:0.3mL.
Further, the mass volume ratio of the graphene oxide and hydrazine hydrate is 100mg:10-30mL.
The beneficial effects of the present invention are:
1) the method for the present invention is based on functional monomer in surface of graphene oxide polymerization, to be attached to graphene oxide table
Film is formed on face, is obtained the graphene of polymer modification with hydrazine hydrate reduction, is improved the dispersibility of graphene.
2) micell polymerization method that the method for the present invention uses is not destroy the surface texture of graphene based on non-covalent bond,
One layer function thin polymer film of graphene surface in-situ preparation assigns graphene phase according to the various characteristics of thin polymer film
The performance answered, such as hydrophily, dispersibility, stability improve dispersibility, the stability of graphene.
3) the method for the present invention energy consumption is low, simple process, chemical substance dosage is few, can process and generate in water, has
Wide application prospect.
Detailed description of the invention
Fig. 1 is the modified method flow schematic diagram of the graphene surface based on non-covalent bond.
Fig. 2 be the graphene surface based on non-covalent bond before modified after transmission electron microscope photo (TEM), (a. stone
Black alkene, b and c polymer modification graphene) (scale -500nm).
Fig. 3 be the graphene surface based on non-covalent bond before modified after Raman spectrum (Raman).
Fig. 4 be the graphene surface based on non-covalent bond before modified after thermogravimetric curve (TGA).
Fig. 5 is that the modified contact angle with water of the graphene surface of graphene and each embodiment based on non-covalent bond becomes
Change, (a. graphene, the ester modified graphene of b. poly 2-hydroxyethyl methacrylate, the graphene of c. Polystyrene, d. are poly-
Acrylonitrile modified graphene).
Specific embodiment
Technical solution of the present invention will be clearly and completely described below.The embodiment described is only the present invention
A part of the embodiment, instead of all the embodiments.
Embodiment 1
A method of the functional monomer polymeric modification graphene based on non-covalent bond, comprising the following steps:
1) by 100mg graphene oxide ultrasonic disperse in 40mL water, 0.0144g dodecyl sulphur is added under stirring
0.3g 2-hydroxyethyl methacrylate (HEMA) monomer is added as dispersing agent in sour sodium, and ultrasound is ventilated 10 points for 30 minutes again
Clock, 0.1g potassium peroxydisulfate is as initiator, after 80 DEG C polymerize 6 hours, 15mL hydrazine hydrate is added, continues heating 2 under the conditions of 100 DEG C
Hour, it is cooled to room temperature, is washed with water to neutrality, obtained after dry in freeze drier (pressure 40Kpa, -40 DEG C of temperature)
Modified graphene.
Embodiment 2
A method of the functional monomer polymeric modification graphene based on non-covalent bond, comprising the following steps:
1) by 100mg graphene oxide ultrasonic disperse in 40mL ultrapure water, 0.0544g dodecane is added under stirring
Base sodium sulfonate is added 0.3ml acrylonitrile (AN) and is used as monomer, ultrasound is ventilated 10 minutes for 30 minutes again, 0.1g mistake as dispersing agent
Ammonium sulfate is as initiator, and after 70 DEG C polymerize 8 hours, 15mL hydrazine hydrate is added, continues heating 2 hours under the conditions of 100 DEG C, cooling
Modified stone is obtained after dry in freeze drier (pressure 40Kpa, -40 DEG C of temperature) with milli-Q water to neutrality to room temperature
Black alkene.
Embodiment 3
A method of the functional monomer polymeric modification graphene based on non-covalent bond, comprising the following steps:
1) by 100mg graphene oxide ultrasonic disperse in 40mL ultrapure water, 0.0729g bromination ten is added under stirring
Six alkyltrimethylammoniums (0.5mmol/L) are used as dispersing agent, and 0.3g styrene (St) is added and is used as monomer, ultrasound is ventilated for 30 minutes again
10 minutes, 0.1g potassium peroxydisulfate was as initiator, and after polymerizeing 6 hours under the conditions of 80 DEG C, 15mL hydrazine hydrate, 100 DEG C of conditions are added
Under continue heating 2 hours, be cooled to room temperature, with milli-Q water to neutrality, in freeze drier (pressure 40Kpa, temperature -40
DEG C) in it is dry after obtain modified graphene.
Fig. 1 is the flow chart of the above various embodiments preparation method.
Fig. 2 be before modified after transmission electron microscope photo, Cong Tuzhong will become apparent from modified post-polymerization object film attachment
On graphene sheet layer.
Fig. 3 be before modified after Raman spectrum, it can be seen that Raman spectrum has almost no change after before modified, this illustrates this
The method of modifying of invention is the method for modifying based on non-covalent bond without result in the surface defect of graphene.
Fig. 4 be before modified after thermogravimetric curve (TGA), condition are as follows: graphene oxide: monomer: initiator: water=100mg:
0.3ml:0.1g:40ml, Cong Tuzhong are obtained, and polymer accounts for 40% in modified graphene complex, and graphene accounts for 60%.
Fig. 5 is that the modified contact angle with water of the graphene surface of graphene and each embodiment based on non-covalent bond becomes
Change, it can be seen that by the modification of different functionalities monomer, graphene surface has different functional groups, their water is caused to connect
The variation of feeler.After hydrophilic monomer 2-hydroxyethyl methacrylate (HEMA) polymeric modification, graphene is hydrophilic；Through benzene second
Alkene is modified, and graphene is hydrophobic；After acrylonitrile modified, hydrophilicrty is higher.
Claims (8)
1. a kind of method of the functional monomer polymeric modification graphene based on non-covalent bond, which is characterized in that including following step
It is rapid:
(1) by graphene oxide ultrasonic disperse Yu Shuizhong；
(2) dispersing agent, the monomer for being able to carry out free radical polymerization, persulfuric acid salt initiator, 60- are separately added under stirring
It polymerize 2-8 hours at 80 DEG C；
(3) hydrazine hydrate is added, continues 2-4 hour of agitating and heating at 80-100 DEG C, is cooled to room temperature, wash to neutrality, pressing
Power 40Kpa, it is dry in freeze drier under the conditions of -40 DEG C of temperature after obtain modified graphene.
2. a kind of method of the functional monomer polymeric modification graphene based on non-covalent bond as described in claim 1, special
Sign is that the mass volume ratio of the graphene oxide and water is 50-100mg:40mL.
3. a kind of method of the functional monomer polymeric modification graphene based on non-covalent bond as described in claim 1, special
Sign is that the mixing speed of step (2) is 300-600r/min, and temperature is 15-30 DEG C.
4. a kind of method of the functional monomer polymeric modification graphene based on non-covalent bond as described in claim 1, special
Sign is, the dispersing agent is emulsifier or surfactant agent, is selected from stearic acid, neopelex, quaternized
Object, sodium soap, lauryl sodium sulfate, sodium alkyl sulfonate, sodium alklyarylsulfonate, pull open powder, rosin soap, polyether-type surface
One of activating agent, cetab, the critical micelle concentration when concentration of dispersing agent in water is lower than 25 DEG C.
5. a kind of method of the functional monomer polymeric modification graphene based on non-covalent bond as claimed in claim 4, special
Sign is that the concentration of the dodecyl sodium sulfate and lauryl sodium sulfate in water is 5mmol/L, hexadecyl
The concentration of trimethylammonium in water is 0.5mmol/L.
6. a kind of method of the functional monomer polymeric modification graphene based on non-covalent bond as described in claim 1, special
Sign is that the monomer is selected from 2-hydroxyethyl methacrylate, acrylonitrile, methyl methacrylate, Glycidyl methacrylate
Glyceride, dimethylaminoethyl methacrylate, methyl acrylate, acrylic acid, methacrylic acid, acrylamide, metering system
One of sour trifluoro ethyl ester, vinylacetate, vinyl chloride, methyl styrene, styrene；The quality of the graphene oxide and monomer
Volume ratio is 100mg:0.1-1mL.
7. a kind of method of the functional monomer polymeric modification graphene based on non-covalent bond as described in claim 1, special
Sign is, the persulfuric acid salt initiator is potassium peroxydisulfate or ammonium persulfate, and the mass volume ratio of initiator and monomer is
0.015-0.1g:0.3mL。
8. a kind of method of the functional monomer polymeric modification graphene based on non-covalent bond as described in claim 1, special
Sign is that the mass volume ratio of the graphene oxide and hydrazine hydrate is 100mg:10-30mL.
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| CN110395724A (en) * | 2019-08-20 | 2019-11-01 | 中国航发北京航空材料研究院 | A kind of functionalization graphene and preparation method thereof |
| CN111334149A (en) * | 2020-04-24 | 2020-06-26 | 旭科新能源股份有限公司 | Polyacrylate/graphene coating liquid, preparation method thereof, high-barrier coating and high-barrier membrane |
| CN112479193A (en) * | 2020-12-17 | 2021-03-12 | 中国科学院宁波材料技术与工程研究所 | Graphene surface charged modification method |
| CN114534600A (en) * | 2022-04-27 | 2022-05-27 | 中北大学 | Industrial continuous preparation equipment and process for graphene powder capable of being directly dispersed in organic system |
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| CN111334149A (en) * | 2020-04-24 | 2020-06-26 | 旭科新能源股份有限公司 | Polyacrylate/graphene coating liquid, preparation method thereof, high-barrier coating and high-barrier membrane |
| CN112479193A (en) * | 2020-12-17 | 2021-03-12 | 中国科学院宁波材料技术与工程研究所 | Graphene surface charged modification method |
| CN114534600A (en) * | 2022-04-27 | 2022-05-27 | 中北大学 | Industrial continuous preparation equipment and process for graphene powder capable of being directly dispersed in organic system |
| CN114534600B (en) * | 2022-04-27 | 2022-09-20 | 中北大学 | Industrial continuous preparation equipment and process for graphene powder capable of being directly dispersed in organic system |
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Application publication date: 20190312 |