CN102040714A - Preparation method of polymer-grafted graphene - Google Patents

Preparation method of polymer-grafted graphene Download PDF

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CN102040714A
CN102040714A CN 201010530369 CN201010530369A CN102040714A CN 102040714 A CN102040714 A CN 102040714A CN 201010530369 CN201010530369 CN 201010530369 CN 201010530369 A CN201010530369 A CN 201010530369A CN 102040714 A CN102040714 A CN 102040714A
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graphene
polymer graft
acrylate
polymer
methacrylate
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CN102040714B (en
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高超
阚兰艳
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Changxin de Technology Co., Ltd.
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Zhejiang University ZJU
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Abstract

The invention discloses a method for grafting a polymer ona surface of graphene. The method comprises the following steps: adding 1 part by weight of graphene or graphene oxide, 10-1000 parts by weight of solvent and 10-1000 parts by weight of vinyl monomer, and adding 0.01-10 parts by weight of initiator under introduction of nitrogen; heating to 55-90 DEG C, and carrying out reaction for 1.5-60 hours; and precipitating, centrifugating, washing, and drying, thus obtaining a product of polymer-grafted graphene. The method is convenient and simple in process, can be used for the large-scale production, is the universal method and ensures that a variety of polymers can be grated onto the graphene. The obtained functionalized graphene has good solubility and good solution processability, is conducive and has extensive application value in micro-nano electronics, machinery, chemical industry, high-performance materials and other fields.

Description

The polymer graft preparation method of graphene
Technical field
The present invention relates to the preparation method of compound, relate in particular to a kind of polymer graft preparation method of graphene.
Background technology
Graphene (Graphene) is a kind of novel carbon material, belongs to a member of carbon family together with carbon nanotube, soccerballene.2004 by the A.K.Geim of Britain by the adhesive tape method peel off natural graphite make (K.S.Novoselov, et al.Science, 2004,306,666-669).It is found at acquisition Nobel Prize in physics in 2010.Graphene be one deck by carbon atom with sp 2The two-dimentional carbon atomic layer that hydridization is formed by connecting, its thickness has only 0.34nm, is the thinnest two-dimensional nano material of finding at present.Find that after deliberation Graphene is the present the highest material of intensity in the world, its strength ratio high-strength carbon fibre is high 20 times, and is also higher 100 times than best iron and steel.Graphene also has the speciality of multiple excellences such as great specific surface area, high thermal conductivity and carrier mobility in addition.Make it at transistor, ultracapacitor is selected the perviousness film, and numerous areas such as strongthener are with a wide range of applications.
But Graphene is difficult to dissolving or disperses in common solvent, thereby has limited the further investigation of its structure properties and industrial widespread use.Discover that chemical modification is the effective ways of preparation solubilized Graphene.As natural graphite under strong oxidizer effects such as the vitriol oil, Potassium Persulfate, Vanadium Pentoxide in FLAKES, potassium permanganate, hydrogen peroxide, through ultra-sonic dispersion, can obtain graphene oxide (V.C.Tung, et al.Nat.Nanotechnol., 2009,4,25-29).Graphene oxide can be dispersed in water and N preferably, in the strong polar organic solvent such as dinethylformamide.
In recent years, the report of more existing modified graphenes was as by trinitride and graphite oxide alkene reaction, polymer chain can be grafted to the functionalization graphene (H.K.He that the Graphene surface makes good dispersity, etal.Chem.Mater.2010,22,5054-5064); By the method that diazonium salt decomposes Graphene is carried out modification, and re-initiation atom transfer radical polymerization (ATRP) (M.Fang, et al.J.Mater.Chem., 2009,19,7098-7105), polymer chain is grafted to the Graphene surface; Utilize the in-situ polycondensation method that nylon is grafted to the Graphene surface, improved its solvability (Z.Xu et al.Macromolecules 2010,43,6716-6723) etc.But, how the common polymer chain is grafted to simply and easily and remains a challenge on the Graphene.
Summary of the invention
The objective of the invention is to overcome the deficiencies in the prior art, a kind of polymer graft preparation method of graphene is provided.
The polymer graft preparation method of graphene is: the Graphene or the graphene oxide that add 1 weight part, the solvent of 10-1000 weight part, the vinyl monomer of 10-1000 weight part, logical nitrogen add the initiator of 0.01～10 weight part down, are heated to 55～90 ℃, reaction 1.5～60h, through precipitation, centrifugal, washing, drying obtains product polymer graft Graphene.
Described vinyl monomer is: vinylbenzene, Sodium styrene sulfonate, methyl methacrylate, butyl methacrylate, hydroxyethyl methylacrylate, glycidyl methacrylate, dimethylaminoethyl methacrylate, diethylaminoethyl methacrylate, the methacrylic tert-butyl acrylate, 3-(iso-butylene acyl-oxygen) propyl trimethoxy silicane, methyl acrylate, butyl acrylate, Hydroxyethyl acrylate, glycidyl acrylate, dimethylaminoethyl acrylate, the vinylformic acid lignocaine ethyl ester, tert-butyl acrylate, acrylamide, the N-N-isopropylacrylamide, methacrylic acid, vinylformic acid, 4-vinylpridine, the 2-vinyl pyridine, 4-vinyl pyrrolidone or vinyl cyanide.
Described solvent is: water, N, dinethylformamide, N,N-dimethylacetamide, tetrahydrofuran (THF), methyl-sulphoxide, N-Methyl pyrrolidone, ethylene glycol, glycol ether, pyridine, ethyl acetate, dioxane, butanone or Virahol.
Described initiator is selected from Potassium Persulphate, ammonium persulphate, 2,2'-Azobis(2,4-dimethylvaleronitrile), Diisopropyl azodicarboxylate, dibenzoyl peroxide or S-WAT.
Content of the present invention is to be raw material with the Graphene, vinyl polymer is grafted to obtains the polymer graft Graphene on the Graphene.Can control polymer weight umber in the grafting to a certain extent by initiator proportioning and reaction times.Utilize atomic force microscope, scanning electronic microscope and transmission electron microscope that polymer graft Graphene pattern is analyzed, also adopt nucleus magnetic resonance, infrared spectra, heat analysis etc. that it is characterized.The polymer graft Graphene for preparing has fabulous solvability, can dissolve in multiple solvent; Have good electrical conductivity and film forming separately, suitable coating, power lubrication, the biological field such as lubricated of being applied to; Meanwhile this polymer graft Graphene is easy to add in the high molecular polymer matrix, thereby can do nano composite material, and prospect has a very wide range of applications.This preparation method and traditional preparation method relatively have tangible advantage, as operation is simple, repeatability high, can be mass-produced etc.
Description of drawings
Fig. 1 is the thermogravimetric curve of polymer graft Graphene, and as can be seen along with the increase in reaction times, the polymer weight in the grafting increases gradually from curve, and the successful grafting of polymkeric substance has been described, i.e. the success of polymer graft Graphene is synthetic;
Fig. 2 is the atomic force microscope photo of synthetic functionalization graphene of the present invention, visible multi-disc polymer graft graphene film among the figure, and it highly is 13nm accordingly, the height of Graphene far away, 0.6-0.8nm.
Embodiment
The polymer graft preparation method of graphene is: the Graphene or the graphene oxide that add 1 weight part, the solvent of 10-1000 weight part, the vinyl monomer of 10-1000 weight part, logical nitrogen add the initiator of 0.01～10 weight part down, are heated to 55～90 ℃, reaction 1.5～60h, through precipitation, centrifugal, washing, drying obtains product polymer graft Graphene.
Described vinyl monomer is: vinylbenzene, Sodium styrene sulfonate, methyl methacrylate, butyl methacrylate, hydroxyethyl methylacrylate, glycidyl methacrylate, dimethylaminoethyl methacrylate, diethylaminoethyl methacrylate, the methacrylic tert-butyl acrylate, 3-(iso-butylene acyl-oxygen) propyl trimethoxy silicane, methyl acrylate, butyl acrylate, Hydroxyethyl acrylate, glycidyl acrylate, dimethylaminoethyl acrylate, the vinylformic acid lignocaine ethyl ester, tert-butyl acrylate, acrylamide, the N-N-isopropylacrylamide, methacrylic acid, vinylformic acid, 4-vinylpridine, the 2-vinyl pyridine, 4-vinyl pyrrolidone or vinyl cyanide.
Described solvent is: water, N, dinethylformamide, N,N-dimethylacetamide, tetrahydrofuran (THF), methyl-sulphoxide, N-Methyl pyrrolidone, ethylene glycol, glycol ether, pyridine, ethyl acetate, dioxane, butanone or Virahol.
Described initiator is selected from Potassium Persulphate, ammonium persulphate, 2,2'-Azobis(2,4-dimethylvaleronitrile), Diisopropyl azodicarboxylate, dibenzoyl peroxide or S-WAT.
The following examples are to further specify of the present invention, rather than limit the scope of the invention.
Embodiment 1:
The graphene oxide that in reaction flask, adds 50.0mg, add 40mL N, dinethylformamide (DMF) and 7.1g glycidyl methacrylate add the 41.0mg Diisopropyl azodicarboxylate behind the stirring 30min under nitrogen protection, be heated to 65 ℃ then, reaction 48h, through precipitation, centrifugal, washing, it is 77% polymer graft Graphene that drying obtains the polymer graft amount, and its thermogravimetric curve as shown in Figure 1; Its atomic force microscope figure as shown in Figure 2, the visible monodispersed polymer graft graphene film of multi-disc.
Embodiment 2:
Adopt the reactions steps identical with embodiment 1, the reaction times is 5.5 hours, obtains the polymer graft amount and be 64% polymer graft Graphene, and its thermogravimetric curve as shown in Figure 1.
Embodiment 3:
Adopt the reactions steps identical with embodiment 1, the Diisopropyl azodicarboxylate of adding is 5mg, obtains the polymer graft amount and be 95% polymer graft Graphene.
Embodiment 4:
Adopt the reactions steps identical with embodiment 1, the 7.1g glycidyl methacrylate changes the hydroxyethyl methylacrylate of 6.5g into, obtains the polymer graft amount and be 85% polymer graft Graphene.
Embodiment 5:
Adopt the reactions steps identical with embodiment 1, the graphene oxide of 50.0mg changes the Graphene of 50.0mg into, obtains poly (glycidyl methacrylate) polymers grafted graft grapheme.
Embodiment 6:
Adopt the reactions steps identical with embodiment 1, the 7.1g glycidyl methacrylate changes the methyl methacrylate of 5.0g into, obtains polymethylmethacrylate polymers grafted graft grapheme.
Embodiment 7:
Adopt the reactions steps identical with embodiment 1, the 7.1g glycidyl methacrylate changes the methacrylic tert-butyl acrylate of 7.1g into, obtains polymethyl tert-butyl acrylate polymers grafted graft grapheme.
Embodiment 8:
Adopt the reactions steps identical with embodiment 1, the 7.1g glycidyl methacrylate changes the vinylbenzene of 5.2g into, obtains the polymer graft Graphene of polystyrene graft.
Embodiment 9:
Adopt the reactions steps identical with embodiment 1,40mLN, dinethylformamide (DMF) changes 40mL water into, and the 7.1g glycidyl methacrylate changes the Sodium styrene sulfonate of 10.3g into, obtains sodium polystyrene sulfonate polymers grafted graft grapheme.
Embodiment 10:
Adopt the reactions steps identical with embodiment 1, the 7.1g glycidyl methacrylate changes the 4-vinylpridine of 5.3g into, obtains poly 4 vinyl pyridine polymers grafted graft grapheme.
Embodiment 11:
Adopt the reactions steps identical with embodiment 1, the 7.1g glycidyl methacrylate changes the N-N-isopropylacrylamide of 5.7g into, obtains poly N-isopropyl acrylamide polymers grafted graft grapheme.
Embodiment 12:
In reaction flask, add 50.0mg graphene oxide, 0.5g N; dinethylformamide, 50g glycidyl methacrylate; under protection of nitrogen gas, stir 30min; add Diisopropyl azodicarboxylate 500mg; mixture reacted 60 hours in 55 ℃ of oil baths, obtained solid product with methanol extraction, dissolved with DMF again; centrifugal, obtain solid product after the drying.
Embodiment 13:
In reaction flask, add 50.0mg graphene oxide, 50g N; dinethylformamide, 0.5g glycidyl methacrylate; under protection of nitrogen gas, stir 30min; add initiator Diisopropyl azodicarboxylate 0.5mg; mixture reacted 1.5 hours in 90 ℃ of oil baths, obtained solid product with methanol extraction, dissolved with DMF again; centrifugal, obtain solid product after the drying.

Claims (4)

1. polymer graft preparation method of graphene, it is characterized in that adding the Graphene or the graphene oxide of 1 weight part, the solvent of 10-1000 weight part, the vinyl monomer of 10-1000 weight part, logical nitrogen adds the initiator of 0.01～10 weight part down, be heated to 55～90 ℃, reaction 1.5～60h is through precipitation, centrifugal, washing, drying obtains product polymer graft Graphene.
2. a kind of polymer graft preparation method of graphene according to claim 1, it is characterized in that: described vinyl monomer is: vinylbenzene, Sodium styrene sulfonate, methyl methacrylate, butyl methacrylate, hydroxyethyl methylacrylate, glycidyl methacrylate, dimethylaminoethyl methacrylate, diethylaminoethyl methacrylate, the methacrylic tert-butyl acrylate, 3-(iso-butylene acyl-oxygen) propyl trimethoxy silicane, methyl acrylate, butyl acrylate, Hydroxyethyl acrylate, glycidyl acrylate, dimethylaminoethyl acrylate, the vinylformic acid lignocaine ethyl ester, tert-butyl acrylate, acrylamide, the N-N-isopropylacrylamide, methacrylic acid, vinylformic acid, 4-vinylpridine, the 2-vinyl pyridine, 4-vinyl pyrrolidone or vinyl cyanide.
3. a kind of polymer graft preparation method of graphene according to claim 1, it is characterized in that: described solvent is: water, N, dinethylformamide, N, N-N,N-DIMETHYLACETAMIDE, tetrahydrofuran (THF), methyl-sulphoxide, N-Methyl pyrrolidone, ethylene glycol, glycol ether, pyridine, ethyl acetate, dioxane, butanone or Virahol.
4. a kind of polymer graft preparation method of graphene according to claim 1, it is characterized in that: described initiator is selected from Potassium Persulphate, ammonium persulphate, 2,2'-Azobis(2,4-dimethylvaleronitrile), Diisopropyl azodicarboxylate, dibenzoyl peroxide or S-WAT.
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