CN102745672A - Preparation method of organic-chain-segment-modified graphene oxide - Google Patents
Preparation method of organic-chain-segment-modified graphene oxide Download PDFInfo
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Abstract
The invention discloses a preparation method of organic-chain-segment-modified graphene oxide. According to the invention, graphite is oxidized under the effects of strong oxidizing agents such as concentrated sulfuric acid, sodium nitrate and potassium permanganate; the oxidized graphite is subjected to ultrasonic dispersion in an organic solvent, such that a graphene oxide dispersion system is prepared; diisocyanate and dihydric alcohol are subjected to a reaction; hydroxyacrylate is used for sealing one end; and an NCO group in the organic chain segment is subjected to a reaction with the prepared graphene oxide, such that the organic-chain-segment-modified graphene oxide is prepared. The organic chain segment contains polymerizable double bonds, such that cross-linking polymerization of the modified graphene oxide and other organic materials can be promoted, and composite materials with special properties can be obtained.
Description
Technical field
The invention belongs to the Graphene technical field, relate in particular to a kind of organic chain shed repair and adorn modified oxidized preparation method of graphene.
Background technology
Graphene has unique electrooptics characteristic, good conductivity, light transmission, very high chemicalstability and thermodynamic stability, makes it aspect electrode, high sensor, the high-performance energy storage device extraordinary application prospect arranged.In addition; Graphene also has the intensity of superelevation; Powerful reactive force between carbon atom makes it become the highest material of present known mechanical strength; And might be widely used among the novel high-strength matrix material as additive, aspect preparation heat conduction, the conducing composite material tempting application prospect is being arranged also.But because graphene-structured is complete, chemicalstability is high; Its surface is inert condition; And stronger Van der Waals force is arranged between graphene film and the sheet, be easy to generate gathering, this has caused great difficulty for the further research and the application of Graphene; Therefore, chemically modified or modification being carried out in the Graphene surface, to improve the intermiscibility and the dispersiveness of itself and organic materials particularly important.
What chemically modified and modification were carried out in the surface of Graphene is earlier with graphite oxidation; The preparation graphene oxide; Carboxyl, hydroxyl and epoxy group(ing) isoreactivity group are contained in the graphene oxide surface; Through the method for chemistry it is modified and modification then, to strengthen the consistency and the dispersiveness of itself and organic polymer material.
Chemically modified to graphene oxide at present mainly contains following several method: (1) utilizes SOCl
2COOH functional group reaction with the graphene oxide surface; React with the alkylamine of long-chain or the Fatty Alcohol(C12-C14 and C12-C18) of long-chain again; Produce acid amides or ester, just can form can be in non-polar solvent (like methylene dichloride, tetrachloromethane) the modified oxidized Graphene of stable dispersion.The alkylamine of long-chain also can react with the epoxide group in the graphene oxide under certain conditions, produces similar modified oxidized Graphene.(2) adopt a series of phenyl and alkyl isocyanate that graphene oxide is reacted ,-NCO group can with graphene oxide in-OH and-the COOH radical reaction, obtain different isocyanate-modified graphene oxides.Stankovichs S etc. carries out functional modification through isocyanic ester to graphene oxide; Obtained the product of a series of different side chains; Contrast with graphene oxide; This isocyanate-modified graphene oxide does not peel off in water fully, but after simple ultrasonication, very easily in N (DMF), N-methylpyrroline (NMP), DMSO 99.8MIN. (DMSO) and hexamethylphosphoramide (HMPA), forms stable colloidal dispersion.(3) modify graphene oxide through diazotization reaction.Q.Su etc. obtain graphene oxide that a series of aryl modify with the aryl diazonium salts reaction with graphene oxide behind hydrazine hydrate reduction, they have solvability preferably in polar aprotic solvent (like DMF, THF, DMSO).(4) graft modification of coupling agent, S.Wang etc. modify graphene oxide with amino silicane coupling agent, be applied in the epoxy resin solidifying system, and the mechanical property of curing system etc. all has raising.
Summary of the invention
Research about graphene oxide surface chemical modification and modification basically all is in the starting stage; The present invention provides a kind of novel organic segment of band acrylic double bond graphene oxide to be carried out the method for surface chemical modification; The surface-treated graphene oxide of this method preparation has two keys that can react; Help the compound and crosslinking polymerization with other material, help to prepare graphene oxide matrix material with property.
Technology of preparing route of the present invention is following:
(1) preparation of graphene oxide: in flask, add the excessive vitriol oil, ice-water bath adds graphite, SODIUMNITRATE, potassium permanganate then respectively; The mass ratio of described graphite, SODIUMNITRATE, potassium permanganate is (2～6): (1～3): (5～10), control reaction temperature are no more than 10 ℃, reaction 1～3h; Be warming up to room temperature then, continue reaction 1～3d, add the water dilution of twice vitriol oil volume; Add ydrogen peroxide 50 again, stirring reaction 1～3h, spinning; Washing and drying prepares graphene oxide through ultrasonic dispersion with graphite oxide in organic solvent.
Described solvent is: N, N N (DMF), methylene dichloride (CHCl
2), tetrachloromethane (CCl
4), one or more the mixed system in the N-methylpyrroline (NMP), DMSO 99.8MIN. (DMSO), hexamethylphosphoramide (HMPA), THF (THF).
The preparation of (2) being with two key organic chain shed repairs to adorn modified oxidized Graphene: in there-necked flask, add a certain amount of vulcabond, be heated to 50～80 ℃; Divalent alcohol is added in the vulcabond, and divalent alcohol is added with the dibutyl tin dilaurate that accounts for total mass 0.2～1.0%, and the mol ratio that the divalent alcohol add-on satisfies vulcabond and divalent alcohol is 2:1; Reaction 2～6h.In reaction system, be added dropwise to hydroxy acrylate then, hydroxy acrylate is added with the stopper that accounts for total mass 0.5～1.0%; The mol ratio that the add-on of hydroxy acrylate satisfies hydroxy acrylate and vulcabond is 1:2, and temperature of reaction is controlled at 60～90 ℃, reaction 2～4h; Obtain the urethane acrylate segment of an end band NCO group; Graphene oxide dispersion system with (1) preparation adds this reaction system again, adds and accounts for total mass 0.1～0.3% dibutyl tin dilaurate, and temperature of reaction is controlled at 60～90 ℃; Continue reaction 1～3h, promptly get graphene oxide with two organic segment modifications of key.
Described vulcabond is: a kind of in tolylene diisocyanate (TDI), diphenylmethanediisocyanate (MDI), hexamethylene diisocyanate (HDI), isophorone diisocyanate (IPDI), dicyclohexyl methane diisocyanate (HMDI), PPDI (PPDI), Methylcyclohexyl diisocyanate (HTDI), the xylylene diisocyanate (XDI).
Described divalent alcohol is: polyether Glycols, polyester diol, Ucar 35, NSC 6366,1,4-butyleneglycol, 1, a kind of in the hydroxy silicon oil of 6-pinakon, hydroxy radical content 0.5～10%.
Described hydroxy acrylate is: a kind of in Hydroxyethyl acrylate, Propylene glycol monoacrylate, Rocryl 400, Rocryl 410, the vinylformic acid hydroxy butyl ester.
Described stopper is: a kind of in MEHQ and the Resorcinol.
The present invention provides a kind of novel organic segment of band acrylic double bond graphene oxide to be carried out the method for surface chemical modification; The surface-treated graphene oxide of this method preparation has two keys that can react; Help the compound and crosslinking polymerization with other material, help to prepare graphene oxide matrix material with property.
Embodiment
Embodiment 1:
The first step, the vitriol oil of adding 50mL in flask, ice-water bath adds 2g graphite, 1g SODIUMNITRATE, 6g potassium permanganate then respectively; Control reaction temperature is no more than 10 ℃, and stirring reaction 1h is warming up to room temperature then, continues reaction 2d; Add the water dilution of 100mL, add the 5mL ydrogen peroxide 50 again, stirring reaction 2h, spinning; Washing and drying, with graphite oxide at N, dinethylformamide (DMF) and methylene dichloride (CHCl
2) prepare graphene oxide through ultrasonic dispersion in the mixed solvent; In second step, the isophorone diisocyanate (IPDI) of adding 0.2mol is heated with stirring to 55 ℃ in the flask of 500mL; In the polyether Glycols of 0.1mol, add the dibutyl tin dilaurate that accounts for total mass 0.5%; Be added dropwise to isophorone diisocyanate (IPDI); Behind the reaction 5h; The Hydroxyethyl acrylate (being dissolved with the MEHQ that accounts for total mass 0.8%) that adds 0.1mol again is warmed up to 75 ℃ and continues reaction 2h, obtains the urethane acrylate segment of an end band NCO group; Graphene oxide dispersion system with the first step preparation adds this reaction system again, adds the dibutyl tin dilaurate that accounts for total mass 0.2%, and temperature of reaction is controlled at 85 ℃, continues reaction 1h, promptly gets the graphene oxide with two organic segment modifications of key.
Embodiment 2:
The first step, the vitriol oil of adding 100mL in flask, ice-water bath adds 6g graphite, 3g SODIUMNITRATE, 15g potassium permanganate then respectively; Control reaction temperature is no more than 10 ℃, and stirring reaction 3h is warming up to room temperature then, continues reaction 3d; Add the water dilution of 200mL, add the 12mL ydrogen peroxide 50 again, stirring reaction 1h; Spinning, washing and drying prepares graphene oxide through ultrasonic dispersion with graphite oxide in DMSO 99.8MIN. (DMSO); In second step, the tolylene diisocyanate (TDI) of adding 0.4mol is heated with stirring to 60 ℃ in the flask of 500mL; At 1 of 0.2mol; Add the dibutyl tin dilaurate that accounts for total mass 0.2% in the 6-pinakon; Be added dropwise to tolylene diisocyanate (TDI), behind the reaction 6h, add the Rocryl 400 (being dissolved with the Resorcinol that accounts for total mass 0.5%) of 0.2mol again; Be warmed up to 70 ℃ and continue reaction 2.5h, obtain the urethane acrylate segment of an end band NCO group; Graphene oxide dispersion system with the first step preparation adds this reaction system again, adds the dibutyl tin dilaurate that accounts for total mass 0.3%, and temperature of reaction is controlled at 75 ℃, continues reaction 3h, promptly gets the graphene oxide with two organic segment modifications of key.
Embodiment 3:
The first step, the vitriol oil of adding 120mL in flask, ice-water bath adds 6g graphite, 6g SODIUMNITRATE, 30g potassium permanganate then respectively; Control reaction temperature is no more than 10 ℃, and stirring reaction 2h is warming up to room temperature then, continues reaction 2d; Add the water dilution of 240mL, add the 15mL ydrogen peroxide 50 again, stirring reaction 2h; Spinning, washing and drying, with graphite oxide at THF (THF) and methylene dichloride (CHCl
2) prepare graphene oxide through ultrasonic dispersion in the mixed solvent; In second step, the diphenylmethanediisocyanate (MDI) of adding 0.5mol is heated with stirring to 50 ℃ in the flask of 500mL; In the hydroxy silicon oil of 0.25mol, add the dibutyl tin dilaurate that accounts for total mass 1.0%; Be added dropwise to diphenylmethanediisocyanate (MDI); Behind the reaction 4h; The vinylformic acid hydroxy butyl ester (being dissolved with the MEHQ that accounts for total mass 0.5%) that adds 0.25mol again is warmed up to 80 ℃ and continues reaction 1h, obtains the urethane acrylate segment of an end band NCO group; Graphene oxide dispersion system with the first step preparation adds this reaction system again, adds the dibutyl tin dilaurate that accounts for total mass 0.1%, and temperature of reaction is controlled at 70 ℃, continues reaction 3h, promptly gets the graphene oxide with two organic segment modifications of key.
Embodiment 4:
The first step, the vitriol oil of adding 50mL in flask, ice-water bath adds 2g graphite, 3g SODIUMNITRATE, 5g potassium permanganate then respectively; Control reaction temperature is no more than 10 ℃, and stirring reaction 1h is warming up to room temperature then, continues reaction 3d; Add the water dilution of 100mL, add the 5mL ydrogen peroxide 50 again, stirring reaction 3h; Spinning, washing and drying, with graphite oxide at tetrachloromethane (CCl
4) and N-methylpyrroline (NMP) mixed solvent in prepare graphene oxide through ultrasonic dispersion; In second step, the hexamethylene diisocyanate (HDI) of adding 0.2mol is heated with stirring to 65 ℃ in the flask of 500mL; In the polyester diol of 0.1mol, add the dibutyl tin dilaurate that accounts for total mass 0.7%; Be added dropwise to hexamethylene diisocyanate (HDI); Behind the reaction 3h; The Hydroxyethyl acrylate (being dissolved with the MEHQ that accounts for total mass 1.0%) that adds 0.1mol again is warmed up to 80 ℃ and continues reaction 1.5h, obtains the urethane acrylate segment of an end band NCO group; Graphene oxide dispersion system with the first step preparation adds this reaction system again, adds the dibutyl tin dilaurate that accounts for total mass 0.2%, and temperature of reaction is controlled at 65 ℃, continues reaction 3h, promptly gets the graphene oxide with two organic segment modifications of key.
Embodiment 5:
The first step, the vitriol oil of adding 60mL in flask, ice-water bath adds 3g graphite, 3g SODIUMNITRATE, 15g potassium permanganate then respectively; Control reaction temperature is no more than 10 ℃, and stirring reaction 3h is warming up to room temperature then, continues reaction 3d; Add the water dilution of 120mL, add the 6mL ydrogen peroxide 50 again, stirring reaction 2h; Spinning, washing and drying prepares graphene oxide through ultrasonic dispersion with graphite oxide in DMSO 99.8MIN. (DMSO) and hexamethylphosphoramide (HMPA) mixed solvent; In second step, the dicyclohexyl methane diisocyanate (HMDI) of adding 0.4mol is heated with stirring to 65 ℃ in the flask of 500mL; In the Ucar 35 of 0.2mol, add the dibutyl tin dilaurate that accounts for total mass 0.5%; Be added dropwise to dicyclohexyl methane diisocyanate (HMDI); Behind the reaction 5h; The Rocryl 410 (being dissolved with the Resorcinol that accounts for total mass 0.6%) that adds 1mol again is warmed up to 90 ℃ and continues reaction 2h, obtains the urethane acrylate segment of an end band NCO group; Graphene oxide dispersion system with the first step preparation adds this reaction system again, adds the dibutyl tin dilaurate that accounts for total mass 0.3%, and temperature of reaction is controlled at 80 ℃, continues reaction 2.5h, promptly gets the graphene oxide with two organic segment modifications of key.
Foregoing description can not limit protection scope of the present invention with this with explanation.Allly conceive equivalence that essence does according to the present invention and change or modify, all should be encompassed within protection scope of the present invention.
Claims (6)
1. modified oxidized preparation method of graphene is adornd in the two key organic chain shed repairs of band, comprises the steps:
(A) preparation of graphene oxide: in reaction vessel, add the excessive vitriol oil, ice-water bath adds graphite, SODIUMNITRATE, potassium permanganate successively; The mass ratio of described graphite, SODIUMNITRATE, potassium permanganate is (2～6): (1～3): (5～10), control reaction temperature are no more than 10 ℃, reaction 1～3h; At room temperature react 1～3d then, add the water dilution of twice vitriol oil volume, add ydrogen peroxide 50 again; Stirring reaction 1～3h; Spinning, washing and drying prepares graphene oxide through ultrasonic dispersion with graphite oxide in organic solvent;
The preparation of (B) being with two key organic chain shed repairs to adorn modified oxidized Graphene: in reaction vessel, add vulcabond, be heated to 50～80 ℃; Divalent alcohol is added in the vulcabond, and the mol ratio that described divalent alcohol add-on satisfies vulcabond and divalent alcohol is 2:1; Described divalent alcohol is added with the dibutyl tin dilaurate that accounts for total mass 0.2～1.0%, reaction 2～6h; In reaction system, be added dropwise to hydroxy acrylate then, the mol ratio that the add-on of described hydroxy acrylate satisfies hydroxy acrylate and vulcabond is 1:2, and described hydroxy acrylate is added with the stopper that accounts for total mass 0.5～1.0%; Temperature of reaction is controlled at 60～90 ℃; React 2～4h, obtain the urethane acrylate segment of the two keys of an end band NCO group the other end band, the graphene oxide with preparation adds this system again; Add and account for total mass 0.1～0.3% dibutyl tin dilaurate; Temperature of reaction is controlled at 60～90 ℃, continues reaction 1～3h, promptly get and be with two modified oxidized Graphenes of the organic segment of key.
2. modified oxidized preparation method of graphene is adornd in organic chain shed repair as claimed in claim 1, it is characterized in that:
Described solvent is N, N N (DMF), methylene dichloride (CHCl
2), tetrachloromethane (CCl
4), one or more the mixed system in the N-methylpyrroline (NMP), DMSO 99.8MIN. (DMSO), hexamethylphosphoramide (HMPA), THF (THF).
3. modified oxidized preparation method of graphene is adornd in organic chain shed repair as claimed in claim 1, it is characterized in that:
Described vulcabond is a kind of in tolylene diisocyanate (TDI), diphenylmethanediisocyanate (MDI), hexamethylene diisocyanate (HDI), isophorone diisocyanate (IPDI), dicyclohexyl methane diisocyanate (HMDI), PPDI (PPDI), Methylcyclohexyl diisocyanate (HTDI), the xylylene diisocyanate (XDI).
4. modified oxidized preparation method of graphene is adornd in organic chain shed repair as claimed in claim 1, it is characterized in that:
Described divalent alcohol is polyether Glycols, polyester diol, Ucar 35, NSC 6366,1,4-butyleneglycol, 1, a kind of in the hydroxy silicon oil of 6-pinakon, hydroxy radical content 0.5～10%.
5. modified oxidized preparation method of graphene is adornd in organic chain shed repair as claimed in claim 1, it is characterized in that:
Described hydroxy acrylate is a kind of in Hydroxyethyl acrylate, Propylene glycol monoacrylate, Rocryl 400, Rocryl 410, the vinylformic acid hydroxy butyl ester.
6. modified oxidized preparation method of graphene is adornd in organic chain shed repair as claimed in claim 1, it is characterized in that:
Described stopper is a kind of in MEHQ and the Resorcinol.
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