CN104140483B - A kind of process for dispersing of SWCN - Google Patents
A kind of process for dispersing of SWCN Download PDFInfo
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Abstract
The invention discloses a kind of process for dispersing of SWCN. The invention provides polymer and preparation method thereof shown in formula I, in formula I, i is the natural number between 20～150. Shown in formula I, polymer and SWCN mix in organic solvent, can realize the dispersion of SWCN in organic solvent. On this basis, remove the compound that obtains polymer shown in formula I and SWCN after described organic solvent, this compound is added to the water, pass into CO2Gas can be realized the dispersion of SWCN in water. The ATRP initator (compound shown in formula II) that use contains pyrenyl group can be guaranteed the effect of only with one carbon pipe of a polymer chain; Utilize polymer and CO shown in formula I2Disperse SWCN, carbon pipe can be dispersed in organic solvent and water, the method is simple and easy to do, mild condition; The SWNTs that utilizes the method to disperse can not reunite, can be dispersed, can be used for further functionalization or industrial processes.
Description
Technical field
The present invention relates to a kind of process for dispersing of SWCN, be specifically related to a kind of by polymer and CO2GasThe method of disperseing SWCN, belongs to carbon nanotube dispersed technical field.
Background technology
Carbon exists numerous allotropes, except well-known diamond, graphite, and fullerene, carbonNanotube and Graphene, because it is at the peculiar property of the aspects such as structure, machinery, electronics, all become nanometer section" favorite " of skill. Wherein, CNT is at nanoelectronics and photoelectronics, vacuum electronics, the compound material of high strengthMaterial, nanosecond medical science and medicine transmission, sensor and brake, nanoscale template and passage, optical element, heat conduction materialThe aspects such as material have all shown boundless application prospect.
But, because CNT is subject to the attraction of Van der Waals force and the impact of hydrophobic interaction, and be easy to assembleTogether, make the dissolubility of CNT in various common solvent, especially water not good, thus serious restrictionThey dispersions in common solvent, and greatly limited their application. Dispersed the grinding of carbon nanomaterialStudy carefully, the application that comprises the aspects such as biocompatibility transport, medicament transport system and optical pickocff is all had veryImportant meaning. In order to address this problem, usually chemical modification by covalent modification or non-covalent modification of peopleMethod is improved the deployment conditions of CNT. Wherein, non-covalent modification is owing to can avoiding interference carbon nanomaterialIntrinsic characteristic, and be subject to increasing researcher's favor.
Summary of the invention
The process for dispersing that the object of this invention is to provide a kind of SWCN, in the present invention, SWCN passes throughPolymer disperses in organic solvent, by polymer and CO2Gas disperses in water, and by thisBright method disperses the SWCN (SWNTs) obtaining can not reunite, can be dispersed.
Polymer shown in formula I provided by the invention,
In formula I, i is the natural number between 20～150.
Wherein, i is specially 22～25,22,23 or 25.
The present invention provides the preparation method of polymer shown in above-mentioned formula I simultaneously, comprises the steps:
In formula I, i is the natural number between 20～150;
(1), under the catalysis of alkali, 1-pyrene methyl alcohol and bromo isobutyl acylbromide nucleo philic substitution reaction obtain compound shown in formula II;
(2) at CuBr and N, N, N', N', N " under the condition of five methyl diethylentriamine (PMDETA) catalysis,Using compound shown in formula II as initator, cause diethylaminoethyl methacrylate (DEAEMA) and carry out atomTransferring free-radical polymerization (ATRP), obtains polymer shown in formula I.
Shown in formula I of the present invention, the preparation flow figure of polymer as shown in Figure 2, specifically adopts ATRP(ATRP) polymer (Py-PDEAEMA) shown in the formula I that contains pyrenyl group, compound letter shown in formula II have been synthesizedBe written as Py-ATRP.
Shown in the prepared formula I of above-mentioned preparation method, in polymer, i is specially 22～25,22,23 or 25.
Above-mentioned preparation method, in step (1), described alkali is to appoint in triethylamine, pyridine and DIPEAA kind of;
The mol ratio of described 1-pyrene methyl alcohol and described bromo isobutyl acylbromide can be 1:1.2～5, specifically can be 1:3;
The mol ratio of described alkali and described bromo isobutyl acylbromide is 1:1;
The reaction time of described nucleophilic substitution is 0.5 day～5 days, specifically can be 0.5 day～2 days, 0.5 day～1 day,1 day～2 days, 0.5 day, 1 day and 2 days; Reaction temperature is 10 DEG C～35 DEG C, specifically can be 25 DEG C.
Above-mentioned preparation method, in step (2), shown in described CuBr and formula II, the mol ratio of compound is 1:1;
Described N, " shown in five methyl diethylentriamine and formula II, the mol ratio of compound is 1:1 for N, N', N', N;
The reaction temperature of described ATRP can be 60 DEG C～100 DEG C, specifically can be 70 DEG C～90 DEG C, 70 DEG C～80 DEG C, 80 DEG C～90 DEG C, 70 DEG C, 80 DEG C or 90 DEG C;
The reaction time of described ATRP can be 6h～24h, specifically can be 10h～16h, 10h～12h,12h～16h, 10h, 12h or 16h.
The present invention further provides polymer shown in formula I in the application disperseing in SWCN.
The present invention further provides the process for dispersing of SWCN, comprised the steps: polymer shown in formula IMix in organic solvent with SWCN, realize described SWCN in organic solvent pointLoose;
In formula I, i is the natural number between 20～150.
Above-mentioned process for dispersing mainly utilizes the pyrenyl group in polymer shown in formula I as polymer and SWCN(SWNTs) medium (as shown in Figure 1) connecting, the pyrenyl group shown in formula I in polymer can pass through π-π and doWith combining with CNT. Because polymer shown in formula I can dissolve in organic solvent, so be compounded withThe SWNTs of this polymer can be disperseed fully in organic solvent;
Shown in formula I, in polymer, i is specially 22～25,22,23 or 25.
In above-mentioned process for dispersing, shown in described SWCN and formula I, the mass ratio of polymer can be 1:4～20,Specifically can be 1:4～10,1:10～20,1:4,1:10 or 1:20;
Described organic solvent be in toluene, dimethylbenzene, ethyl acetate, propyl acetate and chloroform any;
Polymer shown in formula I and shown in SWCN specifically can under ultrasonication, mix, ultrasonic time toolBody can be 30min.
The present invention on this basis, further provides one to pass through CO2Gas disperses SWCN in waterMethod, comprises the steps:
(1) shown in formula I, polymer and SWCN mix in organic solvent; Remove described organic solventAfter obtain the compound of polymer shown in formula I and SWCN, be labeled as polymer/SWNTs compound;
In formula I, i is the natural number between 20～150;
(2) described polymer/SWNTs compound is added to the water, passes into CO2Gas realized described single wall carbon and receivedThe dispersion of mitron in water.
Above-mentioned process for dispersing mainly utilizes polymethylacrylic acid N, N-lignocaine ethyl ester (PDEAEMA) base polymerChain in the aqueous solution can with CO2The characteristic (as shown in Figure 1) of reaction, specifically by passing into CO in reaction system2，Make the tertiary amine groups in polymer shown in formula I protonated and dissolve in water, thereby make to be compounded with polymer shown in formula ISWNTs in water, disperseed fully;
Shown in formula I, in polymer, i is specially 22～25,22,23 or 25.
Above-mentioned process for dispersing, in step (1), described organic solvent is toluene, dimethylbenzene, ethyl acetate, acetic acid thirdIn ester and chloroform any;
In step (2), pass into CO2The flow velocity of gas can be 0.5～2mL/s, specifically can be 1mL/s;
Described in every 1mg, polymer/SWNTs compound passes into CO2The volume of gas can be 30～100mL, specifically canFor 36mL, 41mL, 43mL, 82mL or 86mL.
Utilize the concentration of polymer shown in the single-walled carbon nanotube dispersion liquid Chinese style I that above-mentioned process for dispersing obtains can be1～2mg/mL, specifically can be 1mg/mL or 2mg/mL; The concentration of SWCN can be 0.05～0.5mg/mL,Specifically can be 0.05mg/mL, 0.1mg/mL, 0.2mg/mL or 0.5mg/mL.
The process for dispersing of SWCN provided by the invention has following beneficial effect:
1, use the ATRP initator that contains pyrenyl group, each polymer only contains a pyrenyl group, can guarantee oneThe effect of only with one carbon pipe of individual polymer chain;
2, adopt polymer shown in formula I effectively carbon pipe to be dispersed in organic solvent, in reaction systemPass into CO2After, carbon pipe can be dispersed in water. The method is simple and easy to do, mild condition.
3, the method disperses the SWNTs obtaining can not reunite, can be dispersed, and can be for furtherFunctionalization or industrial processes.
Brief description of the drawings
Fig. 1 is for utilizing polymer P y-PDEAEMA and CO shown in formula I2The signal of gas dispersion SWCNFigure.
Fig. 2 is the flow chart of polymer P y-PDEAEMA shown in synthesis type I.
Fig. 3 is the hydrogen nuclear magnetic resonance spectrogram of initator Py-ATRP (compound shown in formula II).
Fig. 4 is the hydrogen nuclear magnetic resonance spectrogram of polymer P y-PDEAEMA shown in formula I.
Fig. 5 be the Py-PDEAEMA for preparing of embodiment 1 in toluene (concentration is 1mg/mL) withIn toluene, (concentration of Py-PDEAEMA is 1mg/mL to Py-PDEAEMA/SWNT compound, SWNTs'sConcentration is 0.05mg/mL) fluorescence spectrum figure; Wherein interior illustration is Py-PDEAEMA/SWNT compound tolueneThe photo of dispersion liquid.
Fig. 6 passes into CO in embodiment 1-52Before after (left figure) (right figure), Py-PDEAEMA/SWNT is compoundThe photo that thing disperses in water.
Fig. 7 is the transmission electron microscope photo of Py-PDEAEMA/SWNT compound dispersion liquid in water in embodiment 1.
Fig. 8 is the Raman spectrogram of Py-PDEAEMA/SWNT compound and SWNTs in embodiment 1.
Detailed description of the invention
The experimental technique using in following embodiment if no special instructions, is conventional method.
Material, reagent etc. used in following embodiment, if no special instructions, all can obtain from commercial channels.
Embodiment 1,
(1), synthetic Py-PDEAEMA
Flow chart as shown in Figure 2.
A, 116mg1-pyrene methyl alcohol is dropped into 25mL reaction bulb, add the THF that 5mL is dry, 152mg triethylamine(Et3N), stirring and dissolving, ice bath, is dissolved in 345mg bromo isobutyl acylbromide in the THF that 5mL is dry, is placed in and dripsIn liquid funnel, be added dropwise to reaction system, 20min dropwises, and adularescent solid generates, stirring reaction 1 under 25 DEG C of conditionsMy god. After reaction finishes, filter, filtrate is transferred in separatory funnel, add 60mL carrene, respectively with fullWith ammonium chloride solution, saturated sodium bicarbonate solution and saturated nacl aqueous solution extraction, separatory, organic phase is through anhydrous slufuric acidMagnesium is dry, filters, and concentrated, column chromatography (benzinum: carrene=3:1, volume ratio), obtains target productPy-ATRP (compound shown in formula II) 0.37g, yield: 97%.
The nucleus magnetic hydrogen spectrum of Py-ATRP prepared by the present embodiment as shown in Figure 3.
B, the DEAEMA monomer of 5.56g is dropped in the single port flask of a 25mL, add 6mL dryDMF, the initator Py-ATRP of the PMDETA of 35mg and 76mg, through once freezing-after vacuumizing-thawing,Add the cuprous bromide of 28mg. Whole system is after three freezing-vacuumize-thaw cycles, afterwards by flask afterwardsBe placed in 90 DEG C of oil baths and react 12h, reaction finishes the rear cooled with liquid nitrogen cessation reaction of using. Reactant liquor dialysis, freeze-drying. ?To target product Py-PDEAEMA (compound shown in formula I, wherein the value of i is 23) 0.685g, yield: 73.8%,Monomer conversion: 11.3%.
The proton nmr spectra of Py-PDEAEMA prepared by the present embodiment as shown in Figure 4.
Mn,NMR＝4.6kDa,Mn,GPC＝5.1kDa,Mw/Mn＝1.21.
(2) SWCN is distributed in toluene
10mgPy-PDEAEMA is dropped in the single port flask of 25mL, adds 10mL toluene, fully dissolve,Add 0.5mgSWNTs, ultrasonic 30min, SWNTs is dispersed in toluene, obtains polymer concentration to be1mg/mL, the homodisperse toluene solution of SWNTs that SWNTs concentration is 0.05mg/mL.
Py-PDEAEMA prepared by the present embodiment step (1) is dissolved in toluene, and concentration is 1mg/mL, itsFluorescence spectrum as shown in Figure 5; The fluorescence spectrum of the toluene solution that the present embodiment step (2) obtains as shown in Figure 5. ByFig. 5 is known, compared with the fluorescence spectrum of toluene solution and the fluorescence spectrum of Py-PDEAEMA that step (2) obtains,There is obvious cancellation at three characteristic fluorescence peaks at 350～450nm place in pyrene, this is because the energy of pyrenyl group shiftsTo on the carbon tube wall of absorption. Thereby can find out, between the pyrenyl group in Py-PDEAEMA and SWNTs, existVery strong π-π interacts. Interact by this very strong π-π, polymer P y-PDEAEMA can be repaiiedDecorations are to the surface of SWNTs, due to the interacts steric restriction work of the polymeric layer being adsorbed of the Van der Waals between carbon pipeWith offset, thereby improved the dispersiveness of SWNTs.
(3) SWCN is distributed in water
A, the toluene solution that contains polymer/SWNTs compound that step (2) is obtained are spin-dried for, vacuum drying,Obtain polymer/SWNTs compound solid.
The Raman spectrum of polymer/SWNTs compound prepared by the present embodiment as shown in Figure 8. As shown in Figure 8, withThe Raman spectrum of SWNTs is compared, and the D* of SWNTs is with after being connected with polymer P y-PDEAEMA, from 2682cm-1Move to 2664.2cm-1, G is with from 1586cm-1Move to 1589cm-1, D is with from 1349.9cm-1Move to 1354.3cm-1. These Raman shifts show: carbon tube-surface electronic environment around with polymerAfter being connected, there is change in Py-PDEAEMA. And this change is just by the pyrenyl group in Py-PDEAEMA with containThere is the very strong π-π interaction existing between the SWNTs of height conjugated structure to cause.
B, polymer/SWNTs compound 10.5mg of obtaining is dropped in the single port flask of 25mL, add 10mLDeionized water, its photo is as shown in left in Figure 6; Speed with 1mL/s passes into CO in reaction system2, solutionBlackening gradually, after 15min, polymer/SWNTs compound dissolves, and its photo as shown in right in Figure 6, is gatheredCompound concentration is 1mg/mL, the homodisperse aqueous solution of SWNTs that SWNTs concentration is 0.05mg/mL.
The transmission electron microscope photo of the above-mentioned aqueous solution as shown in Figure 7, can be found out by this figure, SWNTs by with polymerPy-PDEAEMA is connected in mutually and in the aqueous solution, has obtained good dispersion.
Embodiment 2,
(1), synthetic Py-PDEAEMA
A and b step are with embodiment 1.
(2) SWCN is distributed in ethyl acetate
10mgPy-PDEAEMA is dropped in the single port flask of 25mL, add 10mL ethyl acetate, fully moltenSeparate, add 1mgSWNTs, ultrasonic 30min, SWNTs is dispersed in ethyl acetate, obtains polymer denseDegree is 1mg/mL, the homodisperse ethyl acetate solution of SWNTs that SWNTs concentration is 0.1mg/mL.
(3) SWCN is distributed in water
The ethyl acetate solution of polymer/SWNTs compound is spin-dried for, and vacuum drying, obtains polymer/SWNTs multipleCompound solid.
In the Raman spectrum of polymer/SWNTs compound prepared by the present embodiment and embodiment 1, polymer/SWNTs is multipleThe Raman spectrum (Fig. 8) of compound, without substantive difference, can be learnt: the pyrenyl group in Py-PDEAEMA and containingThe very strong π-π existing between the SWNTs of height conjugated structure interacts.
Polymer/SWNTs compound 11 mg of obtaining is dropped in the single port flask of 25mL, add 10mL go fromSub-water passes into CO with the speed of 1mL/s in reaction system2, solution is blackening gradually, after 15min, and polymer/SWNTsCompound dissolves, and obtaining polymer concentration is 1mg/mL, and the SWNTs that SWNTs concentration is 0.1mg/mL evenly dividesThe loose aqueous solution.
Transmission electron microscope photo and the embodiment of polymer/SWNTs compound prepared by the present embodiment dispersion liquid in waterIn 1, the transmission electron microscope photo of dispersion liquid (Fig. 7), without significant difference, can be found out: SWNTs obtains in the aqueous solutionGood dispersion.
Embodiment 3,
(1), synthetic Py-PDEAEMA
A. 348mg pyrene methyl alcohol is dropped into 50mL reaction bulb, add the THF that 15mL is dry, 456mg triethylamine(Et3N), stirring and dissolving, ice bath, is dissolved in 1035mg bromo isobutyl acylbromide in the THF that 15mL is dry, is placed inIn dropping funel, be added dropwise to reaction system, 15min dropwises, and adularescent solid generates, stirring at room temperature reaction 0.5My god. After reaction finishes, filter, filtrate is transferred in separatory funnel, add 150mL carrene, respectively with fullWith ammonium chloride solution, saturated sodium bicarbonate solution and saturated nacl aqueous solution extraction, separatory, organic phase is through anhydrous slufuric acidMagnesium is dry, filters, and concentrated, column chromatography (benzinum: carrene=3:1), obtains target product Py-ATRP1.12G, yield: 98%.
B. the DEAEMA monomer of 11.12g is dropped in the single port flask of a 50mL, add 12mL to be driedDMF, the initator Py-ATRP of the PMDETA of 70mg and 152mg, through once freezing-after vacuumizing-thawing,Add the cuprous bromide of 56mg. Whole system is after three freezing-vacuumize-thaw cycles, afterwards by flask afterwardsBe placed in 70 DEG C of oil baths and react 16h, reaction finishes the rear cooled with liquid nitrogen cessation reaction of using. Reactant liquor dialysis, freeze-drying. ?To target product Py-PDEAEMA (value of i is 25) 1.41g, yield: 70.5%.
(2) SWCN is distributed in toluene
20mgPy-PDEAEMA is dropped in the single port flask of 25mL, adds 10mL toluene, fully dissolve,Add 1mgSWNTs, ultrasonic 30min, SWNTs is dispersed in toluene, and obtaining polymer concentration is 2mg/mL,SWNTs concentration is the homodisperse toluene solution of the SWNTs of 0.1mg/mL.
(3) SWCN is distributed in water
The toluene solution of polymer/SWNTs compound is spin-dried for, and vacuum drying, obtains polymer/SWNTs compoundSolid.
In the Raman spectrum of polymer/SWNTs compound prepared by the present embodiment and embodiment 1, polymer/SWNTs is multipleThe Raman spectrum (Fig. 8) of compound, without substantive difference, can be learnt: the pyrenyl group in Py-PDEAEMA and containingThe very strong π-π existing between the SWNTs of height conjugated structure interacts.
Polymer/SWNTs compound 21mg of obtaining is dropped in the single port flask of 25mL, add 10mL go fromSub-water, its photo is as shown in left in Figure 6; Speed with 1mL/s passes into CO in reaction system2, solution graduallyBlackening, after 15min, polymer/SWNTs compound dissolves, and its photo as shown in right in Figure 6, obtains polymerConcentration is the homodisperse aqueous solution of the SWNTs of 0.1mg/mL.
The present embodiment prepare transmission electron microscope photo and the enforcement of the dispersion liquid of polymer/SWNTs compound in waterIn example 1, the transmission electron microscope photo of dispersion liquid (Fig. 7), without significant difference, can be found out: SWNTs obtains in the aqueous solutionArrive good dispersion.
Embodiment 4,
(1), synthetic Py-PDEAEMA
A and b step are with embodiment 3.
(2) SWCN is distributed in ethyl acetate
20mgPy-PDEAEMA is dropped in the single port flask of 25mL, add 10mL ethyl acetate, fully moltenSeparate, add 2mgSWNTs, ultrasonic 30min, SWNTs is dispersed in ethyl acetate, obtains polymer denseDegree is 2mg/mL, the homodisperse ethyl acetate solution of SWNTs that SWNTs concentration is 0.2mg/mL.
(3) SWCN is distributed in water
The ethyl acetate solution of polymer/SWNTs compound is spin-dried for, and vacuum drying, obtains polymer/SWNTs multipleCompound solid.
In the Raman spectrum of polymer/SWNTs compound prepared by the present embodiment and embodiment 1, polymer/SWNTs is multipleThe Raman spectrum of compound, without substantive difference, can be learnt: the pyrenyl group in Py-PDEAEMA and contain height conjugationThe very strong π-π existing between the SWNTs of structure interacts.
Polymer/SWNTs compound 22mg of obtaining is dropped in the single port flask of 25mL, add 10mL go fromSub-water passes into CO with the speed of 1mL/s in reaction system2, solution is blackening gradually, after 15min, and polymer/SWNTsCompound dissolves, and obtaining polymer concentration is 2mg/mL, and the SWNTs that SWNTs concentration is 0.2mg/mL evenly dividesThe loose aqueous solution.
Transmission electron microscope photo and the embodiment of polymer/SWNTs compound prepared by the present embodiment dispersion liquid in waterIn 1, the transmission electron microscope photo of dispersion liquid (Fig. 7), without significant difference, can be found out: SWNTs obtains in the aqueous solutionGood dispersion.
Embodiment 5,
(1), synthetic Py-PDEAEMA
580mg pyrene methyl alcohol is dropped into 100mL reaction bulb, add the THF that 25mL is dry, 760mg triethylamine(Et3N), stirring and dissolving, ice bath, is dissolved in 1725mg bromo isobutyl acylbromide in the THF that 25mL is dry, is placed inIn dropping funel, be added dropwise to reaction system, 20min dropwises, and adularescent solid generates, stirring at room temperature reaction 2 days.After reaction finishes, filter, filtrate is transferred in separatory funnel, add 200mL carrene, use respectively saturated chlorineChange ammonium salt solution, saturated sodium bicarbonate solution and saturated nacl aqueous solution extraction, separatory, organic phase is dry through anhydrous magnesium sulfateDry, filter, concentrated, column chromatography (benzinum: carrene=3:1), obtains target product Py-ATRP1.85g,Yield: 97.4%.
The DEAEMA monomer of 16.68g is dropped in the single port flask of a 100mL, add 18mL to be driedDMF, the initator Py-ATRP of the PMDETA of 105mg and 228mg, through once freezing-vacuumize-thawAfter, add the cuprous bromide of 84mg. Whole system, after three freezing-vacuumize-thaw cycles, afterwards will afterwardsFlask is placed in 80 DEG C of oil baths and reacts 10h, and reaction finishes the rear cooled with liquid nitrogen cessation reaction of using. Reactant liquor dialysis, freeze-drying.Obtain target product Py-PDEAEMA (value of i is 22) 2.35g, yield: 87.9%.
(2) SWCN is distributed in toluene
20mgPy-PDEAEMA is dropped in the single port flask of 25mL, adds 10mL toluene, fully dissolve,Add 5mgSWNTs, ultrasonic 30min, SWNTs is dispersed in toluene, and obtaining polymer concentration is 2mg/mL,SWNTs concentration is the homodisperse toluene solution of the SWNTs of 0.5mg/mL.
(3) SWCN is distributed in water
The toluene solution of polymer/SWNTs compound is spin-dried for, and vacuum drying, obtains polymer/SWNTs compoundSolid.
In the Raman spectrum of polymer/SWNTs compound prepared by the present embodiment and embodiment 1, polymer/SWNTs is multipleThe Raman spectrum (Fig. 8) of compound, without substantive difference, can be learnt: the pyrenyl group in Py-PDEAEMA and containingBetween the SWNTs of height conjugated structure, exist very strong π-π to interact.
Polymer/SWNTs compound 25mg of obtaining is dropped in the single port flask of 25mL, add 10mL go fromSub-water passes into CO with the speed of 1mL/s in reaction system2, solution is blackening gradually, after 15min, and polymer/SWNTsCompound dissolves, and obtaining polymer concentration is 2mg/mL, and the SWNTs that SWNTs concentration is 0.5mg/mL evenly dividesThe loose aqueous solution.
Transmission electron microscope photo and the embodiment of polymer/SWNTs compound prepared by the present embodiment dispersion liquid in waterIn 1, the transmission electron microscope photo of dispersion liquid (Fig. 7), without significant difference, can be found out: SWNTs obtains in the aqueous solutionGood dispersion.
The embodiment of the present invention is tested by fluorescence spectrum, Raman spectrum, transmission electron microscope respectively, shown in discoverable type IBetween pyrenyl group in polymer (Py-PDEAEMA) and SWNTs, exist very strong π-π to interact, by π-πInteract, polymer P y-PDEAEMA can be modified the surface of SWNTs, due to the Van der Waals between carbon pipeThe steric restriction effect of the polymeric layer that interaction is adsorbed is offset, thereby has improved the dispersiveness of SWNTs.
Claims (5)
1. polymer shown in formula I is in the application disperseing in SWCN;
In formula I, i is the natural number between 20～150.
2. a process for dispersing for SWCN, comprises the steps: polymer and single wall shown in formula ICNT mixes in organic solvent, realizes the dispersion of described SWCN in organic solvent;
In formula I, i is the natural number between 20～150.
3. process for dispersing according to claim 2, is characterized in that: described SWCN and formula IShown in the mass ratio of polymer be 1:4～20;
Described organic solvent be in toluene, dimethylbenzene, ethyl acetate, propyl acetate and chloroform any;
Polymer shown in formula I and described SWCN mix under ultrasonication.
4. a process for dispersing for SWCN, comprises the steps:
(1) shown in formula I, polymer and SWCN mix in organic solvent; Described in removal, haveThe compound that obtains polymer shown in formula I and SWCN after machine solvent, is labeled as polymer/SWNTsCompound;
In formula I, i is the natural number between 20～150;
(2) described polymer/SWNTs compound is added to the water, passes into CO2Gas realize described listThe dispersion of wall carbon nano tube in water.
5. process for dispersing according to claim 4, is characterized in that: in step (1), described organicSolvent be in toluene, dimethylbenzene, ethyl acetate, propyl acetate and chloroform any;
In step (2), pass into CO2The flow velocity of gas is 0.5～2mL/s;
Described in every 1mg, polymer/SWNTs compound passes into CO2The volume of gas is 30～100mL.
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| CN104528687B (en) * | 2014-12-26 | 2016-06-15 | 清华大学 | A kind of by the reunion of electrochemical redox reversible regulation and control SWCN and scattered method |
| CN104725630B (en) * | 2015-02-03 | 2016-09-21 | 吉林大学 | Containing pyrene PAEK, preparation method and the application in SWCN/polyether-ether-ketone composite material |
| CN104761670B (en) * | 2015-03-19 | 2017-01-25 | 中科院广州化学有限公司 | Caged silsesquioxane-based star polymer, preparation method and application thereof |
| CN106009466A (en) * | 2016-08-01 | 2016-10-12 | 湖南大学 | Modified nano carbon material, carbon material/polymer composite material and preparation method thereof |
| CN115044156A (en) * | 2022-05-10 | 2022-09-13 | 上海工程技术大学 | GO @ Py-PMMA-b-PDMS composite material and preparation method thereof |
| CN116573634A (en) * | 2022-11-29 | 2023-08-11 | 中国科学院苏州纳米技术与纳米仿生研究所 | Method for transferring carbon nano tube aqueous dispersion liquid into organic phase dispersion liquid |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101181989A (en) * | 2007-11-20 | 2008-05-21 | 浙江大学 | Acid choline biomimetic polymers coated carbon-nano tube and preparation method thereof |
| CN103012639A (en) * | 2012-07-16 | 2013-04-03 | 北京科技大学 | Water-soluble cationic polyelectrolyte with end group provided with fluorophore pyrene, and preparation method and application thereof |
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| US7935767B2 (en) * | 2006-12-21 | 2011-05-03 | E. I. Du Pont De Nemours And Company | Multiblock polymer dispersions of carbon nanotubes |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101181989A (en) * | 2007-11-20 | 2008-05-21 | 浙江大学 | Acid choline biomimetic polymers coated carbon-nano tube and preparation method thereof |
| CN103012639A (en) * | 2012-07-16 | 2013-04-03 | 北京科技大学 | Water-soluble cationic polyelectrolyte with end group provided with fluorophore pyrene, and preparation method and application thereof |
Non-Patent Citations (2)
| Title |
|---|
| Reversible Dispersion of Single-Walled Carbon Nanotubes Based on a CO2-Responsive Dispersant;Yan Ding 等;《Langmuir》;20101006;第26卷(第22期);16667-16671 * |
| Water-Soluble Single-Walled Carbon Nanotubes via Noncovalent Sidewall-Functionalization with a Pyrene-Carrying Ammonium Ion;Naotoshi Nakashima 等;《Chemistry Letters》;20020605;第31卷(第6期);638-639 * |
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