CN106905495B - A kind of preparation method of surface modification of carbon nanotube and composite material - Google Patents

A kind of preparation method of surface modification of carbon nanotube and composite material Download PDF

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CN106905495B
CN106905495B CN201710159944.7A CN201710159944A CN106905495B CN 106905495 B CN106905495 B CN 106905495B CN 201710159944 A CN201710159944 A CN 201710159944A CN 106905495 B CN106905495 B CN 106905495B
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CN106905495A (en
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高婷婷
司淑贤
周国伟
王俊豪
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Qilu University of Technology
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Abstract

The invention discloses the preparation methods of a kind of surface modification of carbon nanotube and composite material, carbon nanotube (CNT) is added in tannic acid (TA) aqueous solution, it is added under triethylene tetramine (TETA) room temperature to stir after ultrasound and CNT is modified, by the concentration for adjusting TA, mixing time and the molar ratio of TA and TETA obtain the preferable CNT-PTA/TETA of extent of polymerization, it is modified that bromine is carried out to CNT-PTA/TETA with 2- bromine isobutyl acylbromide (BiBb) again, cause atom transfer radical polymerization (SI-ATRP) method finally by surface to react to obtain CNT-PTA/TETA-Polymer composite material.The present invention is not under conditions of destroying carbon nanotube chemical structure, pass through the noncovalent interaction between polymer and carbon nanotube, and contain more functional groups using polymer chain, the adhesion strength between carbon nanotube can not only be more effectively reduced, and can be made carbon nano tube surface that there is different functionality according to the difference of introduced functional group.

Description

A kind of preparation method of surface modification of carbon nanotube and composite material
Technical field
The invention belongs to field of composite material preparation, and in particular to the system of a kind of surface modification of carbon nanotube and composite material Preparation Method.
Background technique
Carbon nanotube have stable chemical structure, large specific surface area, and have excellent mechanics, thermodynamics, electricity and Optical property makes it have wide application in numerous areas such as capacitor, photoelectric device, energy-storage battery, electrochemical sensors Prospect, thus become research hotspot in recent years.But since carbon nanotube is sp2Hybrid structure keeps its chemical activity poor, molten Bad dispersibility in agent and polymeric matrix, it is easy to reunite, so that its application be made to be restricted.Thus, by carbon Nanotube carries out surface and is modified, and introduces more functional groups on its surface, becoming improves it in solvent and polymeric matrix The important method of dispersibility, further, it is also possible to which it is more functional to assign carbon nanotube.
Surface modification of carbon nanotube is the important method for improving its dispersibility, mainly there is physical method and chemical method.Change After method generally uses strong acid and strong oxidizer to pre-process, makes its surface with functional groups such as carboxyls, then pass through amide again The reactions such as change, esterification are in its surface grafting polymerization object, to improve the dispersibility of carbon nanotube.But chemical method passes through covalently Key effect, destroys the sp of carbon nanotube2Hybrid structure generates certain influence to its mechanical performance and electric property.China Patent CN103803523A report it is a kind of using highly basic and hydrogen peroxide mixed solution processing carbon nanotube after, make itself and tannic acid Reaction, the carbon nanotube by surface modification treatment is evenly dispersed in water and organic solvent and has higher stability.But Highly basic and dioxygen water pretreatment carbon nanotube can destroy the original chemical structure of carbon nanotube, and the carbon after this method modification is received Nanotube surface functional group is less and single, limits and is further modified to it and its multi-functional.
For the deficiency of surface modification of carbon nanotube method in the prior art, therefore, it is necessary to further study a kind of new The surface modification of carbon nanotube method of type.
Summary of the invention
The present invention overcomes the deficiency of the above method, the present invention provides the preparation side of a kind of carbon nanotube and composite material Method, this method pass through the non-covalent work between polymer and carbon nanotube under conditions of not destroying carbon nanotube chemical structure With obtaining the modified carbon nano-tube material in surface.
The technical scheme adopted by the invention is as follows:
A kind of surface modifying method of carbon nanotube, comprising the following steps:
(1) by the aqueous solution of carbon nanotube (CNT) ultrasonic disperse to tannic acid (TA), triethylene four is added under stiring Amine (TETA), is dried after mixing evenly, obtains CNT-P (TA-TETA)；The mass ratio of described CNT, TA are 1:(0.1-1), TA, The molar ratio of TETA is 1:(1-20)；
(2) Br is introduced into CNT-P (TA-TETA) using acylbromide reaction, is prepared into CNT-P (TA-TETA)-Br；
(3) cause atom transfer radical polymerization (SI-ATRP) reaction using surface and polymer chain is grafted to CNT-P (TA-TETA) in-Br, so that CNT-P (TA-TETA)-Br is prepared into CNT-P (TA-TETA)-Polymer.
In step (1), the concentration of aqueous solution of the tannic acid are as follows: 25-1000 μ g/mL；Reaction condition are as follows: in 20-35 DEG C, revolving speed be 500 ± 1rpm under conditions of stir 0-48h (preferably 2-24h)；Drying condition is to be dried in vacuo 8- at 40-80 DEG C 20h。
In step (2), conventional acylbromide reaction can be used, Br is introduced into CNT-P (TA-TETA), to the method not into Row is particularly limited to.For the pattern of reaction efficiency and finally obtained product, structure, it is preferred that specific method step are as follows: will CNT-P (TA-TETA) and triethylamine are successively added in tetrahydrofuran (THF), and 2- bromine isobutyryl is added dropwise in ice-water bath stirring After bromine (BIBb), drying is washed after stirring to acylbromide fully reacting under room temperature, obtains CNT-P (TA-TETA)-Br.
Preferably, the drying condition is to be dried in vacuo 8-20h at 40-80 DEG C.
In step (3), conventional surface can be used and cause atom transfer radical polymerization (SI-ATRP) reaction for polymer Chain is grafted in CNT-P (TA-TETA)-Br, and the method is not particularly limited.From reaction efficiency and finally obtained production For the patterns of product, structure, it is preferred that specific method step are as follows: after mixing water, methanol, monomer, catalyst, complexant, lead to N2Air is excluded, CNT-P (TA-TETA)-Br is added in above-mentioned solution, N2Under be stirred to react, with surface cause atom transfer from (SI-ATRP) method is polymerize by base, obtains CNT-P (TA-TETA)-Polymer, centrifuge washing is dry.
The monomer is any monomer that can carry out ATRP reaction；Drying condition is to be dried in vacuo at 40-80 DEG C 8-20h。
A kind of carbon nanotube that surface is modified is prepared by the above method of modifying, its main feature is that: the carbon nanotube table Uniformly coat one layer of P (TA-TETA)-Polymer composite material on face, this layer of composite material with a thickness of 2~5nm.The present invention By polymer chain and carbon nanotube by noncovalent interaction in conjunction with, do not destroy original chemical structure of carbon nanotube, the table The modified carbon nano-tube material in face has wide in numerous areas such as capacitor, photoelectric device, energy-storage battery, electrochemical sensors Application prospect.
Compared with prior art, technical solution of the present invention has the following beneficial effects:
Surface modification of carbon nanotube method raw material according to the present invention is inexpensive, and production cost is low, short processing time and peace It is complete simple.Invention further provides more possibilities of surface modification of carbon nanotube, can be by changing in polymerization reaction Monomer introduce more kinds of different functional groups.
The present invention is not under conditions of destroying carbon nanotube chemical structure, by non-total between polymer and carbon nanotube Valence effect, and contain more functional groups using polymer chain, the adhesion strength between carbon nanotube can not only be more effectively reduced, It can be made carbon nano tube surface that there is different functionality according to the difference of introduced functional group again, realize carbon nano tube surface Non-covalent modification and multifunction, with greater advantage.
Detailed description of the invention
Fig. 1 is original carbon nanotubes and the infrared spectroscopy by the modified carbon nano tube compound material in surface in the present invention Figure.
Fig. 2 is high-resolution-ration transmission electric-lens (HRTEM) figure by the modified carbon nano tube compound material in surface.
Specific embodiment
It is noted that described further below be all exemplary, it is intended to provide further instruction to the present invention.Unless another It indicates, all technical and scientific terms used herein has usual with general technical staff of the technical field of the invention The identical meanings of understanding.
It should be noted that term used herein above is merely to describe specific embodiment, and be not intended to restricted root According to exemplary embodiments of the present invention.As used herein, unless the context clearly indicates otherwise, otherwise singular Also it is intended to include plural form, additionally, it should be understood that, when in the present specification using term "comprising" and/or " packet Include " when, indicate existing characteristics, step, operation and/or their combination.
As background technique is introduced, there is some shortcomings for carbon nano-tube modification method in the prior art, to understand Technical problem certainly as above, the invention proposes a kind of surface modifying methods of carbon nanotube, comprising the following steps:
(1) by the aqueous solution of carbon nanotube (CNT) ultrasonic disperse to tannic acid (TA), triethylene four is added under stiring Amine (TETA), is dried after mixing evenly, obtains CNT-P (TA-TETA)；
(2) CNT-P (TA-TETA) and triethylamine of above-mentioned preparation are successively added in tetrahydrofuran (THF), ice-water bath Stirring after 2- bromine isobutyl acylbromide (BIBb) is added dropwise, washs drying after stirring to acylbromide fully reacting under room temperature, obtains CNT- P(TA-TETA)-Br；
(3) after mixing water, methanol, monomer, catalyst, complexant in a reservoir, lead to N2Air is excluded, by CNT-P (TA-TETA)-Br is added in above-mentioned solution, N2Under be stirred to react, with surface cause atom transfer radical polymerization (SI-ATRP) Method, obtains CNT-P (TA-TETA)-Polymer, and centrifuge washing is dry.
In step (1), each structural unit of tannin acid molecule is made of polycyclic aromatic core and active function groups, Active function groups include: phenolic hydroxyl group, hydroxyl etc., have good absorption dispersibility.Triethylene tetramine is thick pale yellow liquid Body is dissolved in water, ethyl alcohol and acid, is slightly soluble in ether；Volatility is low, and hygroscopicity is strong, is in strong basicity.
One of key technology of the invention is step (1): can be by CNT-P (TA- that non-covalent bond effect obtains TETA) polymer, wherein the ammonia that tannic acid (or tannic acid) passes through the functional groups and triethylene tetramine such as the phenolic hydroxyl group of its own Base occurs functional group's condensation reaction and obtains poly- (tannic acid-triethylene tetramine), i.e. P (TA-TETA), then the polymer passes through model De Huali is deposited on the surface of carbon nanotubes, and this active force is sufficiently large, it is sufficient to so that P (TA-TETA) and carbon nanotube jail Consolidation, which is closed, obtains CNT-P (TA-TETA) polymer, and the present invention forms tool after exactly tannic acid being utilized to react with triethylene tetramine There is the polymer of powerful adsorption capacity, thus the CNT-P (TA- formed with carbon nanotube by intermolecular interaction force TETA)。
The concentration of aqueous solution of the tannic acid are as follows: 25-1000 μ g/mL；Reaction condition are as follows: be in 20-35 DEG C, revolving speed 0-48h (preferably 2-24h) is stirred under conditions of 500 ± 1rpm；Drying condition is to be dried in vacuo 8-20h at 40-80 DEG C.
The preferable CNT-PTA/ of extent of polymerization is obtained by the molar ratio of concentration, mixing time and the TA and TETA that adjust TA TETA especially gropes the ratio between the dosage for having obtained carbon nanotube, tannic acid and triethylene tetramine the experiment has found that carbon nanotube, The dosage of tannic acid and triethylene tetramine has finally obtained CNT-P (TA-TETA)-Polymer and its pattern important It influences, the preferable CNT-P of extent of polymerization (TA-TETA) can be obtained by adjusting the ratio between its suitable raw material, to be subsequently generated shape The preferable polymer material of looks provides basis.The ratio between inappropriate raw material, which will lead to, cannot form with uniform clad structure Carbon nano-tube material.Optimized to obtain, the mass ratio of described CNT, TA are 1:(0.1-1), the molar ratio of TA, TETA are 1:(1- 20)。
In step (2), acylbromide reaction is the technical method that this field routinely knows, the skill of specific reaction condition this field Art personnel can routinely determine.The drying condition is to be dried in vacuo 8-20h at 40-80 DEG C.
In step (3), ATRP is the method for Macroscopic single crystal well known to those skilled in the art, it is one multi-component Reaction system, mainly composition includes monomer, initiator, catalyst, complexant and solvent.Specific raw material, raw material dosage and Reaction condition can be obtained routinely.
The monomer is that can carry out any monomer of ATRP reaction, such as can illustrate out, phenylethylene, methyl-prop Olefin(e) acid esters, vinyl cyanide, (methyl) acrylic amide, methacrylic etc..In some embodiments of the invention, The monomer is n-isopropyl acrylamide, dimethylaminoethyl methacrylate, glycidyl methacrylate.
The catalyst is common catalyst in ATRP reaction, such as can be enumerated, and Cu, Ru, Rh, Ni, Pd, Pb were waited Metal ion is crossed, in some embodiments of the invention, the catalyst is CuBr.
The complexant is common complexant in ATRP reaction, such as can be enumerated, containing n-donor ligand, and phosphorous ligand contains Oxygen ligand and some mixed bodies etc., and for copper catalyst system, the most common ligand is containing n-donor ligand, such as 2,2- bipyridyl, N, N, N, N, N "-pentamethyl-diethylenetriamine (PMDETA) and three-(2- dimethylaminoethyl) amine etc..Of the invention some specific In embodiment, the complexant is 2,2- bipyridyl or PMDETA.
The drying condition is to be dried in vacuo 8-20h at 40-80 DEG C.
A kind of carbon nanotube that surface is modified is prepared by the above method of modifying, is uniformly wrapped in the carbon nano tube surface Cover one layer of P (TA-TETA)-Polymer composite material, as shown in Fig. 2, this layer of composite material with a thickness of 2~5nm.
The present invention by polymer chain and carbon nanotube by noncovalent interaction in conjunction with, do not destroy the original of carbon nanotube Chemical structure, the modified carbon nano-tube material in the surface are all in capacitor, photoelectric device, energy-storage battery, electrochemical sensor etc. It is multi-field to have broad application prospects.
In order to enable those skilled in the art can clearly understand technical solution of the present invention, below with reference to tool The embodiment of the body technical solution that the present invention will be described in detail.
Embodiment 1:
(1) 80mL distilled water and 20mg TA are added in beaker；80mg CNT, ultrasound is added into solution under stiring 10min is stirred to react for 24 hours at 25 DEG C after 10 μ L TETA are added.After the reaction was completed with distilled water by obtained product repeatedly Centrifuge washing, dry 12h, obtains CNT-P (TA-TETA) composite material at 50 DEG C.
(2) in the 100mL three-necked flask for being added to CNT-P (TA-TETA) and 50mL THF, stirred at 0 DEG C, dropwise plus Enter 1mL triethylamine and 0.9mL BIBb, is warmed to room temperature lower reaction 4h after reacting 1h at 0 DEG C.After the reaction was completed by obtained production Object is centrifuged repeatedly washing, is dried in vacuo 12h at 60 DEG C, obtains CNT-P (TA-TETA)-Br.
(3) by the mixed liquor of 1.5g n-isopropyl acrylamide (NIPAm) monomer and 30mL 1:1 (v:v) first alcohol and water It is added in tool test tube at 30 DEG C and leads to N2Gas agitating 20min, be then added 165 μ L pentamethyl-diethylenetriamines (PMDETA) and 48mg CuBr, solution become light green color from colourless, continue logical N2Gas agitating 20min.N220mg CNT- is rapidly joined under gas shielded P (TA-TETA)-Br reacts 40min.Obtained product is centrifuged repeatedly washing after the reaction was completed, is dried in vacuo at 40 DEG C 12h obtains CNT-P (TA-TETA)-PNIPAm, infrared spectrogram as shown in Figure 1, from the curve of Fig. 1 as it can be seen that generate CNT-P (TA-TETA)-PNIPAm polymer has amide feature structure absorption peak (C=O, the 1630cm of NIPAm-1Left and right, N-H, 1530cm-1Left and right), show successfully grafted polymer.The structure shape of CNT-P (the TA-TETA)-PNIPAm composite material Looks as indicated with 2, it is clear from figure 2 that carbon nano tube surface is uniformly coated with one layer of composite material, with a thickness of 2~ 5nm, the composite material are P (TA-TETA)-PNIPAm.Can be seen that method of the invention from the above two width figure can successfully obtain To carbon nano tube compound material.
Embodiment 2:
(1) 100mL distilled water and 100mg TA are added in beaker；100mg CNT is added into solution under stiring, surpasses Sound 10min is stirred to react for 24 hours at 25 DEG C after 50 μ L TETA are added.It is with distilled water that obtained product is anti-after the reaction was completed Centrifuge washing is answered, dry 12h at 50 DEG C obtains CNT-P (TA-TETA) composite material.
(2) in the 100mL three-necked flask for being added to CNT-P (TA-TETA) and 50mL THF, stirred at 0 DEG C, dropwise plus Enter 1mL triethylamine and 0.9mL BIBb, is warmed to room temperature lower reaction 4h after reacting 1h at 0 DEG C.After the reaction was completed by obtained production Object is centrifuged repeatedly washing, is dried in vacuo 12h at 60 DEG C, obtains CNT-P (TA-TETA)-Br.
(3) mixed liquor of 1.5g NIPAm monomer and 30mL 1:1 (v:v) first alcohol and water is added to 30 in tool test tube Lead to N at DEG C2Gas agitating 20min, is then added 165 μ L PMDETA and 48mg CuBr, and solution becomes light green color from colourless, continues Logical N2Gas agitating 20min.N220mg CNT-P (TA-TETA)-Br is rapidly joined under gas shielded, reacts 40min.After the reaction was completed Obtained product is centrifuged repeatedly washing, is dried in vacuo 12h at 40 DEG C, obtains CNT-P (TA-TETA)-PNIPAm, structure Pattern is as shown in Figure 2.
Embodiment 3:
(1) 100mL distilled water and 100mg TA are added in beaker；100mg CNT is added into solution under stiring, surpasses Sound 10min is stirred to react for 24 hours at 25 DEG C after 10 μ L TETA are added.It is with distilled water that obtained product is anti-after the reaction was completed Centrifuge washing is answered, dry 12h at 50 DEG C obtains CNT-P (TA-TETA) composite material.
(2) in the 100mL three-necked flask for being added to CNT-P (TA-TETA) and 50mL THF, stirred at 0 DEG C, dropwise plus Enter 1mL triethylamine and 0.9mL BIBb, is warmed to room temperature lower reaction 4h after reacting 1h at 0 DEG C.After the reaction was completed by obtained production Object is centrifuged repeatedly washing, is dried in vacuo 12h at 60 DEG C, obtains CNT-P (TA-TETA)-Br.
(3) mixed liquor of 1.5g NIPAm monomer and 30mL 1:1 (v:v) first alcohol and water is added to 30 in tool test tube Lead to N at DEG C2Gas agitating 20min, is then added 165 μ L PMDETA and 48mg CuBr, and solution becomes light green color from colourless, continues Logical N2Gas agitating 20min.N220mg CNT-P (TA-TETA)-Br is rapidly joined under gas shielded, reacts 40min.After the reaction was completed Obtained product is centrifuged repeatedly washing, is dried in vacuo 12h at 40 DEG C, obtains CNT-P (TA-TETA)-PNIPAm, structure Pattern is as shown in Figure 2.
Embodiment 4:
(1) 100mL distilled water and 100mgTA are added in beaker；100mg CNT is added into solution under stiring, surpasses Sound 10min is stirred to react for 24 hours at 25 DEG C after 200 μ L TETA are added.After the reaction was completed with distilled water by obtained product It is centrifuged repeatedly washing, dry 12h at 50 DEG C obtains CNT-P (TA-TETA) composite material.
(2) in the 100mL three-necked flask for being added to CNT-P (TA-TETA) and 50mL THF, stirred at 0 DEG C, dropwise plus Enter 1mL triethylamine and 0.9mL BIBb, is warmed to room temperature lower reaction 4h after reacting 1h at 0 DEG C.After the reaction was completed by obtained production Object is centrifuged repeatedly washing, is dried in vacuo 12h at 60 DEG C, obtains CNT-P (TA-TETA)-Br.
(3) mixed liquor of 1.5g NIPAm monomer and 30mL 1:1 (v:v) first alcohol and water is added to 30 in tool test tube Lead to N at DEG C2Gas agitating 20min, is then added 165 μ L PMDETA and 48mg CuBr, and solution becomes light green color from colourless, continues Logical N2Gas agitating 20min.N220mg CNT-P (TA-TETA)-Br is rapidly joined under gas shielded, reacts 40min.After the reaction was completed Obtained product is centrifuged repeatedly washing, is dried in vacuo 12h at 40 DEG C, obtains CNT-P (TA-TETA)-PNIPAm, structure Pattern is as shown in Figure 2.
Embodiment 5:
(1) 80mL distilled water and 20mg TA are added in beaker；80mg CNT, ultrasound is added into solution under stiring 10min is stirred to react 2h at 25 DEG C after 10 μ L TETA are added.After the reaction was completed with distilled water by obtained product repeatedly Centrifuge washing, dry 12h, obtains CNT-P (TA-TETA) composite material at 50 DEG C.
(2) in the 100mL three-necked flask for being added to CNT-P (TA-TETA) and 50mL THF, stirred at 0 DEG C, dropwise plus Enter 1mL triethylamine and 0.9mL BIBb, is warmed to room temperature lower reaction 4h after reacting 1h at 0 DEG C.After the reaction was completed by obtained production Object is centrifuged repeatedly washing, is dried in vacuo 12h at 60 DEG C, obtains CNT-P (TA-TETA)-Br.
(3) mixed liquor of 1.5g NIPAm monomer and 30mL 1:1 (v:v) first alcohol and water is added to 30 in tool test tube Lead to N at DEG C2Gas agitating 20min, is then added 165 μ L PMDETA and 48mg CuBr, and solution becomes light green color from colourless, continues Logical N2Gas agitating 20min.N220mg CNT-P (TA-TETA)-Br is rapidly joined under gas shielded, reacts 40min.After the reaction was completed Obtained product is centrifuged repeatedly washing, is dried in vacuo 12h at 40 DEG C, obtains CNT-P (TA-TETA)-PNIPAm, structure Pattern is as shown in Figure 2.
Embodiment 6:
(1) 80mL distilled water and 20mg TA are added in beaker；80mg CNT, ultrasound is added into solution under stiring 10min is stirred to react 48h at 25 DEG C after 10 μ L TETA are added.After the reaction was completed with distilled water by obtained product repeatedly Centrifuge washing, dry 12h, obtains CNT-P (TA-TETA) composite material at 50 DEG C.
(2) in the 100mL three-necked flask for being added to CNT-P (TA-TETA) and 50mL THF, stirred at 0 DEG C, dropwise plus Enter 1mL triethylamine and 0.9mL BIBb, is warmed to room temperature lower reaction 4h after reacting 1h at 0 DEG C.After the reaction was completed by obtained production Object is centrifuged repeatedly washing, is dried in vacuo 12h at 60 DEG C, obtains CNT-P (TA-TETA)-Br.
(3) mixed liquor of 1.5g NIPAm monomer and 30mL 1:1 (v:v) first alcohol and water is added to 30 in tool test tube Lead to N at DEG C2Gas agitating 20min, is then added 165 μ L PMDETA and 48mg CuBr, and solution becomes light green color from colourless, continues Logical N2Gas agitating 20min.N220mg CNT-P (TA-TETA)-Br is rapidly joined under gas shielded, reacts 40min.After the reaction was completed Obtained product is centrifuged repeatedly washing, is dried in vacuo 12h at 40 DEG C, obtains CNT-P (TA-TETA)-PNIPAm, structure Pattern is as shown in Figure 2.
Embodiment 7:
(1) 100mL distilled water and 10mg TA are added in beaker；100mg CNT is added into solution under stiring, surpasses Sound 10min is stirred to react for 24 hours at 25 DEG C after 5 μ L TETA are added.It is with distilled water that obtained product is anti-after the reaction was completed Centrifuge washing is answered, dry 12h at 50 DEG C obtains CNT-P (TA-TETA) composite material.
(2) in the 100mL three-necked flask for being added to CNT-P (TA-TETA) and 50mL THF, stirred at 0 DEG C, dropwise plus Enter 1mL triethylamine and 0.9mL BIBb, is warmed to room temperature lower reaction 4h after reacting 1h at 0 DEG C.After the reaction was completed by obtained production Object is centrifuged repeatedly washing, is dried in vacuo 12h at 60 DEG C, obtains CNT-P (TA-TETA)-Br.
(3) mixed liquor of 1.5g NIPAm monomer and 30mL 1:1 (v:v) first alcohol and water is added to 30 in tool test tube Lead to N at DEG C2Gas agitating 20min, is then added 165 μ L PMDETA and 48mg CuBr, and solution becomes light green color from colourless, continues Logical N2Gas agitating 20min.N220mg CNT-P (TA-TETA)-Br is rapidly joined under gas shielded, reacts 40min.After the reaction was completed Obtained product is centrifuged repeatedly washing, is dried in vacuo 12h at 40 DEG C, obtains CNT-P (TA-TETA)-PNIPAm, structure Pattern is as shown in Figure 2.
Embodiment 8:
(1) 400mL distilled water and 20mg TA are added in beaker；80mg CNT, ultrasound is added into solution under stiring 10min is stirred to react for 24 hours at 25 DEG C after 10 μ L TETA are added.After the reaction was completed with distilled water by obtained product repeatedly Centrifuge washing, dry 12h, obtains CNT-P (TA-TETA) composite material at 50 DEG C.
(2) in the 100mL three-necked flask for being added to CNT-P (TA-TETA) and 50mL THF, stirred at 0 DEG C, dropwise plus Enter 1mL triethylamine and 0.9mL BIBb, is warmed to room temperature lower reaction 4h after reacting 1h at 0 DEG C.After the reaction was completed by obtained production Object is centrifuged repeatedly washing, is dried in vacuo 12h at 60 DEG C, obtains CNT-P (TA-TETA)-Br.
(3) mixed liquor of 1.5g NIPAm monomer and 30mL 1:1 (v:v) first alcohol and water is added to 30 in tool test tube Lead to N at DEG C2Gas agitating 20min, is then added 165 μ L PMDETA and 48mg CuBr, and solution becomes light green color from colourless, continues Logical N2Gas agitating 20min.N220mg CNT-P (TA-TETA)-Br is rapidly joined under gas shielded, reacts 40min.After the reaction was completed Obtained product is centrifuged repeatedly washing, is dried in vacuo 12h at 40 DEG C, obtains CNT-P (TA-TETA)-PNIPAm, structure Pattern is as shown in Figure 2.
Embodiment 9:
(1) 80mL distilled water and 20mg TA are added in beaker；80mg CNT, ultrasound is added into solution under stiring 10min is stirred to react for 24 hours at 25 DEG C after 10 μ L TETA are added.After the reaction was completed with distilled water by obtained product repeatedly Centrifuge washing, dry 12h, obtains CNT-P (TA-TETA) composite material at 50 DEG C.
(2) in the 100mL three-necked flask for being added to CNT-P (TA-TETA) and 50mL THF, stirred at 0 DEG C, dropwise plus Enter 1mL triethylamine and 0.9mL BIBb, is warmed to room temperature lower reaction 4h after reacting 1h at 0 DEG C.After the reaction was completed by obtained production Object is centrifuged repeatedly washing, is dried in vacuo 12h at 60 DEG C, obtains CNT-P (TA-TETA)-Br.
(3) by the mixed of 2mL dimethylaminoethyl methacrylate (DMAEMA) monomer and 20mL 1:1 (v:v) first alcohol and water It closes liquid and is added in tool test tube and lead to N at room temperature2Then 120mg 2,2- bipyridyl and 60.8mg is added in gas agitating 20min CuBr, solution become kermesinus from colourless, continue logical N2Gas agitating 20min.N220mg CNT-P (TA- is rapidly joined under gas shielded TETA)-Br reacts 2h.Obtained product is centrifuged repeatedly washing after the reaction was completed, 12h is dried in vacuo at 40 DEG C, obtains CNT-P(TA-TETA)-PDMAEMA。
Embodiment 10:
(1) 80mL distilled water and 20mg TA are added in beaker；80mg CNT, ultrasound is added into solution under stiring 10min is stirred to react for 24 hours at 25 DEG C after 10 μ L TETA are added.After the reaction was completed with distilled water by obtained product repeatedly Centrifuge washing, dry 12h, obtains CNT-P (TA-TETA) composite material at 50 DEG C.
(2) in the 100mL three-necked flask for being added to CNT-P (TA-TETA) and 50mL THF, stirred at 0 DEG C, dropwise plus Enter 1mL triethylamine and 0.9mL BIBb, is warmed to room temperature lower reaction 4h after reacting 1h at 0 DEG C.After the reaction was completed by obtained production Object is centrifuged repeatedly washing, is dried in vacuo 12h at 60 DEG C, obtains CNT-P (TA-TETA)-Br.
(3) by the mixed liquor of 6mL glycidyl methacrylate (GMA) monomer and 30mL 4:1 (v:v) first alcohol and water It is added in tool test tube and leads to N at room temperature2Then 0.17g 2,2- bipyridyl and 63mg CuBr is added in gas agitating 20min, molten Liquid becomes kermesinus from colourless, continues logical N2Gas agitating 20min.N220mg CNT-P (TA-TETA)-is rapidly joined under gas shielded Br reacts 50min.Obtained product is centrifuged repeatedly washing after the reaction was completed, 12h is dried in vacuo at 40 DEG C, obtains CNT-P (TA-TETA)-PGMA。
The above embodiment is a preferred embodiment of the present invention, but embodiments of the present invention are not by above-described embodiment Limitation, other any changes, modifications, substitutions, combinations, simplifications made without departing from the spirit and principles of the present invention, It should be equivalent substitute mode, be included within the scope of the present invention.

Claims (10)

1. a kind of surface modifying method of carbon nanotube, characterized in that the following steps are included:
(1) by the aqueous solution of carbon nanotube (CNT) ultrasonic disperse to tannic acid (TA), triethylene tetramine is added under stiring (TETA), it dries after mixing evenly, obtains CNT-P (TA-TETA)；The mass ratio of described CNT, TA are 1:(0.1-1), TA, The molar ratio of TETA is 1:(1-20)；
(2) Br is introduced into CNT-P (TA-TETA) using acylbromide reaction, is prepared into CNT-P (TA-TETA)-Br；
(3) cause atom transition free radical polymerization reaction using surface polymer chain is grafted in CNT-P (TA-TETA)-Br, To which CNT-P (TA-TETA)-Br is prepared into CNT-P (TA-TETA)-Polymer.
2. the method as described in claim 1, characterized in that in step (1), the concentration of aqueous solution of the tannic acid are as follows: 25- 1000μg/mL。
3. the method as described in claim 1, characterized in that in step (1), reaction condition are as follows: in 20-35 DEG C, revolving speed 500 0-48h is stirred under conditions of ± 1rpm；Drying condition is to be dried in vacuo 8-20h at 40-80 DEG C.
4. the method as described in claim 1, characterized in that the specific method step of step (2) are as follows: by CNT-P (TA-TETA) It is successively added to triethylamine in tetrahydrofuran (THF), ice-water bath stirring, after 2- bromine isobutyl acylbromide (BIBB) is added dropwise, often Drying is washed after lower stirring to the acylbromide fully reacting of temperature, obtains CNT-P (TA-TETA)-Br.
5. method as claimed in claim 4, characterized in that the drying condition is to be dried in vacuo 8-20h at 40-80 DEG C.
6. the method as described in claim 1, characterized in that the specific method step of step (3) are as follows: by water, methanol, monomer, After catalyst, complexant mixing, lead to N2Air is excluded, CNT-P (TA-TETA)-Br is added in above-mentioned solution, N2Lower stirring is anti- It answers, causes atom transfer radical polymerization (SI-ATRP) method with surface, obtain CNT-P (TA-TETA)-Polymer, be centrifuged Washing, it is dry.
7. method as claimed in claim 6, characterized in that drying condition is to be dried in vacuo 8-20h at 40-80 DEG C.
8. using the modified carbon nanotube in the surface that method according to any one of claims 1 to 7 is prepared.
9. carbon nanotube as claimed in claim 8, characterized in that uniformly coat one layer of P (TA- in the carbon nano tube surface TETA)-Polymer composite material, this layer of composite material with a thickness of 2~5nm.
10. the modified carbon nanotube in surface described in claim 8 or 9 is in capacitor, photoelectric device, energy-storage battery, electrochemistry Application in sensor.
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