CN101224884A - Preparation method of benzene sulfochloride substituted carbon nano-tube and grafting modification method initiated thereby - Google Patents
Preparation method of benzene sulfochloride substituted carbon nano-tube and grafting modification method initiated thereby Download PDFInfo
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- CN101224884A CN101224884A CNA200810080406XA CN200810080406A CN101224884A CN 101224884 A CN101224884 A CN 101224884A CN A200810080406X A CNA200810080406X A CN A200810080406XA CN 200810080406 A CN200810080406 A CN 200810080406A CN 101224884 A CN101224884 A CN 101224884A
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Abstract
The invention relates to a method for processing a carbon nanometer tube so that a special initiation functional group can be formed on the surface, which is utilized to initiate and form graft decoration on the tube surface. The method provided by this invention is that purification treatment is carried out on the carbon tube, the attached catalyst and other impurities on the carbon tube surface, then the purified carbon tube is prepared into a benzene-substituted carbon tube, then substitution reaction for a benzene ring of the benzene-substituted carbon tube is carried out, thus producing benzene sulfonyl chloride-substituted carbon tube. In the invention, the carbon tube used for preparing the benzene sulfonyl chloride substitution can adopt free radical addition reaction.
Description
Technical field
The present invention relates to a kind of carbon nano-tube modified method, be for satisfying the requirement in different application field more exactly, for example can high dispersing in solution, or be used to prepare the carbon nanotube that has ad hoc structure, and carbon nanotube is handled, make it the surface and form specific initiation functional group, and utilize formed particular functional group to cause the method for the grafting and modifying that forms tube-surface.
Background technology
CNT (carbon nano-tube) (carbon nanotubes) is just found a kind of novel carbon structure in 1991, it is the individual layer that is rolled into by the Graphene lamella that carbon atom forms to tens of layers coaxial, seamless, hollow tube body, the distance that is maintained fixed between layer and the layer, about 0.34nm.It is that a kind of to have radial dimension be nanometer scale, and axial dimension is that micron dimension, pipe two ends have the novel carbon structure that soccerballene hemisphere seals.Press the classification of the lamella graphite number of plies, can be divided into Single Walled Carbon Nanotube (Single-walled carbon nanotubes) and multiple-wall carbon nanotube (Multi-walled carbon nanotubes), Single Walled Carbon Nanotube can be regarded as to be curled by the individual layer flake graphite and forms, and multi-walled carbon nano-tubes can be regarded as the Single Walled Carbon Nanotube suit of different diameter and forms.Because the nanometer grade diameter and the micron order length of CNT (carbon nano-tube), it has the length-to-diameter ratio up to 1000, is regarded as quasi-one-dimensional nanometer material.
The mechanical property of discovering carbon nanotube is relevant with its structure.Carbon-carbon bond in the Graphene plane is one of occurring in nature the strongest known chemical bond, sp
2The C=C covalent linkage that hydridization forms is formed.The structure of CNT (carbon nano-tube) is complete Graphene grid, has unique one dimension tracheary element structure, it is by one of the strongest valence link of nature that its perfect hexagon topological framework does not almost have the defective carbon nanotube, therefore carbon nanotube is one of all the most solid known, materials that rigidity is the highest [V.R.Coluci, S.O.Dantas, A.Jorio, D.S.Galvao, Phys.Rev.B 75,2007; A.Pantano, M.C.Boyce, D.M.Parks, Phys.Rev.Lett.91,2003; Z.Gu, H.Peng, R.H.Hauge, R.E.Smalley, J.L.Margrave, NanoLett.2,2002,1009].The carbon nanotube of tactical rule has better mechanical property, and especially the very perfect Single Walled Carbon Nanotube of structure has high mechanical property and great aspect ratio, becomes the best filler of the superpower matrix material of preparation.Yet this can not disperse carbon nanotube in most of solvents, and the practical application carbon nanotube is hindered all the time as filler.Simultaneously, the specific surface area that carbon nanotube is big has big Van der Waals force, causes self seriously reuniting and be difficult to being dispersed in matrices of composite material equably.
Polymer graft is carbon nano-tube modified method in common, because can largely not destroy its electrical properties at the few fault location grafting and modifying soluble high-molecular of carbon nano tube surface, so this method is a kind of alternative mode that is hopeful.Nineteen ninety-five Malyjaszewki etc. proposes the notion of atom transfer radical polymerization (ATRP) first, for radical living polymerization has been opened up a brand-new approach.In numerous controlled reactive polymer grafting methods, atom transfer radical polymerization (ATRP) is high flexible, effective and the most widely used technology, can carry out the grafting of polymer molecule segment under the reaction conditions of gentleness.
Complex compound (catalyzer) three parts that the ATRP initiator system is made up of simple Organohalogen compounds (initiator), low-valent transition metals and suitable part are formed, by a series of redox reaction, between spike and dormancy kind, set up reversible running balance, realized living polymerization and the control of polymericular weight.The initiator homolysis produces the content of free radical and molecular weight size and the distribution that the efficient decision generates polymkeric substance, catalyzer is to contain transistion metal compound and contain the complex compound that strong part such as N, O, P is formed, the main effect of part is to form complex compound with transition metal, make it be dissolved in organic solvent, adjust the redox potential of central metal.
Chinese invention patent 200310121617.0 discloses a kind of responsive to temperature type water-soluble carbon nanometer tube and preparation method thereof, and this method is to make its surface have initiating group after carbon nanotube is handled; Contain two key responsive to temperature type polymerisation with the atom transition free radical polymerization reaction initiation then, obtain the responsive to temperature type water-soluble carbon nanometer tube.Its concrete way is: will handle with the effective acylating agent of the carbon after the strong oxidizing property acid treatment and obtain acylated carbon nano-tube; again the acidylate carbon nanotube is handled with polyvalent alcohol or polyamine and obtained the carbon nanotube that the surface has hydroxyl or amido; the surface being had the carbon nanotube of hydroxyl or amido and alpha-halogen carboxylic acid halides reacts and obtains the carbon nanotube that the surface has initiating group again; the carbon nanotube that again surface is had an initiating group under protection of inert gas with N; N. DMAA or N. N-isopropylacrylamide monomer reaction finally obtain the water miscible carbon nanotube of responsive to temperature type.Initiator is that carboxyl from acidifying carbon pipe begins to react in this method, the amount that is to say initiator is fewer, only produce living radical initiator in port and pipe arm defective, the dispersiveness that not only makes carbon pipe initiator is not finely to influence radical polymerization efficient, and does not make functional polymer amount on the final grafting and modifying high and reduced the functional of matrix material.If improve the amount of surperficial initiator, then need the carbon pipe is carried out more intensive oxidation, to introduce more defects, might reduce the intensity of carbon pipe, and cause the brachymemma of carbon pipe.
At present, the research for the carbon nano-tube modified method of atom transfer radical polymerization graft reaction is centered around carbon nano tube surface fixedly initiator and the monomeric polymerization of realization functionalization, block polymerization and copolymerization expansion substantially.Wherein, construct that efficient initiator carries out and insufficient in carbon nano tube surface, some are initiator molecule and the covalently bound technology barrier that exists of carbon nanotube efficiently.The carbon nano-tube modified range of application of atom transfer radical polymerization graft reaction will be greatly expanded in the solution of this problem, such as the carrier of polymkeric substance reinforcing filler, drug delivery, the load of catalyst particle etc.
Summary of the invention
The invention provides a kind of prior art deficiency that overcomes, can effectively make up the method for efficient initiator at the carbon tube-surface, method is prepared a kind of carbon pipe that has efficient initiator thus, and then realizes the modification grafting processing of carbon nanotube on this carbon pipe basis.The present invention proposes the effective initiator synthetic route of a novelty, initiator provided by the invention can be the new way that has improved living polymerization process controllability in the good dispersiveness of the medium-term and long-term maintenance of organic solvent.
The carbon pipe that has efficient initiating radical of the present invention is meant the carbon pipe that benzene sulfonyl chloride replaces, its preparation method is earlier the carbon pipe to be carried out purification process, catalyzer of giving as an addition on the removal carbon tube-surface and other impurity, then the carbon pipe after the purified processing is prepared as the carbon pipe that benzene replaces, the carbon pipe that benzene is replaced carries out the substitution reaction on the phenyl ring again, generates the carbon pipe that benzene sulfonyl chloride replaces.The carbon pipe for preparing the benzene sulfonyl chloride replacement in the present invention can adopt the free radical addition reaction, and employed sulphonating agent can be the vitriol oil, oleum and sulphur trioxide etc.
An embodiment of the carbon pipe that the preparation benzene sulfonyl chloride replaces is:
(a) the 1 weight part carbon nanotube and 20～60 weight part benzoyl peroxides mixing back of purified processing were reacted 5 hours down at 80 ℃, fully stir in the reaction, subsequently, with toluene and methylene dichloride mixed solvent washing reaction system, drying treatment obtains the carbon nanotube that benzene replaces after filtration again;
(b) carbon nanotube of getting the benzene replacement of 0.5～2g at room temperature fully reacts in the 50mL tetracol phenixin with the 25mL halosulfonic acid, after-filtration is finished in reaction, and with the alternately flushing repeatedly of ethanol and acetone, to leach again thing once more ultra-sonic dispersion in ethanol, to again the product that is scattered in the ethanol be filtered, vacuum drying treatment obtains having the carbon nanotube that benzene sulfonyl chloride replaces then.
It is that the carbon nanotube that replaces with benzene sulfonyl chloride is an initiator that carbon pipe of the present invention is modified grafting method, carries out atom transition free radical polymerization reaction and generate the various high molecular CNT (carbon nano-tube) mixtures of carbon nanotube initiation grafting that replaced by benzene sulfonyl chloride on the carbon pipe.Its concrete practice can be the carbon pipe that benzene sulfonyl chloride is replaced, catalyzer, coordination agent and acrylic acid or the like or styrene monomer are dispersed to and fill in the acetonitrile, use liquid nitrogen freezing then, vacuumize after the sealed reaction system, system is melted, with reaction 12 hours under 60 ℃ of constant temperature behind liquid nitrogen freezing-vacuumize-applying argon gas-thaw process triplicate, water down reaction liquid with methylene dichloride, filtering reaction liquid, filtrate is alternately washed with methylene dichloride and acetone repeatedly, to leach the thing drying treatment again, obtain the carbon nanotube that polymer graft is modified.Used catalyzer can be the halogenide of copper or nickel or rhenium or ruthenium or iron in aforementioned process, and used coordination agent can be PMDETA or quadrol or bipyridine or assorted nitrogen phenanthrene or phenanthroline or triphenyl phosphorus; The monomer that uses comprises vinylformic acid and vinylbenzene and derivative thereof.
An embodiment of carbon pipe atom transfer radical polymerization grafting method of the present invention is the carbon pipe with the benzene sulfonyl chloride replacement of 4～20mg, the catalyzer of 2～10mg, 15 μ L coordination agent and the acrylic acid or the like of 5mL or styrene monomer be dispersed to and fill in the 50-200mL acetonitrile, use liquid nitrogen freezing then, vacuumize after the sealed reaction system, system is melted, with reaction 12 hours under 60 ℃ of constant temperature behind liquid nitrogen freezing-vacuumize-applying argon gas-thaw process triplicate, water down reaction liquid with methylene dichloride, filtering reaction liquid, filtrate is alternately washed with methylene dichloride and acetone repeatedly, to leach the thing drying treatment again, obtain the carbon nanotube that polymer graft is modified.Employed catalyst system can be that halogenide and quadrol, the bipyridine of copper, nickel, rhenium, ruthenium, iron, assorted nitrogen phenanthrene, phenanthroline, triphenyl phosphorus etc. intersect the system of composition.
All the time, realize carbon pipe graft polymerization modify in controllable polymerization and high-density grafting be one of target of pursuing of investigator.The present invention uses for reference the organic chemistry method, for carbon nano tube surface covalent modification initiator molecule provides new approaches and novel method.Carbon nanotube is in good dispersion state all the time among the present invention in reaction process, the macromole evocating agent of gained has good dispersiveness at most of organic solvents, not only improved efficiency of initiation greatly, and increased the controllability of living polymerization process, help the carrying out of carbon tube-surface graft reaction.The characteristic of initiator itself is also very crucial, and relevant report shows that SULPHURYL CHLORIDE is easy to produce free radical as initiator, but dimeric generation is few, thereby has avoided two termination of the irreversible free radical of the early stage appearance of polymerization.Surperficial macromolecular grafted carbon nanotube with method preparation of the present invention has the percentage of grafting height, and the grafting amount is controlled easily, the characteristics of good dispersity in most of organic solvents and polymer monomer.This graft product is particularly suitable for the reinforcing filler as polymkeric substance, has a good application prospect.
Description of drawings
Fig. 1 is a FT-IR spectrum, and X-coordinate is a wavelength among the figure, and curve a is purified carbon nanotube, and curve b is the benzene carbon nanotube in generation, and curve c is the carbon nanotube of sulfonylation, and curve d is macromolecular grafted carbon nanotube.
Fig. 2 is the carbon nanotube thermogravimetric loss curve in different modifying stage, and wherein: curve a is the carbon nanotube of purifying, and curve b is the carbon nanotube of sulfonylation, and curve c is the grafted carbon nanotube.
Fig. 3: the transmission electron microscope picture of product of the present invention (that is: the atom transfer radical polymerization grafted carbon nanotube of benzene sulfonyl carbon nano tube initiation).
Fig. 4: preparation process synoptic diagram of the present invention.
Embodiment
The present invention further specifies in conjunction with specific embodiments.
One, the carbon pipe of preparation benzene sulfonyl chloride replacement
The purification process of carbon nanotube:
At first, the 5.0g carbon nanotube joins in the round-bottomed flask of 1000mL of the acid that fills 500mL, removes remaining catalyst particle at room temperature ultrasonic 6 hours.Subsequently, the sand core filter with 0.45 μ m aperture after mixture waters down with distilled water filters up to there not being remaining acid to exist, and the gained solid thoroughly dewaters in vacuum drying oven.Secondly, based on the different oxidisability of carbon nanotube with non-carbon nanotube impurity (Buckie onion, spherical soccerballene and agraphitic carbon), 200～500 ℃ of oxidations can be removed impurity in 2 hours under the oxidizing atmosphere effect.At last, in order to remove the carboxyl on oxide/carbon nanometer tube surface, annealing is 8 hours under 800 ℃ of argon shields.
It also can be hydrochloric acid or sulfuric acid or nitric acid that the carbon pipe is carried out the employed acid of purification process, also can be the mixture of hydrochloric acid, sulfuric acid, nitric acid.
The carbon nanotube that the preparation phenyl ring replaces:
Carbon nanotube is at first via free-radical modified process.5.0g carbon nanotube and 80g benzoyl peroxide join in the round-bottomed flask of the 1000mL that fills 500mL toluene.Be reflected at and carried out under 80 ℃ 5 hours, use magneton to stir all the time.Subsequently, use toluene and methylene dichloride filtration washing to obtain benzene repeatedly for multi-walled carbon nano-tubes.Remaining liquid is removed 100 ℃ of following vacuum-dryings.
The carbon nanotube that resulting benzene replaces is in the FT-IR spectrometry, and referring to Fig. 1 b, the existence of benzene ring substitution group can be from phenyl ring at 1559cm
-1The C=C stretching vibration and five adjacent hydrogen at 750cm
-1And 680cm
-1Vibration be confirmed.
The carbon nanotube that preparation sulfonylation phenyl ring replaces:
1.0g the carbon nanotube in benzene generation at room temperature in the 50mL tetracol phenixin, reacted 24 hours with the 25mL chlorsulfonic acid, use magneton to stir all the time.Use the sand core funnel of 0.45 μ m aperture filter membrane to filter to mixture, and after alternately washing repeatedly with ethanol and acetone once more ultra-sonic dispersion in ethanol, the carbon nanotube that obtains sulfonylation for three times like this.At last again with product finish-drying in vacuum drying oven.
Two, modify grafting and handle (being polymerization process):
1 of the sulfonylation carbon nanotube of 20mg, the CuBr of 10mg, 15 μ L; 1,4,7; 4-PMDETA and 5mL methyl methacrylate monomer are dispersed in the 100mL round-bottomed flask that fills the 50mL acetonitrile, use the threeway that is full of argon gas to be convenient to the backfill protective gas as bottle stopper.When reaction mixture through liquid nitrogen freezing-vacuumize-applying argon gas-thaw process three times repeatedly, this reaction system all the time under argon shield 60 ℃ of reactions 12 hours.After reaction finishes, water down with methylene dichloride and to use the sand core funnel of 0.45 μ m aperture filter membrane to filter after poising liquid, repeatedly with methylene dichloride and alternately flushing of acetone.Finally, product finish-drying in vacuum drying oven.
The carbon nanotube that obtains after grafting and modifying is handled referring to Fig. 1, is demonstrating 2954,2924 and 2854cm in the FT-IR spectrogram in infrared measurement
-1Triplet (CH
2Or CH
3Stretching vibration), 1732cm
-1(C=O stretching vibration), 1460cm
-1(CH
2Scissoring vibration), 1376cm
-1(CH
3Symmetric deformation) and 720cm
-1(CH
2Rocking vibration) have extremely strong peak value, show to have a large amount of polymethylmethacrylate grafting.
Can obtain the amount of the polymkeric substance in identical reaction and grafting evidence and the grafting from the carbon nanotube thermogravimetric curve analysis of Fig. 2: before the carbon nanotube grafting (Fig. 2 a) and after the grafting (Fig. 2 b) show that in 300 ℃ thermogravimetric loss difference the relative populations of graftomer is about 77.1%; Be considered as the starting temperature that carbon nanotube begins oxidation with 500 ℃, the relative populations that then is fixed to the initiator of carbon nano tube surface is about 2.3%.
Can see intuitively in the transmission electron microscope picture of Fig. 3 that the carbon nano tube surface after the grafting is evenly coating the uniform macromolecule layer of thickness, prove that carbon nanotube macromole evocating agent provided by the invention can cause the atom transfer radical polymerization graft reaction of polymethylmethacrylate in carbon nano tube surface efficiently.As shown in Figure 3.The thickness estimation of the unformed layer of polymethylmethacrylate is between 8～10nm.The protuberance that is higher than polymer layer that the part position occurs may come from the mutual termination between the segment that active homopolymer and carbon nano tube surface are being grown in the system.
Above preparation process is referring to Fig. 4.
That more than provide only is an embodiment, but protection scope of the present invention is not limited in listed examples.
Claims (8)
1. the preparation method of the carbon nanotube of a benzene sulfonyl chloride replacement is characterized in that the carbon pipe of purified processing is prepared as the carbon pipe that benzene replaces, and the carbon pipe that benzene is replaced carries out the substitution reaction on the phenyl ring again, generates the carbon pipe that benzene sulfonyl chloride replaces.
2. preparation method according to claim 1 is characterized in that adopting the free radical addition reaction that the carbon pipe is prepared as the carbon pipe that benzene replaces.
3. preparation method according to claim 2 is characterized in that:
(a) the 1 weight part carbon nanotube and 20～60 weight part benzoyl peroxides mixing back of purified processing were reacted 5 hours down at 80 ℃, fully stir in the reaction, use toluene and methylene dichloride mixed solvent washing reaction system subsequently, drying treatment obtains the carbon nanotube that benzene replaces after filtration again;
(b) carbon nanotube of getting the benzene replacement of 0.5～2g at room temperature fully reacts in the 50mL tetracol phenixin with the 25mL chlorsulfonic acid, after-filtration is finished in reaction, and repeatedly with ethanol and alternately flushing of acetone, to leach the thing ultra-sonic dispersion again in ethanol, the product that is scattered in the ethanol is filtered, through vacuum drying treatment, obtain having the carbon nanotube that benzene sulfonyl chloride replaces then.
4. the preparation method of the grafting and modifying thing that causes of a carbon nanotube that replaces with benzene sulfonyl chloride, it is characterized in that with claim 1 or 2 or 3 described carbon pipes be initiator, on the carbon pipe, carry out the various high molecular CNT (carbon nano-tube) mixture that atom transition free radical polymerization reaction generates the carbon nanotube initiation grafting that is replaced by benzene sulfonyl chloride.
5. preparation method according to claim 4, the carbon pipe that it is characterized in that general's benzene sulfonyl chloride replacement, catalyzer, coordination agent and acrylic acid or the like or styrene monomer are dispersed to and fill in the acetonitrile, use liquid nitrogen freezing then, vacuumize after the sealed reaction system, system is melted, with reaction 12 hours under 60 ℃ of constant temperature behind liquid nitrogen freezing-vacuumize-applying argon gas-thaw process triplicate, water down reaction liquid with methylene dichloride, filtering reaction liquid, filtrate is alternately washed with methylene dichloride and acetone repeatedly, to leach the thing drying treatment again, obtain the carbon nanotube that polymer graft is modified.
6. preparation method according to claim 5 is characterized in that used catalyzer is the halogenide of copper or nickel or rhenium or ruthenium or iron, and used coordination agent is PMDETA or quadrol or bipyridine or assorted nitrogen phenanthrene or phenanthroline or triphenyl phosphorus.
7. preparation method according to claim 6, it is characterized in that carbon pipe with the benzene sulfonyl chloride replacement of 4～20mg, the copper halide catalyzer of 2～10mg, 1 of 15 μ L, 1,4,7, the coordination agent of 4-PMDETA and the acrylic acid or the like of 5mL or styrene monomer are dispersed to and fill in the 50-200mL acetonitrile, use liquid nitrogen freezing then, vacuumize after the sealed reaction system, system is melted, with reaction 12 hours under 60 ℃ of constant temperature behind liquid nitrogen freezing-vacuumize-applying argon gas-thaw process triplicate, water down reaction liquid with methylene dichloride, filtering reaction liquid alternately washes with methylene dichloride and acetone repeatedly to filtrate, to leach the thing drying treatment again, obtain the carbon nanotube that polymer graft is modified.
8. the carbon nanotube of modifying according to the polymer graft of the described arbitrary preparation method preparation of claim 4 to 7.
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| CN106944133A (en) * | 2017-04-17 | 2017-07-14 | 浙江工业大学 | A kind of sulfonic acid carbon nano tube solid acid catalyst and its preparation method and application |
| CN107199050A (en) * | 2017-04-17 | 2017-09-26 | 浙江工业大学 | A kind of sulfonic acid carbon nano tube solid acid and its preparation method and application |
| CN109678877A (en) * | 2019-01-03 | 2019-04-26 | 兰州大学 | Compound with electron mobility and preparation method thereof, organic effect device and preparation method thereof |
| CN115058180A (en) * | 2022-08-11 | 2022-09-16 | 赵子龙 | Water-based composite coating material |
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- 2008-02-02 CN CNA200810080406XA patent/CN101224884A/en active Pending
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106944133A (en) * | 2017-04-17 | 2017-07-14 | 浙江工业大学 | A kind of sulfonic acid carbon nano tube solid acid catalyst and its preparation method and application |
| CN107199050A (en) * | 2017-04-17 | 2017-09-26 | 浙江工业大学 | A kind of sulfonic acid carbon nano tube solid acid and its preparation method and application |
| CN107199050B (en) * | 2017-04-17 | 2019-11-19 | 浙江工业大学 | A kind of sulfonic acid carbon nano tube solid acid and its preparation method and application |
| CN109678877A (en) * | 2019-01-03 | 2019-04-26 | 兰州大学 | Compound with electron mobility and preparation method thereof, organic effect device and preparation method thereof |
| CN115058180A (en) * | 2022-08-11 | 2022-09-16 | 赵子龙 | Water-based composite coating material |
| CN115058180B (en) * | 2022-08-11 | 2023-08-11 | 广东省漆色彩新型材料有限公司 | Water-based composite coating material |
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