CN100486891C - Method for realizing modification of carbon nano-tube by using polymer crystallization - Google Patents
Method for realizing modification of carbon nano-tube by using polymer crystallization Download PDFInfo
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- CN100486891C CN100486891C CNB2007100547140A CN200710054714A CN100486891C CN 100486891 C CN100486891 C CN 100486891C CN B2007100547140 A CNB2007100547140 A CN B2007100547140A CN 200710054714 A CN200710054714 A CN 200710054714A CN 100486891 C CN100486891 C CN 100486891C
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Abstract
The invention relates to a method for realizing decoration of a carbon nano tube through polymer crystallization, in particular to induce polymer crystallization by using supercritical or compressive carbon dioxide as anti-solvent so as to achieve decoration. The method is carried as follows: the polymer prepared under constant temperature is dissolved in organic solvent solution 1; the carbon nano tube is evenly dispersed in the organic solvent under a temperature condition that is higher than the room temperature, so as to obtain a system 2; the ultimate density of the polymer and the carbon nano tube in the organic solvent after mixture is 0.003 to 0.1wt percent and 0.002 to 0.02 wt percent respectively for the mixture solution 1 and the system 2, thereby, a system 3 is obtained upon balance; then the system 3 is moved into a closed reactor and carbon dioxide is added into the reactor till the pressure in the reactor is 5 to 25MPa and be kept for 0.5 to 7 hours, finally the carbon nano tube decorated with the polymer crystallization is obtained after the pressure is reduced to a normal level. The method has simple technique, easy operation, notable effect and being environment protective, therefore, the performance of the carbon nano tube decorated with the polymer crystallization is good.
Description
(1) technical field
The present invention relates to a kind of polymer crystallization that utilizes and realize carbon nano tube modified method, particularly utilize method overcritical or that the compressibility carbonic acid gas is modified as anti-solvent-induced polymer crystallization.
(2) background technology
Carbon nanotube belongs to crystalline state carbon, and its tube wall is the same with graphite-structure.Usually, the low-dimension nano material of production in enormous quantities itself exists many defectives, and dispersiveness is also poor.Particularly the surface tissue of carbon nanotube often influences many performances such as electricity, mechanics and optics.These factors have reduced the high-performance of carbon nanotube as nano material, have influenced the application of carbon nanotube.In order to improve the carbon nano tube surface structure, generally adopt surface modification method, thereby improve carbon nanotube dispersiveness, stability and and other materials between consistency, give its new physics, chemistry, mechanical property and new function.At present, the method for finishing can be divided into organic non covalent bond modification and organic covalent linkage modification two big classes.Organic non covalent bond modification can make carbon nano tube surface have a large amount of organo-functional groups, and does not destroy the big π bonding electron of graphite flake layer self.But the reactive force between the functional group of this finishing and the carbon nano tube surface is not high.Though the reactive force between organic covalent linkage modification merit functional group and the carbon nano tube surface is more intense,, make original good electrical property of carbon nanotube and mechanical property all decrease because of the existence of covalent linkage has destroyed the original structure of carbon nanotube.
Overcritical or compressibility carbonic acid gas all has very high solubleness in most of organic solvents, cause the solvent strength of organic solvent to reduce.For many solutes especially superpolymer, the solvent strength of overcritical or compressibility carbonic acid gas many a little less than than organic solvent, thus show its good solubility-resistence.Utilize SC-CO
2This performance prepared some nano materials, such as C
60/ (CO
2)
0.95(N.F.Christian, A.H.Paul, M.W.Jeremy, H.G.Duncan, J.T.Jeremy, P.Martyn, J.Am.Chem.Soc.2000,122,2480), Eu
2O
3Coated multi-walled carbon nano-tubes (L.Fu, Z.Liu, Y.Liu, B.Han, J.Wang, P.Hu, L.Cao, D.Zhu, Adv.Mater.2004,16,350), platinum/carbon nano-tube nano composite material (J.J.Watkins, J.M.Blackburn, T.J.McCarthy, Chem.Mater.1999,11,213), the nano composite material of metal nanometer line filled with nanotubes (X.R.Ye, Y.Lin, C.Wang, C.M.Wai, Adv.Mater.2003,15,316) and poly-2,4-hexin-1,6-diol ester/carbon nanotube composite materials (X.Dai, Z.Liu, B.Han, Z.Sun, Y.Wang, J.Xu, X.Guo, N.Zhao, J.Chen, Chem.Commun.2004,2190).
Solvent strength overcritical or the compressibility carbonic acid gas can obtain changing by regulating its pressure or temperature.Therefore by control pressure or temperature, can select to separate the polymkeric substance of different molecular weight, it is separated out and crystallization.But up till now, as yet about utilizing bibliographical information overcritical or the polymer-modified carbon nanotube of compressibility carbon dioxide anti-solvent realization, also do not see have other to utilize overcritical or the compressibility carbonic acid gas as anti-solvent, the induced polymer crystalline bibliographical information of growing nonparasitically upon another plant.
(3) summary of the invention
The object of the present invention is to provide a kind of carbon nano-tube modified method of polymer crystallization of utilizing, utilize overcritical especially or the compressibility carbonic acid gas as anti-solvent, method is simple, environmental protection, functional group and the reactive force between the carbon nano tube surface that the carbon nano tube surface that the polymer crystallization of preparing is modified is modified are stronger, do not influence original electrical property of carbon nanotube and mechanical property again.
The technical solution used in the present invention is as follows:
A kind of polymer crystallization that utilizes is realized carbon nano tube modified method: constant temperature prepares the solution 1 that polymkeric substance is dissolved in organic solvent under 20 ℃ the temperature condition being not less than below the polymer melting temperature; Be higher than under the temperature condition of room temperature, even carbon nanotube is scattered in the organic solvent of the same race, obtain system 2; According to certain mixed solution 1 and system 2, mix post polymerization thing and the final concentration of carbon nanotube in organic solvent and be respectively 0.003～0.1wt% and 0.002～0.02wt%, wait for that mixed system balance obtains system 3; System 3 is transferred in the closed reactor, constant temperature feeds carbonic acid gas pressure to the reactor and is 5～25MPa and keeps 0.5～7h under the temperature identical with preparation solution 1, promptly get the carbon nanotube that polymer crystallization is modified after reducing to normal pressure, described organic solvent is dimethylbenzene, dichlorobenzene, glycerol or Virahol, and described polymkeric substance is crystal type or half hitch crystal formation superpolymer.
Preparation is during solution 1, as long as the homothermic temperature is not less than following 20 ℃ of the melt temperature of the polymkeric substance of selecting for use.For example, if the polymer melting temperature of selecting for use is 120 ℃, as long as the homothermic temperature is not less than 100 ℃.
During preparation system 2, temperature is preferably 35～60 ℃, more preferably 45～50 ℃; Carbon nanotube should be dispersed in the organic solvent as far as possible, as adopting the mode of ultra-sonic dispersion.Present method both had been applicable to Single Walled Carbon Nanotube, also was applicable to multi-walled carbon nano-tubes.
Preferably, in the system 3, the concentration of polymkeric substance in organic solvent is 0.006～0.04wt%.
Further, the preferred p-Xylol of described organic solvent or 1,2-dichlorobenzene.Described polymkeric substance is preferably polyethylene, polypropylene or nylon 66, nylon 6, polytetrahydrofuran, polyethylene oxide, polyvinyl alcohol, polyacrylonitrile or polyurethane.
Can feed carbonic acid gas according to the flow velocity of 150～250ml/h in closed reactor, the pressure in the feeding post-reactor is preferably at 7～22MPa.Described closed reactor uses autoclave just passable.
Further, when selecting high density polyethylene(HDPE), it is better that constant temperature carries out the preparation of solution 1 in 100～120 ℃ of scopes.
Concrete, the described polymer crystallization that utilizes is realized carbon nano tube modified method, can carry out according to following steps:
1) constant temperature is dissolved in polymkeric substance and obtains solution 1 in the organic solvent, and temperature must not be lower than following 20 ℃ of the melt temperature of polymkeric substance; At 45～50 ℃ even carbon nanotube is scattered in and obtains system 2 in the organic solvent of the same race; Mixing solutions 1 and system 2, make mixing post polymerization thing and the final concentration of carbon nanotube in organic solvent be respectively 0.006～0.04wt% and 0.002～0.02wt%, wait for that mixed system balance obtains system 3, described organic solvent is p-Xylol or 1, the 2-dichlorobenzene;
2) system 3 is transferred in the homothermic autoclave, temperature is identical with the temperature of preparation during solution 1;
3) flow velocity feeding carbonic acid gas to the pressure with 150～250ml/h is 7～22MPa in autoclave, keeps being depressurized to normal pressure behind 1～4h, promptly gets the carbon nanotube that polymer crystallization is modified.
The present invention has following advantage with respect to prior art:
Present method technology is simple, and is easy and simple to handle, achieves noticeable achievement; Supercritical co is a green solvent, environmental protection; The carbon nanotube microscopic pattern that the polymer crystallization that makes is modified is " mutton string of cash structure ", original good electronics of carbon nanotube and mechanical property had both been kept, solved the not strong problem of reactive force between similar carbon nano tube modified group and carbon nano tube surface again, increase the consistency of carbon nanotube and polymkeric substance, can be widely used in the nano composite material of preparation polymer/carbon nano-tube.
(4) description of drawings
Fig. 1 is the sem photograph of the carbon nanotube modified of the polymer crystallization of the embodiment of the invention 1 preparation;
Fig. 2 is the transmission electron microscope picture of the carbon nanotube modified of the polymer crystallization of the embodiment of the invention 1 preparation.
(5) embodiment:
Below with specific embodiment technical scheme of the present invention is described, but protection scope of the present invention is not limited thereto:
Embodiment 1
110 ℃ of constant temperature of high density polyethylene(HDPE) (HDPE) of 1.0mg are dissolved in the p-Xylol of 4g, meanwhile, the Single Walled Carbon Nanotube SWNTs of ultra-sonic dispersion 0.1mg in 45 ℃～50 ℃ p-Xylol at 1g, treat that HDPE dissolves fully, after SWNTs disperses fully, mix p-Xylol solution and the SWNTs/ p-Xylol dispersion system of 110 ℃ HDPE, the concentration of the HDPE of Xing Chenging is 0.02wt% at last, and the concentration of SWNTs is 0.002wt%.After treating the system balance, the p-Xylol solution of HDPE/SWNTs is transferred to rapidly in 110 ℃ of homothermic autoclaves; In autoclave, inject CO
2To 9MPa, and keep high pressure 3h, slowly be depressurized to normal pressure at last, drive still and take out all products, be the carbon nanotube that high density polyethylene(HDPE) is modified.
Embodiment 2
The HDPE consumption is 0.5mg, and the concentration of the HDPE of Xing Chenging is 0.01wt% at last, and other are with embodiment 1.
Embodiment 3
The HDPE consumption changes 0.3mg into, and the concentration of the HDPE of Xing Chenging is 0.006wt% at last, and other are with embodiment 1.
Embodiment 4
The HDPE consumption changes 2.0mg into, and the concentration of the HDPE of Xing Chenging is 0.04wt% at last, and other are with embodiment 1.
Embodiment 5
The HDPE consumption changes 5.0mg into, and the concentration of the HDPE of Xing Chenging is 0.1wt% at last, and other are with embodiment 1.
Embodiment 6
Feed CO
2Pressure is to 5MPa, and other are with embodiment 1.
Embodiment 7
Feed CO
2Pressure is to 7MPa, and other are with embodiment 1.
Embodiment 8
Feed CO
2Pressure is to 13MPa, and other are with embodiment 1.
Embodiment 9
100 ℃ of constant temperature of high density polyethylene of 1mg are dissolved in 1 of 4g, in the 2-dichlorobenzene, meanwhile, in 45 ℃～50 ℃ at 1 of 1g, the Single Walled Carbon Nanotube SWNTs of ultra-sonic dispersion 0.3mg in the 2-dichlorobenzene, treat that HDPE dissolves fully, after SWNTs disperses fully, with SWNTs/1,1 of the HDPE of 2-dichlorobenzene dispersion system and 100 ℃, the 2-dichlorobenzene solution mixes, and the concentration of the HDPE of Xing Chenging is 0.02wt% at last, and the concentration of SWNTs is 0.006wt%.After treating the system balance, with 1 of HDPE/SWNTs, the 2-dichlorobenzene solution is transferred to rapidly in 100 ℃ of homothermic autoclaves; In autoclave, inject CO
2To 16MPa, and keep high pressure 3h, slowly be depressurized to normal pressure at last, drive still and take out all products, be the carbon nanotube that high density polyethylene(HDPE) is modified.
Embodiment 10
The SWNTs consumption is 0.5mg, and the concentration of the SWNTs of Xing Chenging is 0.01wt% at last, and other are with embodiment 9.
Embodiment 11
The SWNTs consumption is 1.0mg, and the concentration of the SWNTs of Xing Chenging is 0.02wt% at last, and other are with embodiment 9.
Embodiment 12
Feed CO
2Pressure is to 22MPa, and other are with embodiment 9.
Embodiment 13
Feed CO
2Pressure is to 25MPa, and other are with embodiment 9.
Embodiment 14
100 ℃ of constant temperature of high density polyethylene of 0.3mg are dissolved in the p-Xylol of 4g, meanwhile, the multi-walled carbon nano-tubes MWNTs of ultra-sonic dispersion 0.1mg in 45 ℃～50 ℃ p-Xylol at 1g, treat that HDPE dissolves fully, after MWNTs disperses fully, MWNTs/ p-Xylol dispersion system is mixed with the p-Xylol solution of 100 ℃ HDPE, and the concentration of the HDPE of Xing Chenging is 0.006wt% at last, and the concentration of MWNTs is 0.002wt%.After treating the system balance, the p-Xylol solution of HDPE/MWNTs is transferred to rapidly in 100 ℃ of homothermic autoclaves; In autoclave, inject CO
2To 9MPa, and keep high pressure 3h, slowly be depressurized to normal pressure at last, drive still and take out all products, be the carbon nanotube that high density polyethylene(HDPE) is modified.
Embodiment 15
At 30 ℃ multi-walled carbon nano-tubes is scattered in the p-Xylol, other are with embodiment 14.
Embodiment 16
At 60 ℃ multi-walled carbon nano-tubes is scattered in the p-Xylol, other are with embodiment 14.
Embodiment 17
Organic solvent is 1, and the 2-dichlorobenzene feeds CO
2Pressure is to 16MPa, and other are with embodiment 14.
Claims (10)
1. one kind is utilized polymer crystallization to realize carbon nano tube modified method, it is characterized in that described method is for constant temperature prepares the solution 1 that polymkeric substance is dissolved in organic solvent under 20 ℃ the temperature condition being not less than below the polymer melting temperature; Be higher than under the temperature condition of room temperature, even carbon nanotube is scattered in the organic solvent of the same race, obtain system 2; According to certain mixed solution 1 and system 2, mix post polymerization thing and the final concentration of carbon nanotube in organic solvent and be respectively 0.003～0.1wt% and 0.002～0.02wt%, wait for that mixed system balance obtains system 3; System 3 is transferred in the closed reactor, constant temperature feeds carbonic acid gas pressure to the reactor and is 5～25MPa and keeps 0.5～7h under the temperature identical with preparation solution 1, promptly get the carbon nanotube that polymer crystallization is modified after reducing to normal pressure, described organic solvent is dimethylbenzene, dichlorobenzene, glycerol or Virahol, and described polymkeric substance is crystal type or half hitch crystal formation superpolymer.
2. the polymer crystallization that utilizes as claimed in claim 1 is realized carbon nano tube modified method, it is characterized in that the concentration of polymkeric substance in organic solvent is 0.006～0.04wt% in the described system 3.
3. the polymer crystallization that utilizes as claimed in claim 1 is realized carbon nano tube modified method, and the preparation temperature that it is characterized in that described system 2 is 35～60 ℃.
4. the polymer crystallization that utilizes as claimed in claim 1 is realized carbon nano tube modified method, it is characterized in that the flow velocity that described carbonic acid gas feeds is 150～250ml/h.
5. the polymer crystallization that utilizes as claimed in claim 1 is realized carbon nano tube modified method, and it is characterized in that feeding carbonic acid gas pressure to the reactor is 7～22MPa.
6. the polymer crystallization that utilizes as claimed in claim 1 is realized carbon nano tube modified method, it is characterized in that described organic solvent is p-Xylol or 1, the 2-dichlorobenzene.
7. the polymer crystallization that utilizes as claimed in claim 1 is realized carbon nano tube modified method, it is characterized in that described polymkeric substance is polyethylene, polypropylene, nylon 66, nylon 6, polytetrahydrofuran, polyethylene oxide, polyvinyl alcohol, polyacrylonitrile or polyurethane.
8. the polymer crystallization that utilizes as claimed in claim 1 is realized carbon nano tube modified method, it is characterized in that described method carries out according to following steps:
1) constant temperature is dissolved in polymkeric substance and obtains solution 1 in the organic solvent, and temperature must not be lower than following 20 ℃ of the melt temperature of polymkeric substance; At 45～50 ℃ even carbon nanotube is scattered in and obtains system 2 in the organic solvent of the same race; Mixing solutions 1 and system 2, make mixing post polymerization thing and the final concentration of carbon nanotube in organic solvent be respectively 0.006～0.04wt% and 0.002～0.02wt%, wait for that mixed system balance obtains system 3, described organic solvent is p-Xylol or 1, the 2-dichlorobenzene;
2) system 3 is transferred in the homothermic autoclave, temperature is identical with the temperature of preparation during solution 1;
3) flow velocity feeding carbonic acid gas to the pressure with 150～250ml/h is 7～22MPa in autoclave, keeps being depressurized to normal pressure behind 1～4h, promptly gets the carbon nanotube that polymer crystallization is modified.
9. the polymer crystallization that utilizes as claimed in claim 8 is realized carbon nano tube modified method, it is characterized in that described polymkeric substance is polyethylene, polypropylene or nylon 66.
10. the polymer crystallization that utilizes as claimed in claim 8 is realized carbon nano tube modified method, it is characterized in that 100～120 ℃ of constant temperature that are prepared as of described solution 1 are dissolved in high density polyethylene(HDPE) in the organic solvent.
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| CNB2007100547140A CN100486891C (en) | 2007-07-03 | 2007-07-03 | Method for realizing modification of carbon nano-tube by using polymer crystallization |
| PCT/CN2008/001061 WO2009003357A1 (en) | 2007-07-03 | 2008-05-30 | A method for decorating nano carbon tubes with polymer crystal |
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| CNB2007100547140A CN100486891C (en) | 2007-07-03 | 2007-07-03 | Method for realizing modification of carbon nano-tube by using polymer crystallization |
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| CN100486891C (en) * | 2007-07-03 | 2009-05-13 | 郑州大学 | Method for realizing modification of carbon nano-tube by using polymer crystallization |
| CN100590070C (en) * | 2008-04-23 | 2010-02-17 | 郑州大学 | Method for modifying carbon nano-tube by using polyglycol |
| KR101470524B1 (en) * | 2009-06-30 | 2014-12-08 | 한화케미칼 주식회사 | Blending improvement carbon-composite having Carbon-nanotube and its continuous manufacturing method |
| CN101941690A (en) * | 2010-09-09 | 2011-01-12 | 同济大学 | Method for improving dispersibility of single-walled carbon nanotube in aqueous solution |
| CN103668528B (en) * | 2013-12-10 | 2015-11-18 | 苏州大学张家港工业技术研究院 | A kind of carbon nanotube/polyvinyl alcohol composite fibre and preparation method thereof |
| CN107129671B (en) * | 2017-05-27 | 2019-04-02 | 郑州大学 | A kind of preparation method of anisotropic conductive polymer composite |
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| US7754328B2 (en) * | 2003-01-20 | 2010-07-13 | Teijin Limited | Carbon nanotube coated with aromatic condensation polymer |
| CN1331899C (en) * | 2005-12-15 | 2007-08-15 | 上海交通大学 | Method for preparing carbon nano tube/polymer nano composite material |
| CN100410289C (en) * | 2006-03-14 | 2008-08-13 | 同济大学 | Process for in-situ synthesis of amphiphilic polymer modified carbon nanotube |
| CN100486891C (en) * | 2007-07-03 | 2009-05-13 | 郑州大学 | Method for realizing modification of carbon nano-tube by using polymer crystallization |
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