CN108545717A - A kind of method and modified carbon nano-tube of surface modification of carbon nanotube - Google Patents
A kind of method and modified carbon nano-tube of surface modification of carbon nanotube Download PDFInfo
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- CN108545717A CN108545717A CN201810490900.7A CN201810490900A CN108545717A CN 108545717 A CN108545717 A CN 108545717A CN 201810490900 A CN201810490900 A CN 201810490900A CN 108545717 A CN108545717 A CN 108545717A
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical class [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 75
- 239000002041 carbon nanotube Substances 0.000 title claims abstract description 70
- 229910021393 carbon nanotube Inorganic materials 0.000 title claims abstract description 60
- 238000000034 method Methods 0.000 title claims abstract description 46
- 230000004048 modification Effects 0.000 title claims abstract description 18
- 238000012986 modification Methods 0.000 title claims abstract description 18
- 238000006243 chemical reaction Methods 0.000 claims abstract description 22
- 150000001875 compounds Chemical class 0.000 claims abstract description 20
- ZSTLPJLUQNQBDQ-UHFFFAOYSA-N azanylidyne(dihydroxy)-$l^{5}-phosphane Chemical compound OP(O)#N ZSTLPJLUQNQBDQ-UHFFFAOYSA-N 0.000 claims abstract description 17
- 239000002253 acid Substances 0.000 claims abstract description 13
- 239000011230 binding agent Substances 0.000 claims abstract description 11
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 21
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical group CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 15
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 14
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical group OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 9
- 125000000951 phenoxy group Chemical group [H]C1=C([H])C([H])=C(O*)C([H])=C1[H] 0.000 claims description 8
- 239000002904 solvent Substances 0.000 claims description 8
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical group CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 6
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N dimethyl sulfoxide Natural products CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 6
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 6
- 229920000877 Melamine resin Polymers 0.000 claims description 5
- 239000003054 catalyst Substances 0.000 claims description 5
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 5
- RZVAJINKPMORJF-UHFFFAOYSA-N Acetaminophen Chemical compound CC(=O)NC1=CC=C(O)C=C1 RZVAJINKPMORJF-UHFFFAOYSA-N 0.000 claims description 4
- 230000001588 bifunctional effect Effects 0.000 claims description 4
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 claims description 4
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 claims description 3
- 238000002360 preparation method Methods 0.000 claims description 3
- 239000001632 sodium acetate Substances 0.000 claims description 3
- 235000017281 sodium acetate Nutrition 0.000 claims description 3
- WFKAJVHLWXSISD-UHFFFAOYSA-N isobutyramide Chemical compound CC(C)C(N)=O WFKAJVHLWXSISD-UHFFFAOYSA-N 0.000 claims description 2
- ZFSLODLOARCGLH-UHFFFAOYSA-N isocyanuric acid Chemical compound OC1=NC(O)=NC(O)=N1 ZFSLODLOARCGLH-UHFFFAOYSA-N 0.000 claims description 2
- 239000003795 chemical substances by application Substances 0.000 claims 1
- JJWLVOIRVHMVIS-UHFFFAOYSA-N isopropylamine Chemical compound CC(C)N JJWLVOIRVHMVIS-UHFFFAOYSA-N 0.000 claims 1
- 230000000694 effects Effects 0.000 abstract description 5
- 239000002131 composite material Substances 0.000 abstract description 3
- 239000013047 polymeric layer Substances 0.000 abstract description 3
- 238000011065 in-situ storage Methods 0.000 abstract description 2
- 238000006068 polycondensation reaction Methods 0.000 abstract description 2
- 239000002244 precipitate Substances 0.000 abstract description 2
- YVNRUPSDZZZUQJ-UHFFFAOYSA-N [O].NC1=CC=CC=C1 Chemical group [O].NC1=CC=CC=C1 YVNRUPSDZZZUQJ-UHFFFAOYSA-N 0.000 abstract 2
- 239000000203 mixture Substances 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 18
- 239000011248 coating agent Substances 0.000 description 12
- 238000000576 coating method Methods 0.000 description 12
- 229920000642 polymer Polymers 0.000 description 11
- 239000000126 substance Substances 0.000 description 10
- 239000000463 material Substances 0.000 description 8
- 229910052799 carbon Inorganic materials 0.000 description 6
- -1 carbon nano tube compound Chemical class 0.000 description 5
- 239000010410 layer Substances 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- 239000006185 dispersion Substances 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 239000011159 matrix material Substances 0.000 description 4
- 235000011181 potassium carbonates Nutrition 0.000 description 4
- CBCKQZAAMUWICA-UHFFFAOYSA-N 1,4-phenylenediamine Chemical compound NC1=CC=C(N)C=C1 CBCKQZAAMUWICA-UHFFFAOYSA-N 0.000 description 3
- IAZDPXIOMUYVGZ-WFGJKAKNSA-N Dimethyl sulfoxide Chemical group [2H]C([2H])([2H])S(=O)C([2H])([2H])[2H] IAZDPXIOMUYVGZ-WFGJKAKNSA-N 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- 238000013019 agitation Methods 0.000 description 3
- 239000000706 filtrate Substances 0.000 description 3
- 239000000178 monomer Substances 0.000 description 3
- 239000002071 nanotube Substances 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- 229920005989 resin Polymers 0.000 description 3
- 239000011347 resin Substances 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 2
- 238000005253 cladding Methods 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- 125000003700 epoxy group Chemical group 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 239000002105 nanoparticle Substances 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- YNPNZTXNASCQKK-UHFFFAOYSA-N phenanthrene Chemical compound C1=CC=C2C3=CC=CC=C3C=CC2=C1 YNPNZTXNASCQKK-UHFFFAOYSA-N 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 235000011121 sodium hydroxide Nutrition 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 150000005208 1,4-dihydroxybenzenes Chemical class 0.000 description 1
- 238000005160 1H NMR spectroscopy Methods 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 238000010306 acid treatment Methods 0.000 description 1
- 230000009435 amidation Effects 0.000 description 1
- 238000007112 amidation reaction Methods 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 229910001882 dioxygen Inorganic materials 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 230000032050 esterification Effects 0.000 description 1
- 238000005886 esterification reaction Methods 0.000 description 1
- 235000019441 ethanol Nutrition 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 238000007306 functionalization reaction Methods 0.000 description 1
- 210000004209 hair Anatomy 0.000 description 1
- 125000005842 heteroatom Chemical group 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 238000002329 infrared spectrum Methods 0.000 description 1
- 238000009940 knitting Methods 0.000 description 1
- 150000007974 melamines Chemical class 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 238000000053 physical method Methods 0.000 description 1
- 229920002627 poly(phosphazenes) Polymers 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 230000002787 reinforcement Effects 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- 238000012216 screening Methods 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 150000003384 small molecules Chemical class 0.000 description 1
- 238000010129 solution processing Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 239000003643 water by type Substances 0.000 description 1
- 210000002268 wool Anatomy 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/15—Nano-sized carbon materials
- C01B32/158—Carbon nanotubes
- C01B32/168—After-treatment
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G79/00—Macromolecular compounds obtained by reactions forming a linkage containing atoms other than silicon, sulfur, nitrogen, oxygen, and carbon with or without the latter elements in the main chain of the macromolecule
- C08G79/02—Macromolecular compounds obtained by reactions forming a linkage containing atoms other than silicon, sulfur, nitrogen, oxygen, and carbon with or without the latter elements in the main chain of the macromolecule a linkage containing phosphorus
- C08G79/025—Polyphosphazenes
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/01—Crystal-structural characteristics depicted by a TEM-image
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/80—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70
- C01P2002/82—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70 by IR- or Raman-data
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Nanotechnology (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Inorganic Chemistry (AREA)
- Carbon And Carbon Compounds (AREA)
Abstract
The application belongs to technical field of composite materials, and in particular to a kind of method and modified carbon nano-tube of surface modification of carbon nanotube.Method provided by the present invention includes：By carbon nanotube ultrasonic disperse in reaction dissolvent, the first solution is obtained；Hexachlorocyclotriph,sphazene and the first compound are dissolved in reaction dissolvent, the second solution is obtained；Acid binding agent is added in the first solution, then the second solution is slowly added in the first solution, reacts, obtain modified carbon nano-tube；Wherein, first compound is：Six (4 amino-benzene oxygen) rings, three phosphonitrile, or be：The composition of three phosphonitrile containing six (4 amino-benzene oxygen) rings.The present invention is rich in the polymeric layer of a large amount of high activity reactive groups using the method for in-situ precipitate polycondensation in original carbon nanotubes coated with uniform, and method of modifying is one kettle way, and easy to operate and reaction condition is mild, easy to implement.
Description
Technical field
The invention belongs to technical field of composite materials, and in particular to a kind of method and carbon modified of surface modification of carbon nanotube
Nanotube.
Background technology
Since 1991, since S.Iijima has found carbon nanotube (carbon nanotubes, CNTs), CNTs is because of its uniqueness
Structure feature, excellent physical and chemical performance and the potential application value of the following high-tech area receive people concern,
It is quickly become physics, chemistry, biology, material, the study frontier and hot spot of medicine and other fields.CNTs not only has general nanoparticle
The quantum effect of son, but also have the characteristics that large specific surface area, high mechanical strength, conductivity are high, heat-resist, make its performance
Go out special physical and chemical properties, is with a wide range of applications in fields such as electronics, communication, chemical industry, Aeronautics and Astronautics.Mesh
It is preceding to have achieved a large amount of achievement in research in the preparation of CNTs, purifying, functionalization, performance applications etc. both at home and abroad.With
The a large amount of technologies of preparing of CNTs reach its maturity and it is studied it is gradual deeply, the reality that present people more pay close attention to CNTs is answered
With especially using CNTs as the polymer composites of reinforcement.
However, CNTs is easily gathered into bundles or is wound, and compared with other nano-particles, surface with respect to 'inertia',
Dispersion degree in common organic solvent is low, this greatlys restrict the research of its application performance.Moreover, CNTS and matrix
Compatibility is poor with wellability, has seriously affected the interface cohesion and its performance of carbon nano tube compound material.At present, it has been found that logical
Cross and effective surface modification carried out to carbon nanotube, its dispersion performance can be improved, improve its compatibility with basis material and
Wellability improves the performance of carbon nano tube compound material so as to generate good combination interface between basis material.This
Outside, its surface is modified and can also impart to the new performance of carbon nanotube, realized that its molecule assembles, obtain receiving for various superior performances
Rice material, has a extensive future in molectronics, nanoelectronics and nano biological molecules etc..Therefore, carbon is received
Nanotube surface is modified the hot spot having become in carbon nanotube research, and the modification of CNTs is to realize the premise and base of its application value
Plinth.
Surface modification of carbon nanotube is the state and structure for changing the surfaces CNTs by physics, chemical method, improves its
Surface-active improves its dispersibility, increases the compatibility with other materials.Chemical method generally uses strong acid and strong oxidizer pre-
After processing, make its surface with functional groups such as carboxyls, is then reacted again in its surface grafting polymerization by amidation, esterification etc.
Object, to improve the dispersibility of carbon nanotube.But chemical method, by covalent bond effect, the sp2 for destroying carbon nanotube is miscellaneous
Change structure, certain influence is generated to its mechanical performance and electric property.
Chinese patent CN103803523A report it is a kind of using highly basic and hydrogen peroxide mixed solution processing carbon nanotube after,
Make itself and tannin-reaction, the carbon nanotube by surface modification treatment is evenly dispersed in water and organic solvent and has higher
Stability.But highly basic and the dioxygen water pretreatment carbon nanotube meeting original chemical constitution of destroying carbon nanometer tube, and this method
Carbon nano tube surface functional group after modification is less and single, limits and is further modified to it and its multi-functional.
Chinese patent CN102442660A is reported a kind of carbon nano tube surface and is connected the super of sealing end in the form of chemical bond
Branched polysiloxane.This method introduces a large amount of carboxyls by nitric acid treatment carbon nanotube first, make its with structure containing phospho hetero phenanthrene with
The hyperbranched polyorganosiloxane of epoxy group reacts, and it is anti-that carbon nanotube after modified has been grafted a large amount of epoxy group, hydroxyl isoreactivity
Group is answered, obtain good dispersion in resin matrix for carbon nanotube provides very favorable condition with compatibility.Meanwhile
Modified CNT surface contains phospho hetero phenanthrene structure and polysiloxane structure simultaneously, and fire-retardant synergy can occur.But at strong acid
The structure of reason equally meeting destroying carbon nanometer tube, and there is different degrees of fault of construction in dissaving polymer, limit it
Application range.
Physical method includes mainly non-covalent bond method for coating, need not be acidified, not destroy to carbon nano tube surface
Carbon nanotube internal structure belongs to physical modification process.Journal of American ChemistrySociety are 2006
It is reported in 1692-1699 pages of volume 128 of year：Non-covalent bond method for coating is then by the small molecule or polymerization with aromatic rings
Weak pi-pi accumulation effect between object and the graphite-structure of carbon nanotube, and then introduce active amino on the surface of carbon nanotube.So
And what is formed between above-mentioned polymer and carbon nanotube by this method is weak pi-pi bond, is easily detached from, interfacial combined function compared with
Difference steadily cannot uniformly and stably disperse in solution or matrix resin.For surface modification of carbon nanotube in the prior art
The deficiency of method, therefore, it is necessary to further study a kind of method of novel surface modification of carbon nanotube.
Invention content
In view of this, the purpose of the present invention is to provide a kind of method of surface modification of carbon nanotube and modified carbon nano tubes
Pipe, specific technical solution are as follows：
A kind of method of surface modification of carbon nanotube, including：
By carbon nanotube ultrasonic disperse in reaction dissolvent, the first solution is obtained；
Hexachlorocyclotriph,sphazene and the first compound are dissolved in reaction dissolvent, the second solution is obtained；
Acid binding agent is added in the first solution, then the second solution is slowly added in the first solution, reacts, obtain carbon modified
Nanotube；
Wherein, first compound is：Six-(4- amino-benzene oxygens) rings, three phosphonitrile, bifunctional compound and three officials
It can roll into a ball one or more in compound.
Preferably, based on degree of functionality, the molar ratio of the hexachlorocyclotriph,sphazene and first compound is 1.0:(1.05
~1.5)；
The mass ratio of the summation of the hexachlorocyclotriph,sphazene and the first compound and the carbon nanotube is (1~3):1.
Preferably, the temperature of the reaction is 40 DEG C~60 DEG C, and the time is 5h~48h；
The molar ratio of the acid binding agent and the hexachlorocyclotriph,sphazene is (1~2):1.
Preferably, the mass percent concentration of carbon nanotube described in first solution is 0.1%~3%.
Preferably, the bifunctional compound is selected from NH2-R-OH、NH2-R-NH2, in HOOC-R-OH and HO-R-OH
It is one or more；
Wherein, R is-(C6H4)-or-(CH2)n, n=1~10.
Preferably, the trifunctional compound is selected from melamine and/or cyanuric acid.
Preferably, the reaction dissolvent is selected from dimethyl sulfoxide (DMSO), dimethylformamide or dimethylacetylamide；
The acid binding agent is triethylamine, potassium carbonate, sodium acetate or sodium hydroxide.
Preferably, the preparation method of six-(4- amino-benzene oxygens) rings, three phosphonitrile includes：
Hexachlorocyclotriph,sphazene and acamol are reacted under conditions of third solvent and catalyst, obtained
Six-(4- acetylaminos phenoxy group) rings, three phosphonitrile；Three phosphonitrile of described six-(4- acetylaminos phenoxy group) rings is dissolved in the 4th solvent
In, be added the concentrated sulfuric acid or sodium hydroxide be deprotected to get；
Six-(4- acetylaminos phenoxy group) rings, three phosphonitrile is 1 with the molar ratio of the concentrated sulfuric acid or sodium hydroxide:
(100~200).
It is furthermore preferred that the molar ratio of the hexachlorocyclotriph,sphazene, acamol and catalyst is 1:(6.6~
7.2):(9.9~10.8)；
The catalyst is Anhydrous potassium carbonate；
The third solvent is acetone；
4th solvent is methanol.
The present invention also provides a kind of modified carbon nano-tubes obtained by the method.
The beneficial effects of the invention are as follows：
1) present invention uses hexachlorocyclotriph,sphazene and polyfunctional compound for reaction monomers, utilizes in-situ precipitate polycondensation
Method uniformly coats the polymeric layer rich in a large amount of high activity reactive groups in carbon nano tube surface；Method of modifying is one kettle way,
Easy to operate, reaction condition is mild, easy to implement；
2) it is adsorbed in the compound or polymer phase ratio of carbon nano tube surface with existing non-covalent bond, is coated in the present invention
The polymeric layer of carbon nano tube surface is because being height ring cross-linking type structure, the tridimensional network the same similar to knitting wool ball is twined,
Can uniformly, be steadily closely coated on carbon nano tube surface；Under not destroying carbon nanometer tube prototype structure and behavior pattern, help
The uniform and stable dispersion in solution or matrix resin in modified carbon nano-tube；
3) the surface coated poly phosphazene polymer layer of thickness of modified carbon nano-tube can be by carbon nanotube and anti-in the present invention
The consumption proportion between monomer is answered to control, to adapt to the regulation and control of material different performance.
Description of the drawings
In order to more clearly explain the embodiment of the invention or the technical proposal in the existing technology, to embodiment or will show below
There is attached drawing needed in technology description to be briefly described, it should be apparent that, the accompanying drawings in the following description is only this
The embodiment of invention for those of ordinary skill in the art without creative efforts, can also basis
The attached drawing of offer obtains other attached drawings.
Fig. 1 is the infrared spectrogram of carbon nanotube and the carbon nanotube after polymer overmold；
Fig. 2 is projection Electronic Speculum (TEM) figure of the carbon nanotube after polymer overmold.
Specific implementation mode
Below in conjunction with the embodiment of the present invention, technical scheme of the present invention is clearly and completely described, it is clear that
Described embodiments are only a part of the embodiments of the present invention, instead of all the embodiments.Based on the implementation in the present invention
Example, every other embodiment obtained by those of ordinary skill in the art without making creative efforts belong to
The scope of protection of the invention.
Embodiment 1
The method of synthesis six-(4- amino-benzene oxygens) rings, three phosphonitrile (HACP) provided in this embodiment, including：
1, by 10.8g Anhydrous potassium carbonates (K2CO3) grind into powder, it is added to together with 7.8g acamols
In 80mL acetone；At normal temperatures after magnetic agitation 30min, it is passed through high pure nitrogen, 2.5g hexachlorocyclotriph,sphazenes are then added
(HCCP), then at 70 DEG C magnetic agitation is reacted for 24 hours.
It waits for after reaction, being filtered by vacuum after solution is cooled to room temperature, taking filtrate；Filtrate revolving at thick,
It is freeze-dried after excessive deionized water is added, it is six-(4- acetylaminos phenoxy group) rings, three phosphonitrile to obtain white powder.
2, three phosphonitrile of 9g six-(4- acetylaminos phenoxy group) ring is dissolved in 180mL methanol, is then poured slowly into 108mL
The concentrated sulfuric acid, then reaction 4h is stirred at reflux at 80 DEG C.
After reaction, solution is cooled to room temperature, and weak aqua ammonia is added dropwise dropwise until solution to solution under ice salt bath environment
Then pH=8 solution is filtered by vacuum, filtrate pours into waste liquid barrel, after the solid on filter paper is cleaned with a large amount of deionized waters
It is dried in vacuo 48h at 50 DEG C, it is six-(4- amino-benzene oxygens) rings, three phosphonitrile (HACP) to obtain pale solid.
1H NMR(DMSO-d6,ppm,600Hz):6.42–6.53(4H,dd,Ar-H),4.91(2H,Ar-NH2)。
FTIR：In 3438 and 3338cm-1Locate presence-NH2Absorption peak；In 1507 and 1621cm-1There are aromatic ring C-C to stretch at place
Contracting vibration peak；In 1256,1178 and 952cm-1Place corresponds respectively to the characteristic peak of P-O-Ph, P-N-P and P-O-C.
The chemical constitution of six-(4- amino-benzene oxygens) rings, three phosphonitrile is as follows：
Embodiment 2
A kind of method of surface modification of carbon nanotube is present embodiments provided, including：
1,100mg carbon nanotubes are dissolved in 50mLDMSO, after being ultrasonically treated 1h under cell disruptor, it is molten obtains first
Liquid, for use；
2,0.035g HCCP and 0.083g HACP are dissolved in 50mLDMSO, mixing obtains the second solution, for use；
3,2mL acid binding agents triethylamine is first added in the first solution, then the second solution is slowly added dropwise by constant pressure funnel
Into the first solution, about 1h is dripped；Then magnetic agitation reacts 10h at 60 DEG C, then is filtered by vacuum, and collects filter residue；Using
Ethyl alcohol and deionized water distinguish supersound washing 2~3 times at normal temperatures, then are dried in vacuum tank, can obtain cladding thickness
Degree is about the modified carbon nano-tube of 10nm.
It in the present invention, theoretically can be by carbon nanotube, two kinds of reaction monomers and acid binding agent directly in reaction dissolvent
Mixing, then reacted.However, in practical R＆D process, so operation can bring asking for the too fast group's of the being formed packet of reaction rate
Topic, is unfavorable for forming the coating modification of single-root carbon nano-tube.In order to overcome the problem, inventor passes through multiple optimal screening, hair
Now by the above method, reaction rate can be slowed down, conducive to the coating modification of single-root carbon nano-tube is formed.
In the present invention, acid binding agent can also replace other substances such as：Potassium carbonate, sodium acetate or sodium hydroxide.This implementation
The triethylamine that example uses during the reaction, not will produce moisture, therefore use triethylamine as acid binding agent for optimal selection.
Embodiment 3
Method provided in this embodiment, the difference from example 2 is that：HCCP 0.087g；HACP0.021g；It obtains
Coating thickness be 60nm.
Remaining place is substantially the same manner as Example 2, no longer repeats one by one herein.
Embodiment 4
Method provided in this embodiment, the difference from example 2 is that：Carbon nanotube 1g；HCCP0.70g；HACP
1.7g；Obtained coating thickness is 130nm.
Remaining place is substantially the same manner as Example 2, no longer repeats one by one herein.
Embodiment 5
Method provided in this embodiment, the difference from example 2 is that：HCCP 0.052g；0.083gHACP is replaced with
0.050g hydroquinones；Obtained coating thickness is 30nm.
Remaining place is substantially the same manner as Example 2, no longer repeats one by one herein.
Embodiment 6
Method provided in this embodiment, the difference from example 2 is that：HCCP 0.070g；0.083gHACP is replaced with
0.065g p-phenylenediamine；Obtained coating thickness is 50nm.
Remaining place is substantially the same manner as Example 2, no longer repeats one by one herein.
Embodiment 7
Method provided in this embodiment, the difference from example 2 is that：HCCP 0.10g；0.083gHACP is replaced with
0.075g melamines；Obtained coating thickness is 68nm.
Remaining place is substantially the same manner as Example 2, no longer repeats one by one herein.
Embodiment 8
Method provided in this embodiment, the difference from example 2 is that：HCCP 0.10g；0.083gHACP is replaced with
HACP 0.21g and p-phenylenediamine 0.010g；Obtained coating thickness is 66nm.
Remaining place is substantially the same manner as Example 2, no longer repeats one by one herein.
Embodiment 9
Method provided in this embodiment, the difference from example 2 is that：HCCP 0.10g；0.083gHACP is replaced with
HACP 0.21g and melamine 0.011g；Obtained coating thickness is 61nm.
Remaining place is substantially the same manner as Example 2, no longer repeats one by one herein.
Embodiment 10
Method provided in this embodiment, the difference from example 2 is that：HCCP 0.10g；0.083gHACP is replaced with
HACP 0.21g, p-phenylenediamine 0.005g and melamine 0.005g；Obtained coating thickness is 65nm.
Remaining place is substantially the same manner as Example 2, no longer repeats one by one herein.
Embodiment 11
1, appropriate carbon nanotube and the carbon nanotube after polymer overmold are taken, infrared spectrum detection is carried out.Its is infrared
Spectrogram is as shown in Figure 1.
As shown, 1500cm-1And 1160cm-1There is apparent absorption peak in place, corresponds to the characteristic peak of phenyl ring respectively
With the characteristic peak of P=N keys, it was demonstrated that carbon nano tube surface has successfully coated phosphonitrilic polymer layer.
2, the carbon nanotube in right amount after polymer overmold is taken, is scanned using transmission electron microscope (TEM), transmission electron microscope picture
As shown in Figure 2.
It can be seen that by the electron microscope of Fig. 2, dark thin layer occurs in carbon nano tube surface, the thin layer according to Fig. 1
The as phosphonitrilic polymer layer of carbon nano tube surface cladding.
Claims (10)
1. a kind of method of surface modification of carbon nanotube, which is characterized in that including：
By carbon nanotube ultrasonic disperse in reaction dissolvent, the first solution is obtained；
Hexachlorocyclotriph,sphazene and the first compound are dissolved in reaction dissolvent, the second solution is obtained；
Acid binding agent is added in the first solution, then the second solution is slowly added in the first solution, reacts, obtain modified carbon nano tube
Pipe；
Wherein, first compound is：Six-(4- amino-benzene oxygens) rings, three phosphonitrile, bifunctional compound and trifunctional
It is one or more in compound.
2. according to the method described in claim 1, it is characterized in that, based on degree of functionality, the hexachlorocyclotriph,sphazene and described
The molar ratio of one compound is 1.0:(1.05~1.5)；
The mass ratio of the summation of the hexachlorocyclotriph,sphazene and the first compound and the carbon nanotube is (1~3):1.
3. according to the method described in claim 1, it is characterized in that, the temperature of the reaction be 40 DEG C~60 DEG C, time 5h
~48h；
The molar ratio of the acid binding agent and the hexachlorocyclotriph,sphazene is (1~2):1.
4. according to the method described in claim 1, it is characterized in that, the quality percentage of carbon nanotube described in first solution
Specific concentration is 0.1%~3%.
5. according to the method described in claim 1, it is characterized in that, the bifunctional compound is selected from NH2-R-OH、NH2-R-
NH2, it is one or more in HOOC-R-OH and HO-R-OH；
Wherein, R is-(C6H4)-or-(CH2)n, n=1~10.
6. according to the method described in claim 1, it is characterized in that, the trifunctional compound be selected from melamine and/or
Cyanuric acid.
7. according to the method described in claim 1, it is characterized in that, the reaction dissolvent is selected from dimethyl sulfoxide (DMSO), dimethyl methyl
Amide or dimethylacetylamide；
The acid binding agent is triethylamine, potassium carbonate, sodium acetate or sodium hydroxide.
8. according to the method described in claim 1, it is characterized in that, the preparation of six-(4- amino-benzene oxygens) rings, three phosphonitrile
Method includes：
Hexachlorocyclotriph,sphazene and acamol are reacted under conditions of third solvent and catalyst, obtain six-
Three phosphonitrile of (4- acetylaminos phenoxy group) ring；Three phosphonitrile of described six-(4- acetylaminos phenoxy group) rings is dissolved in the 4th solvent,
Be added the concentrated sulfuric acid or sodium hydroxide be deprotected to get；
Six-(4- acetylaminos phenoxy group) rings, three phosphonitrile is 1 with the molar ratio of the concentrated sulfuric acid or sodium hydroxide:(100~
200)。
9. according to the method described in claim 8, it is characterized in that, the hexachlorocyclotriph,sphazene, acamol and urging
The molar ratio of agent is 1:(6.6~7.2):(9.9~10.8)；
The catalyst is Anhydrous potassium carbonate；
The third solvent is acetone；
4th solvent is methanol.
10. the modified carbon nano-tube that the method described in claim 1 to 9 any one obtains.
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