CN103992448B - Polymer grafted carbon nano-tubes and preparing method thereof - Google Patents
Polymer grafted carbon nano-tubes and preparing method thereof Download PDFInfo
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- CN103992448B CN103992448B CN201410161982.2A CN201410161982A CN103992448B CN 103992448 B CN103992448 B CN 103992448B CN 201410161982 A CN201410161982 A CN 201410161982A CN 103992448 B CN103992448 B CN 103992448B
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- carbon nano
- polymer grafted
- cnt
- nano tube
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 42
- 239000002041 carbon nanotube Substances 0.000 title claims abstract description 34
- 229910021393 carbon nanotube Inorganic materials 0.000 title claims abstract description 33
- 229920000642 polymer Polymers 0.000 title claims abstract description 16
- 238000000034 method Methods 0.000 title abstract description 10
- 238000006243 chemical reaction Methods 0.000 claims abstract description 27
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 22
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 12
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 11
- 239000000178 monomer Substances 0.000 claims abstract description 9
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 claims abstract description 7
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 7
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims abstract description 4
- 238000002360 preparation method Methods 0.000 claims description 12
- WFKAJVHLWXSISD-UHFFFAOYSA-N isobutyramide Chemical compound CC(C)C(N)=O WFKAJVHLWXSISD-UHFFFAOYSA-N 0.000 claims description 7
- ZTWTYVWXUKTLCP-UHFFFAOYSA-L ethenyl-dioxido-oxo-$l^{5}-phosphane Chemical compound [O-]P([O-])(=O)C=C ZTWTYVWXUKTLCP-UHFFFAOYSA-L 0.000 claims description 6
- 239000003999 initiator Substances 0.000 claims description 5
- 238000005576 amination reaction Methods 0.000 claims description 4
- ZTWTYVWXUKTLCP-UHFFFAOYSA-N vinylphosphonic acid Chemical class OP(O)(=O)C=C ZTWTYVWXUKTLCP-UHFFFAOYSA-N 0.000 claims description 4
- 239000008367 deionised water Substances 0.000 claims description 3
- 229910021641 deionized water Inorganic materials 0.000 claims description 3
- 239000012535 impurity Substances 0.000 claims description 3
- 239000000376 reactant Substances 0.000 claims description 3
- 239000007787 solid Substances 0.000 claims description 3
- 238000002604 ultrasonography Methods 0.000 claims description 3
- -1 alkenyl phosphonic acid Chemical compound 0.000 claims description 2
- 238000001914 filtration Methods 0.000 claims description 2
- 239000007789 gas Substances 0.000 claims description 2
- 239000002904 solvent Substances 0.000 claims description 2
- 239000002071 nanotube Substances 0.000 claims 2
- 238000006116 polymerization reaction Methods 0.000 claims 1
- 230000008569 process Effects 0.000 abstract description 3
- 238000009210 therapy by ultrasound Methods 0.000 abstract 2
- BNKAXGCRDYRABM-UHFFFAOYSA-N ethenyl dihydrogen phosphate Chemical compound OP(O)(=O)OC=C BNKAXGCRDYRABM-UHFFFAOYSA-N 0.000 abstract 1
- 230000000977 initiatory effect Effects 0.000 abstract 1
- 238000001069 Raman spectroscopy Methods 0.000 description 3
- 239000006185 dispersion Substances 0.000 description 3
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000002086 nanomaterial Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 230000006641 stabilisation Effects 0.000 description 2
- 238000011105 stabilization Methods 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 238000001291 vacuum drying Methods 0.000 description 2
- MHABMANUFPZXEB-UHFFFAOYSA-N O-demethyl-aloesaponarin I Natural products O=C1C2=CC=CC(O)=C2C(=O)C2=C1C=C(O)C(C(O)=O)=C2C MHABMANUFPZXEB-UHFFFAOYSA-N 0.000 description 1
- UATOFRZSCHRPBG-UHFFFAOYSA-N acetamide;hydrate Chemical compound O.CC(N)=O UATOFRZSCHRPBG-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000002242 deionisation method Methods 0.000 description 1
- 238000007306 functionalization reaction Methods 0.000 description 1
- 238000010559 graft polymerization reaction Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000002329 infrared spectrum Methods 0.000 description 1
- 230000010354 integration Effects 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 150000003009 phosphonic acids Chemical class 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 230000002269 spontaneous effect Effects 0.000 description 1
- 238000012430 stability testing Methods 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
Abstract
The invention discloses polymer grafted carbon nano-tubes and a preparing method thereof. The method comprises the steps that: monomer vinyl phosphoric acid and carbon nano-tubes are added into dimethylacetamide, and ultrasonic treatment is performed; under the protection of nitrogen, azodiisobutyronitrile is added for initiating reactions, and the ultrasonic treatment is continuously performed; a reaction device is transferred into oil bath, and the temperature is controlled until the reaction is finished, so that polymer grafted carbon nano-tubes are obtained. The preparing method provided by the invention has the advantages of reasonable process and simple reaction operation, and is capable of obviously improving the dispersity of carbon nano-tubes in water. The polymer grafted carbon nanometer tube has a structure defined in the description.
Description
Technical field
The present invention relates to a kind of polymer grafted carbon nano tube and preparation field, specially PVPA polymer
Grafting carbon nanotube and preparation method thereof.Its dispersibility in water can be significantly improved after the grafting of CNT aggregated thing.
Technical background
CNT, as a kind of widely used carbon nanomaterial, has high intensity and modulus.It is introduced into
Material will make the mechanical property of material, hot property and fire resistance etc. be greatly enhanced.But due to carbon nanometer
The specific surface area of pipe is big, and surface can be high so that they are easy to reunite and form larger-size aggregate, reach the most stable
State, this is a kind of spontaneous process thermodynamically.No matter which field carbon nanomaterial is applied in, forms aggregate and is all
Disadvantageous.Therefore CNT is carried out suitable surface modification treatment improve its dispersibility have become as in recent years research heat
Point.
Summary of the invention
The present invention is directed to the deficiencies in the prior art, it is provided that after a kind of aggregated thing is surface-functionalized, the dispersion in water is steady
Qualitative height, is difficult to the polymer grafted carbon nano tube reunited.
The polymer grafted carbon nano tube i.e. PVPA grafting carbon nanotube that the present invention is above-mentioned, its structure expression
(general structure) is as follows:
The present invention also provides for the above-mentioned PVPA grafting that a kind of synthesis technique is simple to operate, reaction condition is gentle
The preparation method of CNT, preparation process includes:
(1) with dimethyl acetylamide as solvent, in reaction vessel, monomer vinyl phosphonic acids (vinyl phosphonate it is sequentially added into
Monomer) and CNT, this reaction vessel is put in Ultrasound Instrument, with the power more than or equal to 250W at 60～80 DEG C ultrasonic
1～2h；
(2) in the reaction vessel of step (1), nitrogen 0.5～1h it is passed through, to remove the air in reaction system；
(3) under nitrogen protection, in the reaction vessel of step (2), add initiator azodiisobutyronitrile to cause
Polyreaction, and at 60～80 DEG C, continue ultrasonic 1.5～3h；
(4) after ultrasonic end, transferring in oil bath by the reaction vessel in step (3), controlling oil bath temperature is 60～80
DEG C, the lower reaction 6～8h of nitrogen protection；
(5), after step (4) reaction terminates, it is cooled to room temperature, filters out unreacted reactant and solid impurity；Then deionization is used
Water and dimethylacetamide (N, N-dimethylacetamide, DMAC) respectively wash for several times, to remove unreacted monomer and initiator, then
After filtration, at 60～80 DEG C, vacuum drying obtains PVPA grafting carbon nanotube.
The above-mentioned CNT of the present invention is aminated carbon nano tube, from Chengdu organic chemistry company limited of the Chinese Academy of Sciences
Buying, amination ratio is 0.45wt%, diameter range 8-15nm, a length of 50 μm.
Above-mentioned monomer (vinyl phosphonate) structural formula of the present invention is as follows:
As preferably, the dimethyl acetylamide described in step (1), vinyl phosphonate, the consumption proportion of CNT are
20～60 milliliters: 10～30 grams: 0.3～1.0 gram (equal proportion can expand or shrink)；As further preferably, step (1)
Described in dimethyl acetylamide, vinyl phosphonate, the consumption proportion of CNT be 30～60 milliliters: 15～30 grams: 0.5～
1.0 grams.
As preferably, in step (2) consumption proportion of CNT and azodiisobutyronitrile be 0.3～1.0 gram: 0.6～
1.2 grams (equal proportion can expand or shrink)；As further preferably, CNT and azodiisobutyronitrile in step (2)
Consumption proportion be 0.5～1.0 gram: 0.9～1.2 gram.
The PVPA grafting carbon nanotube that the present invention is above-mentioned to prepare reaction equation as follows:
Advantages of the present invention and beneficial effect:
(1) PVPA grafting carbon nanotube synthesis technique of the present invention is reasonable, and reaction condition is gentle.
(2) the PVPA grafting carbon nanotube that prepared by the inventive method, owing to PVPA has strong parent
Aqueous, such that it is able to be greatly improved CNT dispersion stabilization in water；Additionally, selecting amination ratio is 0.45
Wt%, diameter range 8-15nm, the aminated carbon nano tube of a length of 50 μm is as raw material and vinyl phosphonic acid reaction, and yield is high,
Side reaction is few, and raw material utilizes fully, and is not easy to reunite and form larger-size aggregate, and reaction is thoroughly.
Accompanying drawing explanation
The FT-IR figure of Fig. 1 PVPA grafting carbon nanotube (embodiment of the present invention).
The Raman figure of Fig. 2 PVPA grafting carbon nanotube (embodiment of the present invention).
The TG figure of Fig. 3 PVPA grafting carbon nanotube (embodiment of the present invention).
Fig. 4 CNT (a) and PVPA grafting carbon nanotube (b) dispersibility phenogram of 1 hour in water.
Fig. 5 CNT (a) and PVPA grafting carbon nanotube (b) dispersibility of 24 hours in water characterizes
Figure.
Fig. 6 CNT (a) and PVPA grafting carbon nanotube (b) dispersibility phenogram of 1 month in water.
Fig. 7 CNT (a) and PVPA grafting carbon nanotube (b) dispersibility phenogram of 3 months in water.
Detailed description of the invention
Below by specific embodiment, the present invention is described in further detail, but the present invention is not limited solely to following reality
Execute example.Some nonessential improvement that the present invention is made by the person skilled in the art in this field according to present invention and adjusting still
Belong to protection scope of the present invention.
Embodiment:
Experimental raw used in the present embodiment if no special instructions, all can easily obtain from commercial company.
(1) in the 100ml three-neck flask being equipped with nitrogen siphunculus, it is sequentially added into 30ml dimethyl acetylamide 15g vinyl
Phosphonic acids and 0.4g CNT, put in Ultrasound Instrument by above-mentioned three-neck flask, with the power of 250W ultrasonic 1.5h at 80 DEG C；
(2) in the three-neck flask of step (1), it is passed through nitrogen 0.5h, removes the air in reaction system.
(3) temperature controls, at about 70 DEG C, to add the azo of 0.8g in the three-neck flask of step (2) under nitrogen protection
Bis-isobutyronitrile causes graft polymerization reaction, continues ultrasonic 2h.
(4) after ultrasonic end, transferring in oil bath by the three-neck flask in step (3), controlling oil bath temperature is 80 DEG C, nitrogen
8h is reacted under gas shielded.
(5), after reaction terminates, it is cooled to room temperature, filters out unreacted reactant and solid impurity.Then with deionized water and two
Methyl vinyl respectively washs 3 times, removes unreacted monomer and initiator.At 70 DEG C, vacuum drying obtains PVPA grafting
CNT.(infrared spectrum of gained sample, Raman spectrogram and thermogravimetric curve are shown in Fig. 1, Fig. 2 and Fig. 3 respectively).
Comparative example
Other steps, with the step of above-described embodiment, only need the most not introduce CNT.
Embodiment gained properties of sample detects:
It can be seen that CNT is after PVPA is grafted from the FT-IR spectrogram of product, P-OH shakes
Dynamic peak is remarkably reinforced, it was demonstrated that being successfully prepared of PVPA grafting carbon nanotube.
D peak obtained by respectively product Raman being tested and G peak integration, the ratio (I of obtained two peak areasD/
IG).Found that the I of PVPA grafting carbon nanotubeD/IGHigher than original carbon nanotubes, this is due to CNT table
The functionalization in face.
Taking sample 5～10mg, heating rate is 20 DEG C/min, and product is carried out heat stability testing.Produce in reaction
In the thermogravimetric curve of thing, the CNT carbon left reduction after grafting is because being grafted on the polyvinyl of carbon nano tube surface
Caused by the degraded of phosphonic acids.
Take 1.5mg product to be dissolved in 15ml deionized water, the most quiet with the power ultrasonic 1h more than or equal to 100W
Put；Similarity condition processes CNT as object of reference.Number is shot respectively respectively behind 1 hour, 24 hours, 1 month and 3 months
Code photo (Fig. 4-7).It can clearly be seen that CNT dispersibility after PVPA is grafted significantly improves.Three months
After, due to the strongly hydrophilic of PVPA, surface-functionalized after CNT dispersion stabilization remain in that well.
Claims (7)
1. a polymer grafted carbon nano tube, it is characterised in that: its structure expression is as follows:
。
2. the preparation method of the polymer grafted carbon nano tube described in a claim 1, it is characterised in that: preparation process bag
Include:
(1) with dimethyl acetylamide as solvent, in reaction vessel, monomer vinyl phosphonic acids and CNT it are sequentially added into, by this
Reaction vessel is put in Ultrasound Instrument, with ultrasonic 1 ~ 2 h under 60 ~ 80 ° of C of the power more than or equal to 250 W；
(2) in the reaction vessel of step (1), nitrogen 0.5 ~ 1 h it is passed through, to remove the air in reaction system；
(3) in the reaction vessel of step (2), under nitrogen protection, add initiator azodiisobutyronitrile carry out causing polymerization anti-
Should, and under 60 ~ 80 ° of C, continue ultrasonic 1.5 ~ 3 h；
(4) after ultrasonic end, transferring in oil bath by the reaction vessel in step (3), controlling oil bath temperature is 60 ~ 80 ° of C, nitrogen
6 ~ 8 h are reacted under gas shielded；
(5), after step (4) reaction terminates, it is cooled to room temperature, filters out unreacted reactant and solid impurity；Then with deionized water and
Dimethylacetamide respectively washs for several times, and to remove unreacted monomer and initiator, after then filtering, under 60 ~ 80 ° of C, vacuum is done
Dry obtain PVPA grafting carbon nanotube；
Described CNT be amination ratio be 0.45 wt%, diameter range 8-15 nm, the amination of a length of 50 μm
CNT.
The preparation method of polymer grafted carbon nano tube the most according to claim 2, it is characterised in that: described monomer second
The structural formula of alkenyl phosphonic acid is as follows:
。
The preparation method of polymer grafted carbon nano tube the most according to claim 2, it is characterised in that: institute in step (1)
The dimethyl acetylamide stated, vinyl phosphonate, the consumption proportion of CNT are 20 ~ 60 milliliters: 10 ~ 30 grams: 0.3 ~ 1.0 gram.
The preparation method of polymer grafted carbon nano tube the most according to claim 4, it is characterised in that: institute in step (1)
The dimethyl acetylamide stated, vinyl phosphonate, the consumption proportion of CNT are 30 ~ 60 milliliters: 15 ~ 30 grams: 0.5 ~ 1.0 gram.
The preparation method of polymer grafted carbon nano tube the most according to claim 2, it is characterised in that: carbon in step (2)
The consumption proportion of nanotube and azodiisobutyronitrile is 0.3 ~ 1.0 gram: 0.6 ~ 1.2 gram.
The preparation method of polymer grafted carbon nano tube the most according to claim 6, it is characterised in that: carbon in step (2)
The consumption proportion of nanotube and azodiisobutyronitrile is 0.5 ~ 1.0 gram: 0.9 ~ 1.2 gram.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101104511A (en) * | 2006-07-14 | 2008-01-16 | 同济大学 | Method for preparing functional carbon nano-tube and application thereof |
| CN101104668A (en) * | 2006-07-12 | 2008-01-16 | 同济大学 | Method for preparing functional carbon nano-tube and application thereof |
| WO2010001123A1 (en) * | 2008-07-04 | 2010-01-07 | Imperial Innovations Limited | A process for the production of a functionalised carbon nanomaterial |
| CN103386258A (en) * | 2013-06-29 | 2013-11-13 | 浙江工业大学 | Preparation method of polyamide composite nanofiltration membrane containing modified carbon nano tube |
-
2014
- 2014-04-22 CN CN201410161982.2A patent/CN103992448B/en not_active Expired - Fee Related
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101104668A (en) * | 2006-07-12 | 2008-01-16 | 同济大学 | Method for preparing functional carbon nano-tube and application thereof |
| CN101104511A (en) * | 2006-07-14 | 2008-01-16 | 同济大学 | Method for preparing functional carbon nano-tube and application thereof |
| WO2010001123A1 (en) * | 2008-07-04 | 2010-01-07 | Imperial Innovations Limited | A process for the production of a functionalised carbon nanomaterial |
| CN103386258A (en) * | 2013-06-29 | 2013-11-13 | 浙江工业大学 | Preparation method of polyamide composite nanofiltration membrane containing modified carbon nano tube |
Non-Patent Citations (1)
| Title |
|---|
| UV radiation induced flame retardant cellulose fiber by using polyvinylphosphonic acid/carbon nanotube composite coating;Mazeyar Parvinzadeh Gashti等;《Composites : Part B》;20120816(第45期);第282-289页 * |
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