CN113753879A - Temperature-sensitive polymer modified carbon nanotube composite material and preparation method thereof - Google Patents
Temperature-sensitive polymer modified carbon nanotube composite material and preparation method thereof Download PDFInfo
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- CN113753879A CN113753879A CN202010504247.2A CN202010504247A CN113753879A CN 113753879 A CN113753879 A CN 113753879A CN 202010504247 A CN202010504247 A CN 202010504247A CN 113753879 A CN113753879 A CN 113753879A
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical class [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 46
- 239000002131 composite material Substances 0.000 title claims abstract description 28
- 229920000642 polymer Polymers 0.000 title claims abstract description 27
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- 239000002048 multi walled nanotube Substances 0.000 claims abstract description 31
- 239000002041 carbon nanotube Substances 0.000 claims abstract description 24
- 229910021393 carbon nanotube Inorganic materials 0.000 claims abstract description 24
- 229920001400 block copolymer Polymers 0.000 claims abstract description 14
- 238000006243 chemical reaction Methods 0.000 claims abstract description 13
- 229940088644 n,n-dimethylacrylamide Drugs 0.000 claims description 13
- YLGYACDQVQQZSW-UHFFFAOYSA-N n,n-dimethylprop-2-enamide Chemical group CN(C)C(=O)C=C YLGYACDQVQQZSW-UHFFFAOYSA-N 0.000 claims description 13
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 12
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 12
- QNILTEGFHQSKFF-UHFFFAOYSA-N n-propan-2-ylprop-2-enamide Chemical compound CC(C)NC(=O)C=C QNILTEGFHQSKFF-UHFFFAOYSA-N 0.000 claims description 11
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 claims description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 8
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 6
- 229910052757 nitrogen Inorganic materials 0.000 claims description 6
- TVDSBUOJIPERQY-UHFFFAOYSA-N prop-2-yn-1-ol Chemical compound OCC#C TVDSBUOJIPERQY-UHFFFAOYSA-N 0.000 claims description 4
- 238000001291 vacuum drying Methods 0.000 claims description 4
- 239000007795 chemical reaction product Substances 0.000 claims description 3
- JZCCFEFSEZPSOG-UHFFFAOYSA-L copper(II) sulfate pentahydrate Chemical compound O.O.O.O.O.[Cu+2].[O-]S([O-])(=O)=O JZCCFEFSEZPSOG-UHFFFAOYSA-L 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- 238000010992 reflux Methods 0.000 claims description 3
- 235000010378 sodium ascorbate Nutrition 0.000 claims description 3
- 229960005055 sodium ascorbate Drugs 0.000 claims description 3
- PPASLZSBLFJQEF-RKJRWTFHSA-M sodium ascorbate Substances [Na+].OC[C@@H](O)[C@H]1OC(=O)C(O)=C1[O-] PPASLZSBLFJQEF-RKJRWTFHSA-M 0.000 claims description 3
- PPASLZSBLFJQEF-RXSVEWSESA-M sodium-L-ascorbate Chemical compound [Na+].OC[C@H](O)[C@H]1OC(=O)C(O)=C1[O-] PPASLZSBLFJQEF-RXSVEWSESA-M 0.000 claims description 3
- 238000001132 ultrasonic dispersion Methods 0.000 claims description 2
- YICILWNDMQTUIY-UHFFFAOYSA-N 2-methylidenepentanamide Chemical compound CCCC(=C)C(N)=O YICILWNDMQTUIY-UHFFFAOYSA-N 0.000 claims 1
- 239000000203 mixture Substances 0.000 claims 1
- 239000000463 material Substances 0.000 abstract description 3
- 125000000304 alkynyl group Chemical group 0.000 abstract description 2
- 125000000852 azido group Chemical group *N=[N+]=[N-] 0.000 abstract description 2
- 239000003153 chemical reaction reagent Substances 0.000 abstract description 2
- 230000000704 physical effect Effects 0.000 abstract description 2
- 238000001035 drying Methods 0.000 description 6
- 238000005406 washing Methods 0.000 description 6
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 4
- 229920001577 copolymer Polymers 0.000 description 4
- 238000001914 filtration Methods 0.000 description 4
- 239000012528 membrane Substances 0.000 description 4
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 4
- 239000004810 polytetrafluoroethylene Substances 0.000 description 4
- 239000011541 reaction mixture Substances 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 239000013590 bulk material Substances 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 230000004580 weight loss Effects 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 238000012512 characterization method Methods 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 238000004090 dissolution Methods 0.000 description 2
- 239000013067 intermediate product Substances 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 229920002939 poly(N,N-dimethylacrylamides) Polymers 0.000 description 2
- 229920003213 poly(N-isopropyl acrylamide) Polymers 0.000 description 2
- -1 polytetrafluoroethylene Polymers 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 238000000967 suction filtration Methods 0.000 description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 2
- 238000009210 therapy by ultrasound Methods 0.000 description 2
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- 238000005299 abrasion Methods 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000007385 chemical modification Methods 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 239000011557 critical solution Substances 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 238000012844 infrared spectroscopy analysis Methods 0.000 description 1
- 238000002329 infrared spectrum Methods 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 238000005461 lubrication Methods 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 239000002071 nanotube Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 230000035939 shock Effects 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 238000004627 transmission electron microscopy Methods 0.000 description 1
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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
- C01B32/174—Derivatisation; Solubilisation; Dispersion in solvents
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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
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2202/00—Structure or properties of carbon nanotubes
- C01B2202/06—Multi-walled nanotubes
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Abstract
The invention discloses a temperature-sensitive polymer modified carbon nanotube composite material and a preparation method thereof, wherein the temperature-sensitive polymer modified carbon nanotube composite material is prepared by click chemical reaction between alkynyl on the surface of a multi-wall carbon nanotube and block copolymer chain-end azido, the material obviously improves the solubility and the dispersibility of the carbon nanotube in a reagent, and simultaneously can keep the structure and the excellent physical properties of the carbon nanotube, and in addition, the novel modified polymer has strong enough binding force with the carbon nanotube.
Description
Technical Field
The invention relates to the technical field of new materials, in particular to a temperature-sensitive polymer modified carbon nanotube composite material and a preparation method thereof.
Background
Since the discovery of carbon nanotubes in japan Iijima in 1991, great interest has been generated by many scientists due to their unique structure, extremely high mechanical, electrical and chemical stability. The carbon nano tube is a special one-dimensional nano material which is formed by combining high-bonding-energy C ═ C double bonds, has a large pi-pi conjugated system and a very high aspect ratio, and has a plurality of excellent properties, such as heat resistance, corrosion resistance, thermal shock resistance, excellent heat transfer and electrical conductivity, self-lubrication, biocompatibility and the like. A series of comprehensive physical and chemical properties of the carbon nano tube enable the carbon nano tube to have important application prospects in the field of preparing high-performance abrasion-resistant composite materials, and the carbon nano tube composite materials are an important direction for the research of the carbon nano tube.
However, the carbon nanotubes are not soluble in water or organic solvents, and are difficult to be well dispersed and effectively combined in a composite matrix, so that the application field and performance of the carbon nanotubes are limited. The application of carbon nanotubes to the field of composite materials requires two key problems to be solved, namely, the dispersion of the nanotubes and the effective combination with the bulk material. This generally requires surface modification of the carbon nanotubes to allow for efficient dispersion in a selected solvent system, while having appropriate surface functional groups to allow for strong interactions with the bulk material to achieve effective bonding with the bulk material.
Disclosure of Invention
In view of this, the invention provides a temperature-sensitive polymer modified carbon nanotube composite material and a preparation method thereof.
The key point of the research is to explore a new method for modifying the surface of the carbon nano tube, and a new method for introducing a temperature-sensitive polymer into the surface of the carbon nano tube is researched by adopting a means of combining surface chemical treatment and covalent modification, so that a new temperature-sensitive polymer modified carbon nano tube composite material is synthesized.
The technical scheme is as follows:
the key point of the temperature-sensitive polymer modified carbon nanotube composite material is that the structural formula is as follows:
wherein R is a poly-N, N-dimethylacrylamide/poly-N-isopropylacrylamide block copolymer.
The second object of the present invention is:
the preparation method of the temperature-sensitive polymer modified carbon nanotube composite material is characterized by comprising the following steps:
(1) dispersing multi-walled carbon nanotubes with hydroxyl on the surface in toluene-2, 4-diisocyanate, reacting for 72 hours at 70-90 ℃ under the protection of nitrogen, filtering and washing reaction products, and drying in vacuum to obtain preliminarily modified multi-walled carbon nanotubes;
(2) taking 1-100 mg of the preliminarily modified multi-walled carbon nano-tube, injecting anhydrous toluene under the protection of nitrogen, adding propargyl alcohol after ultrasonic dispersion, carrying out reflux reaction at 90-110 ℃ for 48h, and carrying out suction filtration, washing and drying after the reaction is finished to obtain the alkynyl-modified multi-walled carbon nano-tube;
(3) taking 1-4mg of the alkynylated multi-walled carbon nanotube, dispersing with water, performing ultrasonic treatment, mixing with the dissolved poly-N, N-dimethylacrylamide/poly-N-isopropylacrylamide block copolymer, raising the temperature of a reaction system to 40-60 ℃, and adding 1-71.2 mg of sodium ascorbate and 1-36.0 mg of copper sulfate pentahydrate;
(4) and (3) keeping the reaction system at 40-60 ℃ for reacting for 24h, filtering, washing and drying in vacuum to obtain the temperature-sensitive polymer covalently modified carbon nanotube composite material.
The number of layers of the multi-walled carbon nanotube in the step (1) is 2-100.
And (3) mixing the alkynyl-modified multi-walled carbon nanotube and a poly (N, N-dimethylacrylamide)/poly (N-isopropylacrylamide) block copolymer in the step (2), wherein the concentration of the poly (N, N-dimethylacrylamide)/poly (N-isopropylacrylamide) block copolymer is 1-3 mg/mL.
In the step (1), 1-100 mg of the multi-walled carbon nanotube with hydroxyl on the surface is dispersed in 1-50 ml of toluene-2, 4-diisocyanate.
The vacuum drying in the steps (2) and (4) is vacuum drying for 24 hours at the temperature of 30-50 ℃.
The invention provides a temperature-sensitive polymer modified carbon nanotube composite material and a preparation method thereof, wherein the temperature-sensitive polymer modified carbon nanotube composite material is prepared by click chemical reaction between alkynyl on the surface of a multi-wall carbon nanotube and block copolymer chain-end azido, and the material can change the surface hydrophilic/hydrophobic properties of the carbon nanotube at different temperatures, and is specifically represented as follows: when the temperature is lower than the critical dissolution temperature (55 ℃) of the poly-N, N-dimethylacrylamide/poly-N-isopropylacrylamide segmented copolymer, the prepared temperature-sensitive polymer modified carbon nano tube has good water dispersibility, and conversely, when the temperature is higher than the critical dissolution temperature (55 ℃) of the copolymer, the prepared temperature-sensitive polymer modified carbon nano tube is gradually agglomerated in water.
Compared with the prior art, the invention has the beneficial effects that: the prepared temperature-sensitive polymer modified carbon nanotube composite material obviously improves the solubility and the dispersibility of the carbon nanotube in a reagent, can keep the structure and the excellent physical property of the carbon nanotube, and has strong enough binding force with the carbon nanotube.
Drawings
FIG. 1 is a reaction scheme of example 1;
FIG. 2 is an infrared spectrum of an alkynyl-modified multi-walled carbon nanotube;
FIG. 3 is a TG curve of an alkynyl-modified multi-walled carbon nanotube;
FIG. 4 is a TGA test result of a covalently modified carbon nanotube composite of poly N, N-dimethylacrylamide/poly N-isopropylacrylamide block copolymer;
FIG. 5 is a TEM characterization of multi-walled carbon nanotubes before and after copolymer modification;
FIG. 6 is a transmission electron microscope analysis of the solubility of a carbon nanotube composite covalently modified with poly-N, N-dimethylacrylamide/poly-N-isopropylacrylamide block copolymer.
Detailed Description
The following examples are intended to illustrate the invention but are not intended to limit the scope of the invention. The starting materials used in the examples are all commercially available products unless otherwise specified.
Example 1, the reaction scheme of this example is shown in figure 1.
1. Dispersing 1-100 mg of multi-walled (2-100 layers of) carbon nanotubes (named as MWNT-OH) with hydroxyl on the surface into 1-50 mL of toluene-2, 4-diisocyanate (TDI), reacting for 72h at 70-90 ℃ under the protection of nitrogen, filtering a reaction product by using a polytetrafluoroethylene membrane (PTFE membrane with the pore diameter of 200nm), washing for several times by using anhydrous toluene to remove residual TDI, and then drying for 24h at 30-50 ℃ in vacuum to obtain the TDI modified multi-walled carbon nanotubes (named as MWNT-NCO);
2. adding 1-100 mg of MWNT-NCO into a 100m L round-bottom flask, injecting 1-15 mL of anhydrous toluene by using an injector under the protection of nitrogen, ultrasonically dispersing for 30min, adding 1-6 mL of propiolic alcohol (PPL), carrying out reflux reaction at 90-110 ℃ for 48h, after the reaction is finished, carrying out suction filtration by using a 200nm PTFE membrane, washing for 3 times by using Tetrahydrofuran (THF), and drying in a vacuum box to obtain an alkynyl-modified multi-walled carbon nanotube which is marked as MWNTs;
the results of the infrared spectroscopic analysis of the raw material MWNT-OH, the intermediate product MWNT-NCO and the MWNTs are respectively shown in FIG. 2, the results of the thermogravimetric curves of the raw material MWNT-OH, the intermediate product MWNT-NCO and the MWNTs are contrastively analyzed, the results are shown in FIG. 3, curves A, B, C in FIGS. 2 and 3 respectively correspond to the MWNT-OH, the MWNT-NCO and the MWNTs, and therefore the alkynyl-modified multi-wall carbon nano-tube is successfully prepared;
3. adding 1-180 mg of poly-N, N-dimethylacrylamide/poly-N-isopropylacrylamide segmented copolymer (the critical solution temperature is 55 ℃, the CAS number is 151954-97-1) and 1-55 mL of water into a 100mL single-neck bottle, raising the reaction temperature to 40-60 ℃ after fully dissolving, dispersing 1-4mg of the alkynyl-modified multi-walled carbon nanotube prepared in the step 2 with 1-5 mL of water, adding into the single-neck bottle after ultrasonic treatment for 5min, keeping the final concentration of the polymer at 1-3 mg/mL, and adding 1-71.2 mg of sodium ascorbate and 1-36.0 mg of copper sulfate pentahydrate;
4. and (2) reacting the reaction mixture at 40-60 ℃ for 24h, filtering the reaction mixture by using a polytetrafluoroethylene membrane (the aperture is 200nm), washing the reaction mixture for several times by using water, ammonia water and methanol to remove residual polymers, and finally drying the reaction mixture in vacuum to obtain the temperature-sensitive polymer poly-N, N-dimethylacrylamide/poly-N-isopropylacrylamide block copolymer covalently modified carbon nanotube composite material.
The comparison of MWNT-DMA508 and MWNT-DMA255-NIPAN227 shows that the thermal weight loss analysis of the poly-N, N-dimethylacrylamide carbon nanotube composite material purchased from the market is performed, and the results are shown in FIG. 4, wherein curves a and b are the thermal weight loss curves of the commercially available MWNT-DMA508 at 30 ℃ and 55 ℃, and curves c and d are the thermal weight loss curves of the MWNT-DMA255-NIPAN at 30 ℃ and 55 ℃, respectively, and the comparison shows that the poly-N, N-dimethylacrylamide/poly-N-isopropylacrylamide block copolymer has been successfully modified on the multi-walled carbon nanotube.
TEM characterization is performed on MWNT-OH as a raw material and the temperature-sensitive polymer poly-modified carbon nanotube composite material prepared in this example, and the results are shown in C and F in FIG. 5, which shows that the original unmodified multi-walled carbon nanotube with hydroxyl (FIG. 5C) is coated with a layer of temperature-sensitive polymer (FIG. 5F) on the periphery after chemical modification.
The solubility of the temperature-sensitive polymer poly-modified carbon nanotube composite material prepared in this example was analyzed by transmission electron microscopy, and the result is shown in fig. 6. Wherein, the graphs A and B show that the temperature-sensitive polymer poly-modified carbon nano tube composite material has poor dispersity at the temperature when the temperature of the aqueous solution is more than 60 ℃, and the graphs D and E show that the temperature-sensitive polymer poly-modified carbon nano tube composite material has good dispersity when the temperature of the aqueous solution is reduced to 40 ℃.
Finally, it should be noted that the above-mentioned description is only a preferred embodiment of the present invention, and those skilled in the art can make various similar representations without departing from the spirit and scope of the present invention.
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CN1513757A (en) * | 2003-07-31 | 2004-07-21 | 上海交通大学 | Preparation method of block polymer grafted carbon nanotubes |
CN1556032A (en) * | 2003-12-30 | 2004-12-22 | 上海交通大学 | Temperature-sensitive water-soluble carbon nanotubes and preparation method thereof |
CN101177262A (en) * | 2007-11-08 | 2008-05-14 | 浙江大学 | A method for preparing water-soluble and highly biocompatible carbon nanotubes |
CN101234758A (en) * | 2008-02-02 | 2008-08-06 | 兰州大学 | Preparation method of carbon nanotube substituted by benzyl chloride and grafting modification method initiated by it |
CN101555006A (en) * | 2009-05-12 | 2009-10-14 | 青岛大学 | Preparation method of modified carbon nanotube |
WO2017170928A1 (en) * | 2016-03-30 | 2017-10-05 | 国立大学法人東北大学 | Composite material |
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CN1513757A (en) * | 2003-07-31 | 2004-07-21 | 上海交通大学 | Preparation method of block polymer grafted carbon nanotubes |
CN1556032A (en) * | 2003-12-30 | 2004-12-22 | 上海交通大学 | Temperature-sensitive water-soluble carbon nanotubes and preparation method thereof |
CN101177262A (en) * | 2007-11-08 | 2008-05-14 | 浙江大学 | A method for preparing water-soluble and highly biocompatible carbon nanotubes |
CN101234758A (en) * | 2008-02-02 | 2008-08-06 | 兰州大学 | Preparation method of carbon nanotube substituted by benzyl chloride and grafting modification method initiated by it |
CN101555006A (en) * | 2009-05-12 | 2009-10-14 | 青岛大学 | Preparation method of modified carbon nanotube |
WO2017170928A1 (en) * | 2016-03-30 | 2017-10-05 | 国立大学法人東北大学 | Composite material |
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