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 PDF

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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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carbon nanotube
walled carbon
carbon nanotubes
temperature
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陈勇
孙陆逸
孙培入
王松
段宏林
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Chongqing University of Science and Technology
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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

Temperature-sensitive polymer modified carbon nanotube composite material and preparation method thereof
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:
Figure BDA0002525936920000021
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.

Claims (6)

1.一种温敏聚合物修饰的碳纳米管复合材料,其特征在于其结构式如下:1. a carbon nanotube composite material modified by a thermosensitive polymer is characterized in that its structural formula is as follows:
Figure FDA0002525936910000011
Figure FDA0002525936910000011
其中,R为聚N,N-二甲基丙烯酰胺/聚N-异丙基丙烯酰胺嵌段共聚物。Wherein, R is a poly-N,N-dimethylacrylamide/poly-N-isopropylacrylamide block copolymer.
2.一种根据权利要求1所述的温敏聚合物修饰的碳纳米管复合材料的制备方法,其特征在于包括以下步骤:2. a preparation method of the carbon nanotube composite material modified by thermosensitive polymer according to claim 1, is characterized in that comprising the following steps: (1)将表面带羟基的多壁碳纳米管分散在甲苯-2,4-二异氰酸酯中,在氮气保护下于70℃~90℃反应72h,反应产物经过滤、洗涤后,真空干燥,得到经初步修饰的多壁碳纳米管;(1) Disperse the multi-walled carbon nanotubes with hydroxyl groups on the surface in toluene-2,4-diisocyanate, and react under nitrogen protection at 70°C to 90°C for 72 hours. The reaction product is filtered, washed, and dried in vacuum to obtain Preliminarily modified multi-walled carbon nanotubes; (2)取1~100mg所述经初步修饰的多壁碳纳米管,在氮气保护下注入无水甲苯,超声分散后加入丙炔醇,于90℃~110℃回流反应48h,反应结束后抽滤、洗涤并干燥,得到炔基修饰的多壁碳纳米管;(2) Take 1-100 mg of the preliminarily modified multi-walled carbon nanotubes, inject anhydrous toluene under nitrogen protection, add propargyl alcohol after ultrasonic dispersion, reflux at 90°C to 110°C for 48 hours, and pump Filter, wash and dry to obtain alkynyl-modified multi-walled carbon nanotubes; (3)取1-4mg所述炔基化多壁碳纳米管用水散后超声,然后与溶解后的聚N,N-二甲基丙烯酰胺/聚N-异丙基丙烯酰胺嵌段共聚物混合,将反应体系温度升高至40-60℃,再加入1~71.2mg抗坏血酸钠和1~36.0mg五水硫酸铜;(3) Disperse 1-4 mg of the alkynylated multi-walled carbon nanotubes with water and then sonicate, then mix with the dissolved poly-N,N-dimethylacrylamide/poly-N-isopropylacrylamide block copolymer Mixing, raising the temperature of the reaction system to 40-60°C, and then adding 1-71.2 mg of sodium ascorbate and 1-36.0 mg of copper sulfate pentahydrate; (4)将反应体系保持在40~60℃反应24h后过滤、洗涤、真空干燥,即可得到一种温敏聚合物修饰的碳纳米管复合材料。(4) The reaction system is kept at 40-60° C. for 24 hours, filtered, washed and dried in vacuum to obtain a temperature-sensitive polymer-modified carbon nanotube composite material. 3.根据权利要求2所述的制备方法,其特征在于:步骤(1)中所述多壁碳纳米管的层数为2~100层。3 . The preparation method according to claim 2 , wherein the number of layers of the multi-walled carbon nanotubes in step (1) is 2-100 layers. 4 . 4.根据权利要求2或3所述的制备方法,其特征在于:步骤(3)中所述炔基修饰的多壁碳纳米管与聚N,N-二甲基丙烯酰胺/聚N-异丙基丙烯酰胺嵌段共聚物混合后,其中的聚N,N-二甲基丙烯酰胺/聚N-异丙基丙烯酰胺嵌段共聚物浓度为1~3mg/mL。4. The preparation method according to claim 2 or 3, characterized in that: the alkynyl-modified multi-walled carbon nanotubes described in step (3) and poly-N,N-dimethylacrylamide/poly-N-iso After the propylacrylamide block copolymer is mixed, the concentration of the poly-N,N-dimethylacrylamide/poly-N-isopropylacrylamide block copolymer is 1-3 mg/mL. 5.根据权利要求2所述的制备方法,其特征在于:步骤(1)中表面带羟基的多壁碳纳米管为1~100mg,分散在1~50ml甲苯-2,4-二异氰酸酯中。5 . The preparation method according to claim 2 , wherein in step (1), 1-100 mg of multi-walled carbon nanotubes with hydroxyl groups on the surface are dispersed in 1-50 ml of toluene-2,4-diisocyanate. 6 . 6.根据权利要求4所述的制备方法,其特征在于:步骤(2)和(4)中所述的真空干燥为在30℃~50℃下真空干燥24h。6 . The preparation method according to claim 4 , wherein the vacuum drying in steps (2) and (4) is vacuum drying at 30° C. to 50° C. for 24 hours. 7 .
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Application publication date: 20211207