阅读说明：本技术 碳基复合材料的制备方法 (Preparation method of carbon-based composite material ) 是由 袁奕琳 徐丹丹 何为 于 2021-09-17 设计创作，主要内容包括：本发明公开了一种碳基复合材料的制备方法；将改性碳纳米管研磨并分散在无水乙醇中,得到改性碳纳米管悬浮液；将高分子树脂溶解在所述改性碳纳米管悬液中,加入硬化剂,超声振荡与搅拌,干燥,得到碳基复合材料。其中,改性碳纳米管由11-羰基-Β-乙酰乳香酸改性碳纳米管；制得的碳基复合材料具有较高力学性能以及优良的导热性与导电性能,使其在燃料电池双极板中具有广泛的应用。(The invention discloses a preparation method of a carbon-based composite material; grinding and dispersing the modified carbon nano tube in absolute ethyl alcohol to obtain modified carbon nano tube suspension; and dissolving polymer resin in the modified carbon nanotube suspension, adding a hardening agent, performing ultrasonic oscillation and stirring, and drying to obtain the carbon-based composite material. Wherein the modified carbon nanotube is a 11-carbonyl-BETA-acetyl boswellic acid modified carbon nanotube; the prepared carbon-based composite material has high mechanical property and excellent thermal conductivity and electrical conductivity, so that the carbon-based composite material has wide application in fuel cell bipolar plates.)

1. A carbon-based composite material comprises a modified carbon nanotube and a high molecular resin;

the modified carbon nanotube is a 11-carbonyl-BETA-acetyl boswellic acid modified carbon nanotube;

the polymer resin is one or a mixture of polyimide, epoxy resin, bismaleimide resin and polyacrylic resin.

2. Use of a carbon-based composite material according to claim 1 for the preparation of a fuel cell bipolar plate.

3. A method of preparing a carbon-based composite material as defined in claim 1, comprising:

grinding and dispersing the modified carbon nano tube in absolute ethyl alcohol to obtain modified carbon nano tube suspension;

and dissolving polymer resin in the modified carbon nanotube suspension, adding a hardening agent, performing ultrasonic oscillation and stirring, and drying to obtain the carbon-based composite material.

4. The method of claim 3, wherein the carbon-based composite material comprises: the weight ratio of the modified carbon nano tube to the polymer resin to the hardening agent is 1.8-2.5: 1: 0.2-0.4.

5. The method of claim 3, wherein the carbon-based composite material comprises: the preparation method of the modified carbon nano tube comprises the following steps: pouring the multi-walled carbon nano-tube into a beaker mixed acid solution, and carrying out ball milling to obtain a ball-milled carbon nano-tube;

and (2) uniformly mixing the 11-carbonyl-BETA-acetyl mastic acid and the ball-milled carbon nano tube, adding a catalyst, and performing ultrasonic treatment, reflux, filtration, washing and drying to obtain the modified carbon nano tube.

6. The method of claim 5, wherein the carbon-based composite material comprises: the weight ratio of the 11-carbonyl-BETA-acetyl boswellic acid to the ball-milled carbon nano tube is 2.5-4.5: 1.

7. A carbon-based composite material obtained by the production method according to any one of claims 3 to 6, characterized in that: the bending strength of the carbon-based composite material is higher than 131 MPa.

8. Use of the modified carbon nanotubes of claim 1 to increase the thermal conductivity of a carbon-based composite.

Technical Field

The invention belongs to the technical field of carbon-based materials, and particularly relates to a preparation method of a carbon-based composite material.

Background

The carbon nanotube has unique mechanical, electrical and optical properties and good performance on nanometer scale, so that the carbon nanotube is widely applied to the aspects of molecular sieve, drug delivery, particle exchange, seawater desalination and the like. As a main representative of carbon nanotube macroscopic materials, the carbon nanotube film not only retains the microscopic properties of the carbon nanotubes, but also has the advantages of good mechanical properties, stable chemical properties and the like. The preparation and application of the carbon nano tube are widely concerned by scholars at home and abroad.

The carbon nano tube has a structure similar to a macromolecule, and is compounded with the macromolecule to form a complete combination interface, so that the composite material with excellent performance can be obtained. The performance of the composite material formed by the carbon nanotubes and the polymer also depends on the loading amount of the carbon nanotubes, the specific gravity of the carbon nanotubes in the composite material can be increased through functionalization treatment, the dispersibility of the carbon nanotubes in the composite material is obviously improved compared with the carbon nanotubes without functionalization, and meanwhile, the mechanical performance of the composite material can be enhanced through the entrance of the carbon nanotubes. The prior art, for example, publication No. CN109851776A discloses a polyaryletherketone/carbon nanotube composite material, a preparation method thereof and a polyaryletherketone/carbon nanotube composite material film; the carbon nano tube is filled in the polyaryletherketone matrix in an in-situ polymerization mode, and the carbon nano tube and a fluorene conjugated structure in a polymer molecular chain form a pi-pi stacking effect, so that the carbon nano tube is favorably dispersed in the polyaryletherketone matrix, and the prepared polyaryletherketone/carbon nano tube composite material has better heat conduction performance.

Disclosure of Invention

The invention aims to provide a carbon-based composite material with high mechanical property and excellent thermal conductivity and electrical conductivity, so that the carbon-based composite material can be widely applied to fuel cell bipolar plates.

The technical scheme adopted by the invention for realizing the purpose is as follows:

a carbon-based composite material comprises a modified carbon nanotube and a high molecular resin;

wherein the modified carbon nanotube is a 11-carbonyl-BETA-acetyl boswellic acid modified carbon nanotube;

the polymer resin is one or more of polyimide, epoxy resin, bismaleimide resin, phenolic resin and polyacrylic resin.

The modified carbon nanotube is obtained by modifying the carbon nanotube with 11-carbonyl-BETA-acetyl mastic acid, and is used as a component of the carbon-based composite material to be compounded with the polymer resin to prepare the carbon-based composite material, so that the mechanical property of the carbon-based composite material is improved, and the carbon-based composite material has higher impact strength and bending strength; meanwhile, the thermal conductivity and the electrical conductivity of the carbon-based composite material are improved, probably because the modified carbon nano tube can be firmly combined with the polymer resin, and the carbon-based composite material with excellent performance is further obtained, so that the carbon-based composite material has wide application in fuel cell bipolar plates.

The invention also discloses the application of the carbon-based composite material in the preparation of the bipolar plate of the fuel cell.

The invention also discloses a preparation method of the carbon-based composite material, which comprises the following steps:

grinding and dispersing the modified carbon nano tube in absolute ethyl alcohol to obtain modified carbon nano tube suspension;

and dissolving the polymer resin in the modified carbon nanotube suspension, adding a hardening agent, performing ultrasonic oscillation and stirring, and drying to obtain the carbon-based composite material.

Further, the weight ratio of the modified carbon nanotube to the polymer resin to the hardener is 1.8-2.5: 1: 0.2-0.4.

Furthermore, the hardening agent is one of dibenzyl dimethylamine, diethylenetriamine and pyromellitic dianhydride.

Further, the preparation method of the modified carbon nanotube comprises the following steps: pouring the multi-walled carbon nano-tube into a beaker mixed acid solution, and carrying out ball milling to obtain a ball-milled acidified carbon nano-tube;

and (2) uniformly mixing the 11-carbonyl-BETA-acetyl mastic acid and the ball-milled carbon nano tube, adding a catalyst, and performing ultrasonic treatment, reflux, filtration, washing and drying to obtain the modified carbon nano tube.

Furthermore, the volume ratio of sulfuric acid to nitric acid in the mixed acid solution is 2-4: 1, so that the carbon nano tube is carboxylated to generate more active groups, and a foundation is laid for modification of the carbon nano tube.

Furthermore, the weight ratio of the multi-walled carbon nanotube to the mixed acid solution is 1-5: 20-50.

Further, the weight ratio of the 11-carbonyl-BETA-acetyl boswellic acid to the acidified carbon nanotube is 2.5-4.5: 1; the 11-carbonyl-BETA-acetyl mastic acid and the active groups contained in the acidified carbon nano tube are subjected to physical and chemical reaction to obtain the modified carbon nano tube with better performance.

The invention also discloses that the bending strength of the carbon-based composite material is higher than 131 MPa.

The invention also discloses the application of the modified carbon nano tube in improving the thermal conductivity of the carbon-based composite material.

The invention adopts 11-carbonyl-BETA-acetyl mastic acid modified carbon nano tube to obtain the modified carbon nano tube, and takes the modified carbon nano tube as the component of the carbon-based composite material to be compounded with the polymer resin to prepare the carbon-based composite material, thereby having the following beneficial effects: the carbon-based composite material has excellent mechanical property, so that the carbon-based composite material has higher impact strength and bending strength; meanwhile, the thermal conductivity and the electrical conductivity of the carbon-based composite material are improved, probably because the modified carbon nano tube can be firmly combined with the polymer resin, and the carbon-based composite material with excellent performance is further obtained, so that the carbon-based composite material has wide application in fuel cell bipolar plates. Therefore, the carbon-based composite material has high mechanical property and excellent thermal conductivity and electrical conductivity, and can be widely applied to fuel cell bipolar plates.

Drawings

FIG. 1 is an infrared spectrum of pure multi-walled carbon nanotubes, acidified carbon nanotubes in comparative example 1, modified carbon nanotubes in example 1, and carbon-based composite material in example 1;

FIG. 2 is a thermal conductivity of a carbon-based composite material;

FIG. 3 is an impact strength of a carbon-based composite material;

FIG. 4 is a graph of the bending strength of a carbon-based composite material;

fig. 5 is a volume resistance of a carbon-based composite material.

Detailed Description

The example content does not have any impact on the scope of the invention as claimed. The technical scheme of the invention is further described in detail by combining the detailed description and the attached drawings; the experimental methods described in the following examples of the present invention are all conventional methods unless otherwise specified; the reagents and materials are commercially available, unless otherwise specified.

In some embodiments of the present invention, the method for preparing the modified carbon nanotube comprises: pouring the multi-walled carbon nano tube into a beaker filled with mixed acid solution, wherein the volume ratio of 98% sulfuric acid to 70% nitric acid is 2-4: 1, ball milling is carried out for 18-24 h at the rotating speed of 200-300 r/min, the weight ratio of the ball (the ratio of the big ball to the small ball is 2-3: 1) to the carbon nano tube is 40-50: 1, and nitrogen is used as protective gas to obtain the ball-milled carbon nano tube;

placing 11-carbonyl-BETA-acetyl boswellic acid into absolute ethyl alcohol, completely dissolving the absolute ethyl alcohol at 40-50 ℃, wherein the content of 11-carbonyl-BETA-acetyl boswellic acid is 10-20 wt%, uniformly mixing the 11-carbonyl-BETA-acetyl boswellic acid solution and the ball-milled carbon nano tube, wherein the weight ratio of 11-carbonyl-BETA-acetyl boswellic acid to the ball-milled carbon nano tube is 2.5-4.5: 1, adding 0.05-0.15% of DMAP (dimethyl formamide) of the total content of reactants, performing ultrasonic dispersion for 30-60 min, performing reflux reaction on the obtained mixed solution at 75-90 ℃ for 2-4 h, performing vacuum filtration, sequentially washing the mixed solution to be neutral by using cyclohexane and deionized water respectively, and drying the mixed solution at 60-80 ℃ to obtain the modified carbon nano tube.

In some embodiments of the present invention, a method of preparing a carbon-based composite material comprises:

grinding and dispersing 5-10 parts by weight of modified carbon nanotubes in 200-300 parts by weight of absolute ethyl alcohol, and performing ultrasonic oscillation at room temperature for 0.5-1.5 hours to obtain a modified carbon nanotube suspension;

dissolving high polymer resin in the modified carbon nanotube suspension, performing ultrasonic oscillation for 2-4 hours to remove air bubbles and redundant solvent in liquid, then adding a hardening agent, wherein the weight ratio of the modified carbon nanotube to the high polymer resin to the hardening agent is 1.8-2.5: 1: 0.2-0.4, continuously performing ultrasonic oscillation and stirring, wherein the stirring speed is 1200-1800 rpm, the stirring time is 1-2 hours, and placing the mixture at 40-50 ℃ for drying to obtain the carbon-based composite material.

Further, the preparation method of the carbon-based composite material adopts the following preferable measures:

grinding and dispersing 5-10 parts by weight of modified carbon nanotubes in 200-300 parts by weight of absolute ethyl alcohol, and performing ultrasonic oscillation at room temperature for 0.5-1.5 hours to obtain a modified carbon nanotube suspension;

dissolving high molecular resin in the modified carbon nanotube suspension, performing ultrasonic oscillation for 2-4 hours to remove bubbles and redundant solvents in liquid, then adding a hardening agent and 7-nitro-1 (3H) -isobenzofuranone, wherein the weight ratio of the modified carbon nanotube to the high molecular resin to the hardening agent to the 7-nitro-1 (3H) -isobenzofuranone is 1.8-2.5: 1: 0.2-0.4: 0.05-0.15, continuously performing ultrasonic oscillation and stirring, wherein the stirring speed is 1200-1800 rpm, the stirring time is 1-2 hours, and drying at 40-50 ℃ to obtain the carbon-based composite material. The addition of 7-nitro-1 (3H) -isobenzofuranone can cause physicochemical reaction with the modified carbon nanotube to affect the structure of the modified carbon nanotube; on the other hand, the carbon-based composite material and the hardening agent can promote the modified carbon nano tube and the polymer resin to be firmly combined, and the carbon-based composite material with better mechanical property and thermal conductivity is obtained.

Example 1

A method of preparing a carbon-based composite material, comprising:

grinding and dispersing 8 parts of modified carbon nano tube in 250 parts of absolute ethyl alcohol according to parts by weight, and performing ultrasonic oscillation for 1 hour at room temperature to obtain modified carbon nano tube suspension;

dissolving polyacrylic resin in the modified carbon nanotube suspension, performing ultrasonic oscillation for 3 hours to remove air bubbles and redundant solvent in the liquid, then adding benzyl dimethyl amine, wherein the weight ratio of the modified carbon nanotube to the polyacrylic resin to the benzyl dimethyl amine is 2.1:1:0.23, continuously performing ultrasonic oscillation and stirring, wherein the stirring speed is 1500rpm, the stirring time is 1 hour, and placing the carbon-based composite material at 45 ℃ for drying to obtain the carbon-based composite material.

Specifically, in this embodiment, the preparation method of the modified carbon nanotube comprises: pouring multi-wall carbon nanotubes (purchased from Oncun novel carbon material Hezhou Co., Ltd.) into a beaker filled with mixed acid solution, wherein the volume ratio of sulfuric acid with the concentration of 98% to nitric acid with the concentration of 70% is 2:1, ball milling is carried out for 18h, the rotating speed is 200r/min, the weight ratio of balls (the ratio of large balls to small balls is 2:1, the diameter size of the large balls is 14mm, the diameter size of the small balls is 6mm) to the carbon nanotubes is 40:1, and nitrogen is used as protective gas to obtain the ball-milled carbon nanotubes;

placing 11-carbonyl-BETA-acetyl boswellic acid into absolute ethyl alcohol, completely dissolving the absolute ethyl alcohol at 45 ℃, wherein the content of 11-carbonyl-BETA-acetyl boswellic acid is 13.5 wt%, uniformly mixing the 11-carbonyl-BETA-acetyl boswellic acid solution and the ball-milled carbon nano tube, wherein the weight ratio of 11-carbonyl-BETA-acetyl boswellic acid to the ball-milled carbon nano tube is 2.5:1, adding 0.055% DMAP of the total content of reactants, performing ultrasonic dispersion for 30min, performing reflux reaction on the obtained mixed solution at 80 ℃ for 4h, performing vacuum filtration, sequentially washing the mixed solution to be neutral by using cyclohexane and deionized water respectively, and drying the mixed solution at 60 ℃ to obtain the modified carbon nano tube.

Example 2

The preparation method of the carbon-based composite material is the same as the embodiment 1 in other steps, and is different from the embodiment 1 in that:

grinding and dispersing 5.5 parts of modified carbon nano tube in 200 parts of absolute ethyl alcohol according to parts by weight, and performing ultrasonic oscillation at room temperature for 0.5h to obtain modified carbon nano tube suspension;

dissolving epoxy resin in the modified carbon nanotube suspension, carrying out ultrasonic oscillation for 2h to remove air bubbles and redundant solvent in the liquid, then adding diethylenetriamine, wherein the weight ratio of the modified carbon nanotube to the epoxy resin is 1.8:1:0.25, continuously carrying out ultrasonic oscillation and stirring, wherein the stirring speed is 1200rpm, the stirring time is 2h, and placing the carbon-based composite material at 40 ℃ for drying to obtain the carbon-based composite material.

In this example, the preparation method of the modified carbon nanotube was the same as in example 1.

Example 3

The preparation method of the carbon-based composite material is the same as the embodiment 1 in other steps, and is different from the embodiment 1 in that:

dissolving polyacrylic resin in the modified carbon nanotube suspension, performing ultrasonic oscillation for 3 hours to remove air bubbles and redundant solvent in the liquid, then adding benzyl dimethyl amine, wherein the weight ratio of the modified carbon nanotube to the polyacrylic resin to the benzyl dimethyl amine is 2.5:1:0.3, continuously performing ultrasonic oscillation and stirring, wherein the stirring speed is 1500rpm, the stirring time is 1 hour, and placing the carbon-based composite material at 45 ℃ for drying to obtain the carbon-based composite material.

In this example, the preparation method of the modified carbon nanotube was the same as in example 1.

Example 4

The preparation method of the carbon-based composite material is the same as the embodiment 1 in other steps, and is different from the embodiment 1 in that:

in this embodiment, the preparation method of the modified carbon nanotube comprises: pouring the multi-wall carbon nano tube into a beaker filled with mixed acid solution, wherein the volume ratio of 98% sulfuric acid to 70% nitric acid is 3:1, ball milling is carried out for 20h, the rotating speed is 250r/min, the weight ratio of balls (the ratio of large balls to small balls is 2:1, the diameter size of the large balls is 14mm, and the diameter size of the small balls is 6mm) to the carbon nano tube is 45:1, and nitrogen is used as protective gas to obtain the ball-milled carbon nano tube;

placing 11-carbonyl-BETA-acetyl boswellic acid into absolute ethyl alcohol, completely dissolving the absolute ethyl alcohol at 45 ℃, wherein the content of 11-carbonyl-BETA-acetyl boswellic acid is 16.5 wt%, uniformly mixing the 11-carbonyl-BETA-acetyl boswellic acid solution and the ball-milled carbon nano tube, wherein the weight ratio of 11-carbonyl-BETA-acetyl boswellic acid to the ball-milled carbon nano tube is 3.5:1, adding 0.075% DMAP of the total content of reactants, performing ultrasonic dispersion for 40min, performing reflux reaction on the obtained mixed solution at 85 ℃ for 3h, performing vacuum filtration, respectively washing the mixed solution to be neutral by using cyclohexane and deionized water in sequence, and drying the mixed solution at 70 ℃ to obtain the modified carbon nano tube.

Example 5

The preparation method of the carbon-based composite material is the same as the embodiment 1 in other steps, and is different from the embodiment 1 in that:

in this embodiment, the preparation method of the modified carbon nanotube comprises: pouring the multi-wall carbon nano tube into a beaker filled with mixed acid solution, wherein the volume ratio of 98% sulfuric acid to 70% nitric acid is 3:1, ball milling is carried out for 20h, the rotating speed is 250r/min, the weight ratio of balls (the ratio of large balls to small balls is 2:1, the diameter size of the large balls is 14mm, and the diameter size of the small balls is 6mm) to the carbon nano tube is 45:1, and nitrogen is used as protective gas to obtain the ball-milled carbon nano tube;

placing 11-carbonyl-BETA-acetyl boswellic acid into absolute ethyl alcohol, completely dissolving the absolute ethyl alcohol at 45 ℃, wherein the content of 11-carbonyl-BETA-acetyl boswellic acid is 16.5 wt%, uniformly mixing the 11-carbonyl-BETA-acetyl boswellic acid solution and the ball-milled carbon nano tube, wherein the weight ratio of 11-carbonyl-BETA-acetyl boswellic acid to the ball-milled carbon nano tube is 4.5:1, adding 0.055% DMAP of the total content of reactants, performing ultrasonic dispersion for 40min, performing reflux reaction on the obtained mixed solution at 90 ℃ for 3h, performing vacuum filtration, sequentially washing the mixed solution to be neutral by using cyclohexane and deionized water respectively, and drying the mixed solution at 75 ℃ to obtain the modified carbon nano tube.

Example 6

The preparation method of the carbon-based composite material is the same as the embodiment 1 in other steps, and is different from the embodiment 1 in that:

dissolving polyacrylic resin in the modified carbon nanotube suspension, carrying out ultrasonic oscillation for 3H to remove air bubbles and redundant solvent in the liquid, then adding p-benzyldimethylamine and 7-nitro-1 (3H) -isobenzofuranone, wherein the weight ratio of the modified carbon nanotube, the polyacrylic resin, the p-benzyldimethylamine to the 7-nitro-1 (3H) -isobenzofuranone is 2.1:1:0.23:0.05, continuously carrying out ultrasonic oscillation and stirring, wherein the stirring speed is 1500rpm, the stirring time is 1H, and drying at 45 ℃ to obtain the carbon-based composite material.

Example 7

The preparation method of the carbon-based composite material is the same as the embodiment 1 in other steps, and is different from the embodiment 1 in that: wherein the weight ratio of the modified carbon nano tube, the polyacrylic resin, the dibenzyl dimethylamine to the 7-nitro-1 (3H) -isobenzofuranone is 2.1:1:0.23: 0.1.

Example 8

The preparation method of the carbon-based composite material is the same as the embodiment 1 in other steps, and is different from the embodiment 1 in that: wherein the weight ratio of the modified carbon nano tube, the polyacrylic resin, the dibenzyl dimethylamine to the 7-nitro-1 (3H) -isobenzofuranone is 2.1:1:0.23: 0.15.

Example 9

A method for preparing a carbon-based composite material, the other steps being the same as in example 7, except that:

in this embodiment, the preparation method of the carbon nanotube includes: pouring multi-wall carbon nanotubes (purchased from Oncun novel carbon material Hezhou Co., Ltd.) into a beaker filled with mixed acid solution, wherein the volume ratio of sulfuric acid with the concentration of 98% to nitric acid with the concentration of 70% is 2:1, ball milling is carried out for 18h, the rotating speed is 200r/min, the weight ratio of balls (the ratio of large balls to small balls is 2:1, the diameter size of the large balls is 14mm, the diameter size of the small balls is 6mm) to the carbon nanotubes is 40:1, and nitrogen is used as protective gas to obtain the acidified carbon nanotubes after ball milling.

Comparative example 1

The preparation method of the carbon-based composite material is the same as the embodiment 1 in other steps, and is different from the embodiment 1 in that:

in this embodiment, the preparation method of the modified carbon nanotube comprises: pouring multi-wall carbon nanotubes (purchased from Oncun novel carbon material Hezhou Co., Ltd.) into a beaker filled with mixed acid solution, wherein the volume ratio of sulfuric acid with the concentration of 98% to nitric acid with the concentration of 70% is 2:1, ball milling is carried out for 18h, the rotating speed is 200r/min, the weight ratio of balls (the ratio of large balls to small balls is 2:1, the diameter size of the large balls is 14mm, the diameter size of the small balls is 6mm) to the carbon nanotubes is 40:1, and nitrogen is used as protective gas to obtain the acidified carbon nanotubes after ball milling.

Comparative example 2

A method of preparing a carbon-based composite material, comprising:

grinding and dispersing 8 parts of multi-walled carbon nanotubes (purchased from Oncung novel carbon material Hezhou Co., Ltd.) in 250 parts of absolute ethyl alcohol by weight, and ultrasonically oscillating for 1h at room temperature to obtain a multi-walled carbon nanotube suspension;

dissolving polyacrylic resin in the modified carbon nanotube suspension, performing ultrasonic oscillation for 3 hours to remove bubbles and redundant solvent in the liquid, then adding benzyl dimethyl amine, wherein the weight ratio of the multi-walled carbon nanotube, the polyacrylic resin and the benzyl dimethyl amine is 2.1:1:0.23, continuously performing ultrasonic oscillation and stirring, wherein the stirring speed is 1500rpm, the stirring time is 1 hour, and drying at 45 ℃ to obtain the carbon-based composite material.

Test example 1

1. Determination of carbon-based composite material infrared spectrogram

The measurement is carried out by adopting a 360Nicolet AVATAR infrared spectrometer, KBr is pressed into tablets, and the measurement range is 400-4000 cm^-1。

FIG. 1 is an infrared spectrum of pure multi-walled carbon nanotubes, acidified carbon nanotubes in comparative example 1, modified carbon nanotubes in example 1, and carbon-based composite material in example 1. Curves a, b, c, d are the infrared spectra of pure multi-walled carbon nanotubes, acidified carbon nanotubes in comparative example 1, modified carbon nanotubes in example 1, and carbon-based composite material in example 1, respectively; as can be seen from FIG. 1, the pure multi-walled carbon nanotubes are 3652.6cm^-1The absorption peak appeared nearby may be caused by adsorbing a small amount of impurities, and may also be caused by a small amount of hydroxyl groups existing at the defect position of the absorption peak; the IR spectrum of the acidified carbon nanotubes of comparative example 1 was at 3658.4cm^-1The characteristic absorption occurring nearby is the stretching vibration of-OH in carboxyl; at 1648.7cm^-1The characteristic absorption peak appeared nearby is the stretching vibration of C ═ O in the carboxyl; at 1261.5-1027.4 cm^-1The wide absorption peak appears as the stretching vibration of the C-O bond; the IR spectrum of the modified carbon nanotube in example 1 was 2986.9cm^-1、2851.7cm^-1Stretching vibration of methyl and methylene appears nearby; at 1746.3cm^-1An ester group stretching vibration absorption peak appears nearby; at 1678.2cm^-1Stretching vibration with a characteristic absorption peak of C ═ C appearing nearby; therefore, the 11-carbonyl-BETA-acetyl boswellic acid modified carbon nanotube is adopted to obtain a modified carbon nanotube; the infrared spectrum of the carbon-based composite material in the example 1 has little change with the peak pattern of the infrared spectrum of the modified carbon nano tube in the example 1, and is 2988.3cm^-1、2854.2cm^-1Characteristic absorption peaks of methyl and methylene groups appearing nearbyEnhancing; at 1648.3cm^-1The characteristic absorption peak of C ═ O in the carboxyl group appearing nearby is also enhanced; this shows that carbon-based composite materials are prepared by using the modified carbon nanotubes and the polyacrylic resin.

Test example 2

1. Determination of thermal conductivity of carbon-based composite

The thermal conductivity of the materials was measured using a thermal conductivity analyzer model TCT416 from NETZSCH, Germany, by the hot wire method (dynamic absolute measurement method) using the standard ISO 8894, EN993-14/15(DIN 51046). The size of the test sample is 5mm multiplied by 35mm, the test time is 1.5h, the temperature of the heater is 55 ℃, the temperature of the cold end is 25 ℃, the voltage reading values of the high-low end thermocouple and the low-low end thermocouple are respectively recorded, and the heat conductivity coefficient (namely the heat conductivity) of the test sample is obtained through the calculation software of the instrument. The magnitude of the thermal conductivity value represents the thermal conductivity of the material, and the physical meaning is the heat passing through a unit vertical area in unit time under a unit temperature gradient.

Fig. 2 is a thermal conductivity of a carbon-based composite material. As can be seen from FIG. 2, the thermal conductivity of the carbon-based composite materials in examples 1 to 5 was higher than 32.5 W.m^-1·K^-1Comparing example 1 with comparative example 1 and comparative example 2, the thermal conductivity of the carbon-based composite material in example 1 is higher than that in comparative example 1 and comparative example 2, which shows that the thermal conductivity of the carbon-based composite material is improved by using 11-carbonyl-BETA-acetyl boswellic acid modified carbon nano-tubes as raw materials of the carbon-based composite material; thermal conductivity of the carbon-based composites of examples 6-8 is higher than 40KJ/cm²Comparing example 1 with example 7, and example 9 with comparative example 1, the thermal conductivity of the carbon-based composite material in example 7 is higher than that in example 1, and the thermal conductivity of the carbon-based composite material in example 9 is higher than that in comparative example 1, which shows that the thermal conductivity of the carbon-based composite material is further improved by adding 7-nitro-1 (3H) -isobenzofuranone during the preparation process of the carbon-based composite material.

2. Determination of impact toughness of carbon-based composite material

The results were averaged over 5 measurements in an impact tester, type Charpy XCJ-L, operating at room temperature, according to ISO 179-2, with an impact energy of 5J and unnotched specimens having dimensions of 60 mm. times.10 mm. times.5 mm.

FIG. 3 is an impact strength of a carbon-based composite material. As can be seen from FIG. 3, the impact strength of the carbon-based composite materials of examples 1 to 5 was higher than 22.5KJ/cm²Comparing example 1 with comparative example 1 and comparative example 2, the impact strength of the carbon-based composite material in example 1 is higher than that of comparative example 1 and comparative example 2, which shows that the impact strength of the carbon-based composite material is improved by using 11-carbonyl-BETA-acetyl boswellic acid modified carbon nano-tubes as a raw material of the carbon-based composite material; examples 6-8 wherein the impact strength of the carbon-based composite was higher than 26.5KJ/cm²Comparing example 1 with example 7, and example 9 with comparative example 1, the impact strength of the carbon-based composite material in example 7 is higher than that in example 1, and the impact strength of the carbon-based composite material in example 9 is higher than that in comparative example 1, which shows that the impact strength of the carbon-based composite material is further improved by adding 7-nitro-1 (3H) -isobenzofuranone during the preparation process of the carbon-based composite material.

3. Determination of bending strength of carbon-based composite material

The bending strength of the test specimen was measured by an AGS-J electronic universal tester available from Shimadzu corporation, Japan, and an average value was obtained by 5 measurements using GB/T1043-2008 as a test standard.

FIG. 4 is a graph of the bending strength of a carbon-based composite material. As can be seen from fig. 4, the flexural strength of the carbon-based composite materials in examples 1 to 5 is higher than 131MPa, the impact strength of the carbon-based composite material in example 1 is higher than that of comparative examples 1 and 2, and comparative example 1 and 2 are compared, which indicates that the flexural strength of the carbon-based composite material is improved by using the 11-carbonyl-beta-acetyl boswellic acid modified carbon nanotube as the raw material of the carbon-based composite material; the bending strength of the carbon-based composite materials in examples 6 to 8 is higher than 140MPa, the bending strength of the carbon-based composite materials in example 1 and example 7 and example 9 and comparative example 1 are compared, the bending strength of the carbon-based composite material in example 7 is higher than that of example 1, and the bending strength of the carbon-based composite material in example 9 is higher than that of comparative example 1, which shows that the bending strength of the carbon-based composite material is further improved by adding 7-nitro-1 (3H) -isobenzofuranone in the preparation process of the carbon-based composite material.

4. Determination of conductive Properties of carbon-based composite materials

Fully drying the carbon-based composite material, putting the carbon-based composite material into a cavity prepared from engineering plastics, compacting the two ends of the carbon-based composite material by using a copper bar, pressing the carbon-based composite material into a cylindrical sample, testing the resistance of the compacted carbon nano tube powder under the pressure, and calculating the volume resistivity.

Fig. 5 is a volume resistance of a carbon-based composite material. As can be seen from fig. 5, the volume resistance of the carbon-based composite materials in examples 1 to 5 is lower than 0.042 Ω · cm, the volume resistance of the carbon-based composite material in example 1 is lower than that of comparative examples 1 and 2, and the volume resistance of the carbon-based composite material in example 1 is lower than that of comparative examples 1 and 2, which shows that the volume resistance of the carbon-based composite material is reduced and the conductivity of the carbon-based composite material is improved by using the 11-carbonyl-beta-acetyl boswellic acid modified carbon nanotube; comparing example 1 with example 7, and example 9 with comparative example 1, the volume resistance of the carbon-based composite material in example 7 is not obviously different from that in example 1, and the volume resistance of the carbon-based composite material in example 9 is also not obviously different from that in comparative example 1, which shows that the addition of 7-nitro-1 (3H) -isobenzofuranone in the preparation process of the carbon-based composite material has no obvious influence on the conductivity of the carbon-based composite material.

Conventional operations in the operation steps of the present invention are well known to those skilled in the art and will not be described herein.

The above embodiments are merely illustrative, and not restrictive, and those skilled in the art can make various changes and modifications without departing from the spirit and scope of the invention. Therefore, all equivalent technical solutions also belong to the scope of the present invention, and the protection scope of the present invention should be defined by the claims.