CN115611266A - Preparation method of oxygen-nitrogen metal doped nano carbon material and application of oxygen-nitrogen metal doped nano carbon material in rubber - Google Patents

Preparation method of oxygen-nitrogen metal doped nano carbon material and application of oxygen-nitrogen metal doped nano carbon material in rubber Download PDF

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CN115611266A
CN115611266A CN202211334853.XA CN202211334853A CN115611266A CN 115611266 A CN115611266 A CN 115611266A CN 202211334853 A CN202211334853 A CN 202211334853A CN 115611266 A CN115611266 A CN 115611266A
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nitrogen
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CN115611266B (en
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赵建林
赵宝文
田志
王莎莎
李金红
任斌
栾广扬
桂鉴臣
石娟
王毅
张兴
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Hebei Baoli Engineering Equipment Group Co Ltd
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Abstract

The invention relates to a preparation method of an oxygen-nitrogen metal doped nano carbon material and application thereof in rubber, wherein the preparation method comprises the following steps: mixing cysteine, glutamic acid, polyethylene glycol and an activating agent, keeping the temperature at 45-55 ℃ for 20-40min, stirring for 20-40min after gel formation begins, adding an imidazole auxiliary agent and a metal salt at the same time, stirring to form a gel for 1-3h, standing, cleaning, filtering, freezing and drying to obtain a solid; the activating agent is hexadecyl trimethyl ammonium bromide and hexamethylenetetramine with the mass ratio of (1-3) to (1); b: and C, carbonizing the solid obtained in the step A at 700-900 ℃ for 1-3h in a protective gas atmosphere, and cooling to room temperature to obtain the carbon material. The carbon material prepared by the method is used for preparing the rubber support, and can enhance the mechanical property of the rubber support.

Description

Preparation method of oxygen-nitrogen metal doped nano carbon material and application of oxygen-nitrogen metal doped nano carbon material in rubber
Technical Field
The invention relates to a preparation method of an oxygen-nitrogen metal doped nano carbon material and application of the oxygen-nitrogen metal doped nano carbon material in rubber, belonging to the technical field of carbon materials.
Background
The nano material is a new material with specific performance prepared by regulating a substance structure in a nano level (1-100 nm). At present, the development of the rubber industry is closely related to the use of nano materials, and the rubber industry uses a large amount of nano materials as fillers, and the dosage of the fillers is only second to the consumption of rubber. Such as nano calcium carbonate, nano silicon dioxide, nano zinc oxide, nano kaolin, nano carbon materials and the like.
Carbon is one of the most common elements distributed in nature except by sp 3 Hybridization to form a single bond, also in sp 3 And sp hybridization forms stable double bonds and triple bonds, so allotropes with widely different structures and properties can be formed, such as zero-dimensional carbon black and fullerene, one-dimensional carbon nanotubes and carbon nanofibers, two-dimensional graphene and the like. The carbon material can be used as a filler to be added into rubber, so that the physical, thermal, electrical and gas/liquid barrier properties of the rubber can be enhanced, and the production cost of rubber products can be reduced. At present, carbon materials commonly used in rubber are graphite, carbon black, graphene oxide, carbon fibers and carbon nanotubes, but carbon nanotubes are used as carbon nanotubesThe rice materials have strong intermolecular force, are easy to agglomerate, are difficult to disperse in common polymer base materials, cause processing difficulty, and cannot fully exert the due reinforcing effect, such as easy agglomeration in a rubber matrix and difficult good combination with the rubber matrix.
In view of this, a method for improving the performance of carbon material is needed to meet the requirement of rubber reinforcement.
Disclosure of Invention
The invention aims to overcome the defects in the prior art and provide a preparation method of an oxygen-nitrogen metal doped nano carbon material capable of effectively reinforcing the mechanical property of rubber.
In order to realize the purpose, the technical scheme adopted by the invention is as follows:
subject of the technology 1
The preparation method of the oxygen-nitrogen metal doped nano carbon material comprises the following steps:
a: mixing cysteine, glutamic acid, polyethylene glycol and activating agent, keeping the temperature at 45-55 ℃ for 20-40min, stirring for 20-40min after gel formation begins, adding imidazole auxiliary agent and metal salt at the same time, stirring to be gelatinous for 1-3h, standing, cleaning, filtering, freezing and drying to obtain a solid; the activating agent is hexadecyl trimethyl ammonium bromide and hexamethylenetetramine with the mass ratio of (1-3) to (1);
b: and C, carbonizing the solid obtained in the step A at 700-900 ℃ for 1-3h in a protective gas atmosphere, and cooling to room temperature to obtain the carbon material.
In some embodiments of the present invention, the mass ratio of the cysteine, the glutamic acid, the polyethylene glycol, the activator, the imidazole synergist and the metal salt is 3:3:0.4-1:1.3-2.5:1.5-2.8:3.6-4.4.
In some embodiments of the invention, the imidazole co-agent is 1-ethyl-3-methylimidazolium dicyanamide salt and 1- (3-aminopropyl) -imidazole in a mass ratio of 1:1.
In some embodiments of the invention, the activators are cetyltrimethylammonium bromide and hexamethylenetetramine in a mass ratio of 2:1.
In the inventionIn some embodiments, the metal salt is selected from CdN 2 O 6 .4H 2 O、Na 2 SnO 3 ·3H 2 O、CuSO 4 ·5H 2 O、PbCO 3 One or a combination of any two or more of them.
In some embodiments of the invention, the metal salt is CuSO 4 ·5H 2 O。
In some embodiments of the present invention, the mass ratio of the amino acid, the polyethylene glycol, the activator, the imidazole adjuvant and the metal salt is 3:3:1:2:2:4.
in some embodiments of the present invention, in the step B, the protective gas is continuously introduced at a rate of 15 to 30 mL/min.
In some embodiments of the invention, in the step B, the temperature is raised from room temperature to 280-320 ℃ at a rate of 1.2-1.5 ℃/min, then raised to 700-900 ℃ at a rate of 2-2.2 ℃/min, then kept for 1-3 hours, then lowered to 500 ℃ at a rate of 5 ℃/min, and finally naturally cooled to room temperature, so as to obtain the carbon material.
Subject matter two
The application of the oxygen-nitrogen metal doped nano carbon material obtained by the preparation method provided by the technical subject I in the field of rubber.
In some embodiments of the invention, the application is the preparation of rubber mounts.
In some embodiments of the invention, the raw materials of the rubber support comprise, by mass ratio of 100:40:5:1:1:2, natural rubber, an oxygen-nitrogen metal doped nano carbon material, znO, stearic acid, an accelerant and sulfur; the mass ratio of the accelerant to the accelerator is 1:0.5:0.2:2:0.2 of dibenzothiazyl Disulfide (DM), N-cyclohexyl-2-benzothiazolesulfenamide (CZ), dimethylthiuram disulfide (TMTD), dithiodimorpholine (DTDM) and 2-mercaptobenzothiazole (M).
The preparation process of the rubber support comprises the following steps: plasticating 100g of natural rubber in an internal mixer for 30s, and extracting the cork; adding 40g of the oxygen-nitrogen metal doped nano carbon material into an internal mixer, mixing until a torque curve area is stable; adding 5g of ZnO and 1g of stearic acid together, and adjusting the torque value to maintain the temperature of the material at 140 ℃ and discharging glue after 90 s; the mixing time is kept for 6 min; plasticating and discharging in an open mill, cooling to room temperature, adding a vulcanization system in the open mill again, mixing 2g of sulfur and 1g of accelerator into the rubber sheet, performing triangular wrapping and rolling for three times respectively, and discharging to obtain rubber compound; and putting the mixed rubber into a mold to be vulcanized and molded to obtain the rubber, wherein the vulcanization temperature is 145 ℃, and the vulcanization time is 180s.
Adopt the produced beneficial effect of above-mentioned technical scheme to lie in:
in the method provided by the invention, the components are matched and cooperated, and metal elements are doped simultaneously, so that the prepared oxygen-nitrogen metal doped nano carbon material has the specific surface area of 500-750 m2/g and the pore volume of 0.41-0.80 cm 3 (ii) in terms of/g. The carbon material prepared by the method is used for preparing rubber, and a rubber mechanical property test is carried out, wherein the hardness (IRHD) is 59-60, the tensile strength is 18-23MPa, the elongation at break is 522-597%, the constant compression permanent deformation (70 ℃ multiplied by 24 h) is 20-25%, the bonding peel strength of the rubber and a steel plate is 11-14 KN/m, the bonding peel strength of the rubber and a tetrafluoro plate is 9-11 KN/m, and the air aging resistance test (168 ℃ multiplied by 70 h) is as follows: hardness change 2~4, tensile strength change rate of minus 8 to minus 10 percent, elongation at break change rate of minus 12 to minus 15 percent, ozone aging resistance (25pphm, 20 percent elongation, 40 ℃ multiplied by 96 h) and no crack.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below, and it is obvious that the drawings in the following description are some embodiments of the present invention, and other drawings can be obtained by those skilled in the art without creative efforts.
FIG. 1 is a nitrogen adsorption/desorption graph of a carbon material in example 1 of the present invention;
FIG. 2 is an XPS chart of nitrogen in the carbon material for an electrode according to example 1 of the present invention;
FIG. 3 is an XPS chart of oxygen in an electrode carbon material according to example 1 of the present invention;
FIG. 4 is an XPS chart of copper as an electrode carbon material in example 1 of the present invention.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the following description of the present invention is given for clarity and completeness.
Each of the substances used in the present examples was commercially available. Wherein the polyethylene glycol adopts polyethylene glycol-400, the average molecular mass of which is 400, and the polyethylene glycol is purchased from Shanghai Aladdin Biotechnology GmbH, model number: p103737.
Example 1
The preparation method of the oxygen-nitrogen metal doped nano carbon material comprises the following steps:
a: mixing cysteine, glutamic acid, polyethylene glycol-400 and an activating agent, keeping the temperature at 50 ℃ for 30min, stirring for 30min after gel formation begins, adding an imidazole auxiliary agent and a metal salt at the same time, stirring to form a gel for 2h, standing, cleaning, filtering, freezing and drying to obtain a solid; the activating agent is hexadecyl trimethyl ammonium bromide and hexamethylene tetramine with the mass ratio of 2:1; the imidazole adjuvant agent is 1-ethyl-3-methylimidazolium dicyanamide salt and 1- (3-aminopropyl) -imidazole in a mass ratio of 1:1; the metal salt is CuSO 4 ·5H 2 O; the mass ratio of the cysteine to the glutamic acid to the polyethylene glycol-400 to the activating agent to the imidazole auxiliary agent to the metal salt is 3:3:1:2:2:4;
b: and C, carbonizing the solid obtained in the step A in a nitrogen atmosphere, continuously introducing nitrogen at the rate of 20mL/min, specifically, heating the solid from room temperature to 300 ℃ at the rate of 1.4 ℃/min, heating the solid to 800 ℃ at the rate of 2.1 ℃/min, keeping the temperature for 2 hours, cooling the solid to 500 ℃ at the rate of 5 ℃/min, and naturally cooling the solid to room temperature to obtain the carbon material.
The parameters of the prepared carbon material are as follows: specific surface area 685 m 2 Per g, pore volume 0.71 cm 3 /g。
Performing nitrogen adsorption and desorption performance test on the prepared carbon material, as shown in figure 1; the composition characterization of nitrogen, oxygen and copper on the prepared carbon material is respectively shown in fig. 2, fig. 3 and fig. 4, and it can be seen that the carbon material of the invention is successfully doped with nitrogen-oxygen-copper element.
Example 2
The preparation method of the oxygen-nitrogen metal doped nano carbon material comprises the following steps:
a: mixing cysteine, glutamic acid, polyethylene glycol-400 and an activating agent, keeping the temperature at 45 ℃ for 40min, stirring for 20min after gel formation begins, adding an imidazole auxiliary agent and a metal salt at the same time, stirring to form a gel for 1h, standing, cleaning, filtering, freezing and drying to obtain a solid; the activating agent is hexadecyl trimethyl ammonium bromide and hexamethylene tetramine with the mass ratio of 1:1; the imidazole adjuvant agent is 1-ethyl-3-methylimidazolium dicyanamide salt and 1- (3-aminopropyl) -imidazole in a mass ratio of 1:1; the metal salt is CdN 2 O 6 .4H 2 O; the mass ratio of the cysteine to the glutamic acid to the polyethylene glycol-400 to the activating agent to the imidazole auxiliary agent to the metal salt is 3:3:0.4:2.5:1.5:4.4;
b: and C, carbonizing the solid obtained in the step A in a nitrogen atmosphere, continuously introducing nitrogen at the rate of 30mL/min, specifically, heating the solid from room temperature to 320 ℃ at the rate of 1.2 ℃/min, heating the solid to 900 ℃ at the rate of 2 ℃/min, keeping the temperature for 1 hour, cooling the solid to 500 ℃ at the rate of 5 ℃/min, and naturally cooling the solid to room temperature to obtain the carbon material.
The parameters of the prepared carbon material are as follows: specific surface area 610m 2 Per g, pore volume 0.63 cm 3 /g。
Example 3
The preparation method of the oxygen-nitrogen metal doped nano carbon material comprises the following steps:
a: mixing cysteine, glutamic acid, polyethylene glycol-400 and an activating agent, keeping the temperature at 55 ℃ for 20min, stirring for 40min after gel formation begins, adding an imidazole auxiliary agent and a metal salt at the same time, stirring to be gelatinous for 3h, standing, cleaning, filtering, freezing and drying to obtain a solid; the activating agent is hexadecyl trimethyl ammonium bromide and hexamethylene tetramine with the mass ratio of 3:1; the imidazole auxiliary agent is 1-ethyl-3-methylimidazolium dicyanamide salt and 1- (3-aminopropyl) -imidazole in the mass ratio of 1:1; the metal salt is Na 2 SnO 3 ·3H 2 O; the mass ratio of the cysteine to the glutamic acid to the polyethylene glycol-400 to the activating agent to the imidazole auxiliary agent to the metal salt is 3:3:0.6:1.3: 2.8:3.6;
b: and C, carbonizing the solid obtained in the step A in a nitrogen atmosphere, continuously introducing nitrogen at a speed of 15mL/min, specifically, heating the solid to 280 ℃ from room temperature at a speed of 1.5 ℃/min, heating the solid to 700 ℃ at a speed of 2.2 ℃/min, keeping the temperature for 3 hours, cooling the solid to 500 ℃ at a speed of 5 ℃/min, and naturally cooling the solid to room temperature to obtain the carbon material.
The parameters of the prepared carbon material are as follows: specific surface area 750 m 2 Per g, pore volume 0.8 cm 3 /g。
Example 4
The preparation method of the oxygen-nitrogen metal doped nano carbon material comprises the following steps:
a: mixing cysteine, glutamic acid, polyethylene glycol-400 and an activating agent, keeping the temperature at 50 ℃ for 30min, stirring for 30min after gel formation begins, adding an imidazole auxiliary agent and a metal salt at the same time, stirring to form a gel for 2h, standing, cleaning, filtering, freezing and drying to obtain a solid; the activating agent is hexadecyl trimethyl ammonium bromide and hexamethylene tetramine with the mass ratio of 2:1; the imidazole adjuvant agent is 1-ethyl-3-methylimidazolium dicyanamide salt and 1- (3-aminopropyl) -imidazole in a mass ratio of 1:1; the metal salt being PbCO 3 (ii) a The mass ratio of the cysteine to the glutamic acid to the polyethylene glycol-400 to the activating agent to the imidazole auxiliary agent to the metal salt is 3:3:0.8:1.8:2.5:3.8 of the total weight of the mixture;
b: and C, carbonizing the solid obtained in the step A in a nitrogen atmosphere, continuously introducing nitrogen at the rate of 20mL/min, specifically, heating the solid from room temperature to 300 ℃ at the rate of 1.4 ℃/min, heating the solid to 800 ℃ at the rate of 2.1 ℃/min, keeping the temperature for 2 hours, cooling the solid to 500 ℃ at the rate of 5 ℃/min, and naturally cooling the solid to room temperature to obtain the carbon material.
The parameters of the prepared carbon material are as follows: specific surface area 549 m 2 Perg, pore volume 0.48 cm 3 /g。
Example 5
The preparation method of the oxygen-nitrogen metal doped nano carbon material comprises the following steps:
a: mixing cysteine, glutamic acid, polyethylene glycol-400 and an activating agent, keeping the temperature at 50 ℃ for 30min, stirring for 30min after gel formation begins, adding an imidazole auxiliary agent and a metal salt at the same time, stirring to form a gel for 1-3h, standing, cleaning, filtering, and freeze-drying to obtain a solid; the activating agent is hexadecyl trimethyl ammonium bromide and hexamethylene tetramine with the mass ratio of 2:1; the imidazole adjuvant agent is 1-ethyl-3-methylimidazolium dicyanamide salt and 1- (3-aminopropyl) -imidazole in a mass ratio of 1:1; the metal salt is CdN with the mass ratio of 1:1 2 O 6 .4H 2 O and PbCO 3 (ii) a The mass ratio of the cysteine to the glutamic acid to the polyethylene glycol-400 to the activating agent to the imidazole auxiliary agent to the metal salt is 3:3:0.5:2.2:1.8:4.2;
b: and C, carbonizing the solid obtained in the step A in a nitrogen atmosphere, continuously introducing nitrogen at the rate of 20mL/min, specifically, heating the solid from room temperature to 300 ℃ at the rate of 1.4 ℃/min, heating the solid to 800 ℃ at the rate of 2.1 ℃/min, keeping the temperature for 2 hours, cooling the solid to 500 ℃ at the rate of 5 ℃/min, and naturally cooling the solid to room temperature to obtain the carbon material.
The parameters of the prepared carbon material are as follows: specific surface area 500 m 2 Per g, pore volume 0.41 cm 3 /g。
Effect example 1
The oxygen-nitrogen metal-doped nanocarbon materials prepared in examples 1 to 5 were used to prepare rubber mount samples 1 to 5 by the following methods:
the preparation method of the rubber support comprises the following steps:
plasticating 100g of natural rubber in an internal mixer for 30s, and extracting the cork; adding 40g of the oxygen-nitrogen metal doped nano carbon material into an internal mixer, mixing until a torque curve area is stable; adding 5g of ZnO and 1g of stearic acid together, and adjusting the torque value to maintain the temperature of the material at 140 ℃ and discharging glue after 90 s; the mixing time is kept for 6 min; plasticating and discharging in an open mill, cooling to room temperature, adding a vulcanization system in the open mill again, mixing 2g of sulfur and 1g of accelerator into the rubber sheet, performing triangular wrapping and rolling for three times respectively, and discharging to obtain rubber compound; and putting the mixed rubber into a mold to be vulcanized and molded to obtain the rubber, wherein the vulcanization temperature is 145 ℃, and the vulcanization time is 180s. Wherein the mass ratio of the accelerator is 1:0.5:0.2:2:0.2 of dibenzothiazole Disulfide (DM), N-cyclohexyl-2-benzothiazolehypoxanthamide (CZ), dimethylthiuram disulfide (TMTD), dithiodimorpholine (DTDM), 2-mercaptobenzothiazole (M).
According to GB, JT/T4-2019, the obtained rubber support is subjected to a performance detection test, and the results are shown in the following table 1:
TABLE 1 Properties of rubber bearing samples prepared in examples 1 to 5
Figure 835319DEST_PATH_IMAGE001
Comparative example 1
The preparation method of the oxygen-nitrogen metal doped nano carbon material comprises the following steps:
a: mixing glutamic acid, polyethylene glycol-400 and an activating agent, keeping the temperature at 50 ℃ for 30min, stirring for 30min after gel formation begins, adding an imidazole auxiliary agent and a metal salt at the same time, stirring to be in a gel state for 2h, standing, cleaning, filtering, freezing and drying to obtain a solid; the activating agent is hexadecyl trimethyl ammonium bromide and hexamethylene tetramine with the mass ratio of 2:1; the imidazole adjuvant agent is 1-ethyl-3-methylimidazolium dicyanamide salt and 1- (3-aminopropyl) -imidazole in a mass ratio of 1:1; the metal salt is CuSO 4 ·5H 2 O; the mass ratio of the glutamic acid to the polyethylene glycol-400 to the activating agent to the imidazole auxiliary agent to the metal salt is 6:1:2:2:4;
b: and C, carbonizing the solid obtained in the step A in a nitrogen atmosphere, continuously introducing nitrogen at the rate of 20mL/min, specifically, heating the solid from room temperature to 300 ℃ at the rate of 1.4 ℃/min, heating the solid to 800 ℃ at the rate of 2.1 ℃/min, keeping the temperature for 2 hours, cooling the solid to 500 ℃ at the rate of 5 ℃/min, and naturally cooling the solid to room temperature to obtain the carbon material.
Comparative example 2
The preparation method of the oxygen-nitrogen metal doped nano carbon material comprises the following steps:
a: mixing cysteine, polyethylene glycol-400 and an activating agent, keeping the temperature at 50 ℃ for 30min, stirring for 30min after gel formation begins, adding an imidazole auxiliary agent and a metal salt at the same time, stirring to form a gel for 2h, standing, cleaning, filtering, freezing and drying to obtain a solid; the activating agent is hexadecyl trimethyl ammonium bromide and hexamethylene tetramine with the mass ratio of 2:1; the imidazole auxiliary agent is 1-ethyl-3-methylimidazolium dicyanamide salt and 1- (3-aminopropyl) -imidazole in the mass ratio of 1:1; the metal salt is CuSO 4 ·5H 2 O; the mass ratio of the cysteine to the polyethylene glycol-400 to the activator to the imidazole auxiliary agent to the metal salt is 6:1:2:2:4;
b: and C, carbonizing the solid obtained in the step A in a nitrogen atmosphere, continuously introducing nitrogen at the rate of 20mL/min, specifically, heating the solid from room temperature to 300 ℃ at the rate of 1.4 ℃/min, heating the solid to 800 ℃ at the rate of 2.1 ℃/min, keeping the temperature for 2 hours, cooling the solid to 500 ℃ at the rate of 5 ℃/min, and naturally cooling the solid to room temperature to obtain the carbon material.
Comparative example 3
The preparation method of the oxygen-nitrogen metal doped nano carbon material comprises the following steps:
a: mixing cysteine, glutamic acid, polyethylene glycol-400 and activating agent, keeping the temperature at 50 ℃ for 30min, stirring for 30min after gel formation begins, adding 1- (3-aminopropyl) -imidazole and metal salt at the same time, stirring to form gel for 2h, standing, cleaning, filtering, and freeze-drying to obtain solid; the activating agent is hexadecyl trimethyl ammonium bromide and hexamethylene tetramine with the mass ratio of 2:1; the metal salt is CuSO 4 ·5H 2 O; the mass ratio of the cysteine to the glutamic acid to the polyethylene glycol-400 to the activator to the 1- (3-aminopropyl) -imidazole to the metal salt is 3:3:1:2:2:4;
b: and C, carbonizing the solid obtained in the step A in a nitrogen atmosphere, continuously introducing nitrogen at the rate of 20mL/min, specifically, heating the solid from room temperature to 300 ℃ at the rate of 1.4 ℃/min, heating the solid to 800 ℃ at the rate of 2.1 ℃/min, keeping the temperature for 2 hours, cooling the solid to 500 ℃ at the rate of 5 ℃/min, and naturally cooling the solid to room temperature to obtain the carbon material.
Comparative example 4
The preparation method of the oxygen-nitrogen metal doped nano carbon material comprises the following steps:
a: mixing cysteine, glutamic acid, polyethylene glycol-400 and an activating agent, keeping the temperature at 50 ℃ for 30min, stirring for 30min after gel formation begins, adding 1-ethyl-3-methylimidazolium dicyanamide salt and metal salt at the same time, stirring to form a gel for 2h, standing, cleaning, filtering, and freeze-drying to obtain a solid; the activating agent is hexadecyl trimethyl ammonium bromide and hexamethylene tetramine with the mass ratio of 2:1; the metal salt is CuSO 4 ·5H 2 O; the mass ratio of the cysteine to the glutamic acid to the polyethylene glycol-400 to the activator to the 1-ethyl-3-methylimidazolium dicyanamide salt to the metal salt is 3:3:1:2:2:4;
b: and C, carbonizing the solid obtained in the step A in a nitrogen atmosphere, continuously introducing nitrogen at the rate of 20mL/min, specifically, heating the solid from room temperature to 300 ℃ at the rate of 1.4 ℃/min, heating the solid to 800 ℃ at the rate of 2.1 ℃/min, keeping the temperature for 2 hours, cooling the solid to 500 ℃ at the rate of 5 ℃/min, and naturally cooling the solid to room temperature to obtain the carbon material.
Comparative example 5
The preparation method of the oxygen-nitrogen metal doped nano carbon material comprises the following steps:
a: mixing cysteine, aspartic acid, polyethylene glycol-400 and an activating agent, keeping the temperature at 50 ℃ for 30min, stirring for 30min after gel formation begins, adding an imidazole auxiliary agent and a metal salt at the same time, stirring to form a gel for 2h, standing, cleaning, filtering, and freeze-drying to obtain a solid; the activating agent is hexadecyl trimethyl ammonium bromide and hexamethylene tetramine with the mass ratio of 2:1; the imidazole auxiliary agent is 1-ethyl-3-methylimidazolium dicyanamide salt and 1- (3-aminopropyl) -imidazole in the mass ratio of 1:1; the metal salt is CuSO 4 ·5H 2 O; the mass ratio of the cysteine, the aspartic acid, the polyethylene glycol-400, the activating agent, the imidazole auxiliary agent and the metal salt is 3:3:1:2:2:4;
b: and C, carbonizing the solid obtained in the step A in a nitrogen atmosphere, continuously introducing nitrogen at the rate of 20mL/min, specifically, heating the solid from room temperature to 300 ℃ at the rate of 1.4 ℃/min, heating the solid to 800 ℃ at the rate of 2.1 ℃/min, keeping the temperature for 2 hours, cooling the solid to 500 ℃ at the rate of 5 ℃/min, and naturally cooling the solid to room temperature to obtain the carbon material.
Comparative example 6
The preparation method of the oxygen-nitrogen metal doped nano carbon material comprises the following steps:
a: mixing lysine, glutamic acid, polyethylene glycol-400 and activating agent, keeping the temperature at 50 ℃ for 30min, stirring for 30min after gel formation begins, adding imidazole adjuvant and metal salt at the same time, stirring to form gel for 2h, standing, cleaning, filtering, and freeze-drying to obtain solid; the activating agent is hexadecyl trimethyl ammonium bromide and hexamethylene tetramine with the mass ratio of 2:1; the imidazole adjuvant agent is 1-ethyl-3-methylimidazolium dicyanamide salt and 1- (3-aminopropyl) -imidazole in a mass ratio of 1:1; the metal salt is CuSO 4 ·5H 2 O; the mass ratio of lysine, glutamic acid, polyethylene glycol-400, the activating agent, the imidazole assistant agent and the metal salt is 3:3:1:2:2:4;
b: and C, carbonizing the solid obtained in the step A in a nitrogen atmosphere, continuously introducing nitrogen at the rate of 20mL/min, specifically, heating the solid from room temperature to 300 ℃ at the rate of 1.4 ℃/min, heating the solid to 800 ℃ at the rate of 2.1 ℃/min, keeping the temperature for 2 hours, cooling the solid to 500 ℃ at the rate of 5 ℃/min, and naturally cooling the solid to room temperature to obtain the carbon material.
Comparative example 7
The preparation method of the oxygen-nitrogen metal doped nano carbon material comprises the following steps:
a: mixing cysteine, glutamic acid, polyethylene glycol-400 and an activating agent, keeping the temperature at 50 ℃ for 30min, stirring for 30min after gel formation begins, adding the imidazole auxiliary agent at the same time, stirring to form a gel for 2h, standing, cleaning, filtering, freezing and drying to obtain a solid; the activating agent is hexadecyl trimethyl ammonium bromide and hexamethylene tetramine with the mass ratio of 2:1; the imidazole adjuvant agent is 1-ethyl-3-methylimidazolium dicyanamide salt and 1- (3-aminopropyl) -imidazole in a mass ratio of 1:1; the metal salt is CuSO 4 ·5H 2 O; what is needed isThe mass ratio of the cysteine to the glutamic acid to the polyethylene glycol-400 to the activating agent to the imidazole auxiliary agent is 3:3:1:2:2;
b: and C, carbonizing the solid obtained in the step A in a nitrogen atmosphere, continuously introducing nitrogen at the rate of 20mL/min, specifically, heating the solid from room temperature to 300 ℃ at the rate of 1.4 ℃/min, heating the solid to 800 ℃ at the rate of 2.1 ℃/min, keeping the temperature for 2 hours, cooling the solid to 500 ℃ at the rate of 5 ℃/min, and naturally cooling the solid to room temperature to obtain the carbon material.
Effect example 2
The carbon materials prepared in comparative examples 1 to 7 were used to prepare rubber mount comparative samples 1 to 7 by the following methods:
the preparation method of the rubber support comprises the following steps:
plasticating 100g of natural rubber in an internal mixer for 30 seconds, and extracting a suppository; adding 40g of the oxygen-nitrogen metal doped nano carbon material into an internal mixer, mixing until a torque curve area is stable; adding 5g of ZnO and 1g of stearic acid together, and adjusting the torque value to maintain the temperature of the material at 140 ℃ and discharging glue after 90 s; the mixing time is kept for 6 min; plasticating and discharging in an open mill, cooling to room temperature, adding a vulcanization system in the open mill again, mixing 2g of sulfur and 1g of accelerator into the rubber sheet, performing triangular wrapping and rolling for three times respectively, and discharging to obtain rubber compound; and putting the mixed rubber into a mold to be vulcanized and molded to obtain the rubber, wherein the vulcanization temperature is 145 ℃, and the vulcanization time is 180s. Wherein the mass ratio of the accelerator is 1:0.5:0.2:2:0.2 of dibenzothiazole Disulfide (DM), N-cyclohexyl-2-benzothiazolehypoxanthamide (CZ), dimethylthiuram disulfide (TMTD), dithiodimorpholine (DTDM), 2-mercaptobenzothiazole (M).
According to GB, JT/T4-2019, the obtained rubber support is subjected to a performance detection test, and the results are shown in the following table 2:
TABLE 2
Figure 70516DEST_PATH_IMAGE002
Finally, it should be noted that: the above examples are only intended to illustrate the technical solution of the present invention, and not to limit it; although the present invention has been described in detail with reference to the foregoing embodiments, it will be understood by those of ordinary skill in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some technical features may be equivalently replaced; and such modifications or substitutions do not depart from the spirit and scope of the corresponding technical solutions of the embodiments of the present invention.

Claims (10)

1. The preparation method of the oxygen-nitrogen metal doped nano carbon material is characterized by comprising the following steps of:
a: mixing cysteine, glutamic acid, polyethylene glycol and activating agent, keeping the temperature at 45-55 ℃ for 20-40min, stirring for 20-40min after gel formation begins, adding imidazole auxiliary agent and metal salt at the same time, stirring to be gelatinous for 1-3h, standing, cleaning, filtering, freezing and drying to obtain a solid; the activating agent is hexadecyl trimethyl ammonium bromide and hexamethylenetetramine with the mass ratio of (1-3) to (1);
b: and C, carbonizing the solid obtained in the step A at 700-900 ℃ for 1-3h in a protective gas atmosphere, and cooling to room temperature to obtain the carbon material.
2. The method for preparing an oxygen-nitrogen metal doped nano carbon material according to claim 1, wherein the mass ratio of the cysteine, the glutamic acid, the polyethylene glycol, the activator, the imidazole assistant agent and the metal salt is 3:3:0.4-1:1.3-2.5:1.5-2.8:3.6-4.4.
3. The method for producing an oxygen-nitrogen metal-doped nanocarbon material according to claim 1, wherein the imidazole adjuvant is 1-ethyl-3-methylimidazolium dicyanamide salt and 1- (3-aminopropyl) -imidazole in a mass ratio of 1:1.
4. The method for producing an oxygen-nitrogen metal-doped nanocarbon material according to claim 1, wherein the metal salt is selected from CdN 2 O 6 .4H 2 O、Na 2 SnO 3 ·3H 2 O、CuSO 4 ·5H 2 O、PbCO 3 One or a combination of any two or more of them.
5. The method for producing an oxygen-nitrogen metal-doped nanocarbon material according to claim 1, wherein the metal salt is CuSO 4 ·5H 2 O。
6. The method for preparing an oxygen-nitrogen metal-doped nanocarbon material according to claim 1, wherein the mass ratio of the amino acid, the polyethylene glycol, the activator, the imidazole assistant agent and the metal salt is 3:3:1:2:2:4.
7. the method according to claim 1, wherein the protective gas is continuously introduced at a rate of 15 to 30mL/min in the step B.
8. The method for preparing an oxygen-nitrogen-metal-doped nanocarbon material according to claim 1, wherein in the step B, the carbon material is obtained by raising the temperature from room temperature to 280 to 320 ℃ at a rate of 1.2 to 1.5 ℃/min, then raising the temperature to 700 to 900 ℃ at a rate of 2 to 2.2 ℃/min, then maintaining the temperature for 1 to 3 hours, then lowering the temperature to 500 ℃ at a rate of 5 ℃/min, and finally naturally lowering the temperature to room temperature.
9. Application of the oxygen-nitrogen metal doped nano carbon material obtained by the preparation method according to any one of claims 1 to 8 in the field of rubber.
10. Use according to claim 9 for the preparation of rubber bearings.
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