CN112573502A

CN112573502A - Aromatic cyano/aromatic alkynyl porous carbon material and preparation method thereof

Info

Publication number: CN112573502A
Application number: CN202011400793.8A
Authority: CN
Inventors: 杨刚; 胡江淮; 周涛; 肖航
Original assignee: Sichuan University
Current assignee: Sichuan University
Priority date: 2020-09-11
Filing date: 2020-12-02
Publication date: 2021-03-30
Anticipated expiration: 2040-12-02
Also published as: CN112573502B

Abstract

The invention discloses an aromatic cyano group/aromatic alkynyl porous carbon material and a preparation method thereof, wherein the porous carbon material is prepared by the following steps: (1) uniformly blending the resin matrix and the reinforcing component; (2) pressing and molding the blending product; (3) curing the blending product after pressure forming in an inert gas atmosphere: (4) preserving heat and carbonizing the cured product in an inert gas atmosphere; and after the carbonization is finished, cooling the obtained product to room temperature along with the furnace. The invention takes the aromatic cyano-group or/and aromatic alkynyl resin monomer as a carbonization precursor, and combines a powder metallurgy process to prepare the porous carbon material with excellent thermal stability, mechanical strength, conductivity and electromagnetic shielding performance.

Description

Aromatic cyano/aromatic alkynyl porous carbon material and preparation method thereof

Technical Field

The invention belongs to the technical field of carbon materials, and particularly relates to an arylcyano/aralkynyl porous carbon material and a preparation method thereof.

Background

The porous carbon material is a carbon material with different pore structures, and the pore diameter of the porous carbon material can be regulated according to the requirements of practical application (such as the size of adsorbed molecules) so that the size of the porous carbon material is between a nanometer micro-pore and a micrometer macro-pore. The porous carbon material has the properties of the carbon material, such as light weight, good heat resistance, good corrosion resistance, good conductivity, low price and the like; meanwhile, the introduction of the pore structure enables the porous structure to have the characteristics of large specific surface area, controllable pore channel structure, adjustable pore diameter and the like. The porous carbon material has wide application in the fields of new energy, packaging, automobiles, military affairs, aerospace and the like.

The porous carbon material is generally synthesized by using a carbon source as a base material by an activation method or a template method.

The activation method is a conventional method for preparing a porous carbon material, and includes physical activation mainly by some oxidizing gases (water vapor, CO) and chemical activation₂Air, O₂Etc.) as an activating agent, so that part of carbon atoms in the carbon source material are gasified, and a new aperture is formed in the carbon source material or the original pore channel is enlarged, thereby playing the role of activating the carbon source material and forming the porous carbon material with rich pores. The mechanism of chemical activation is complex, and it is believed that chemicals affect the pyrolysis process or react with carbon atoms in the carbon source material to form a developed pore structure. Therefore, the preparation process of the activation method is complex, and the size and the morphology of the aperture in the material are difficult to be really controlled.

The template method utilizes the structure guiding function of the template and the orderliness of the structure thereof, controls the structure of the material by changing the size and the shape of the pore space inside the template, and greatly ensures the controllability of the shape and the size of the pore channel of the material due to the occupying function of the template in the matrix material. The method mainly comprises two important links, namely organic substance carbonization in a nanometer space between inorganic templates (the organic carbon source refers to an organic precursor material containing carbon atoms, such as organic micromolecules or macromolecular resin, biomass and the like) and separation of a final carbonized product from the templates. The template method not only can regulate and control the pore structure of the carbon material at the nanometer level, but also has excellent performance in the aspects of ordering and regularization regulation and control of the pore structure. However, the template method also has some problems, such as complicated procedure, need to synthesize the template first, difficulty in controlling the macroporous structure, easiness in depositing the carbon source, and the like.

In addition to the research on the preparation method in the research on the preparation process of the porous carbon material, the selection of the carbon source is another main research direction, and the selection space of the carbon source is large for the porous carbon material. The polymer composite material is a common precursor for preparing the porous carbon material, and has the advantages of controllable structure, flexible molecular design and stable performance. Different polymer composite materials can be carbonized to prepare carbon materials with different forms, such as carbon fibers, carbon foams, carbon nano-microspheres and the like; however, the porous carbon materials prepared from the polymer composite materials generally have mechanical and electromagnetic shielding properties and are difficult to meet the application requirements in the fields of aerospace and the like.

Therefore, the development of a suitable carbon source precursor material and an effective processing method for preparing the porous carbon material with excellent mechanical and electromagnetic shielding properties are one of the urgent needs at present, and the method has very important significance for the application of the porous carbon material in the fields of new energy, military, aerospace and the like.

Disclosure of Invention

In view of the above problems in the prior art, an object of the present invention is to provide an aromatic cyano group/aromatic alkynyl group porous carbon material and a preparation method thereof, so as to obtain a porous carbon material having excellent mechanical strength, electrical conductivity and electromagnetic shielding property, and to simplify a preparation process of the porous carbon material.

In order to achieve the purpose, the preparation method of the aromatic cyano/aromatic alkynyl porous carbon material provided by the invention comprises the following steps:

(1) uniformly blending a resin matrix and a reinforcing component, wherein the mass ratio of the resin matrix to the reinforcing component is 1: (0.01-2);

the resin matrix is composed of at least one resin monomer; the resin monomer is an aromatic cyano resin monomer or/and an aromatic alkynyl resin monomer; the reinforcing component is at least one of graphene oxide, carbon nano tubes, glass fibers and transition metal carbon/nitride (MXene);

(2) pressing and forming the blend;

(3) curing the mixture after pressure forming in an inert gas atmosphere according to the following temperature gradient:

T_m＜T≤T_mkeeping the temperature at 50 ℃ for 2-6 h;

T_m+50℃＜T≤T_mkeeping the temperature at 200 ℃ for 2-6 h;

in the formula, T_mIs the melting temperature of the resin matrix;

(4) heating the cured product to 500-1100 ℃ at a heating rate of 2-15 ℃/min in an inert gas atmosphere, and preserving heat for carbonization for 0.5-3 h;

and after carbonization, cooling the obtained product to room temperature along with the furnace to obtain the porous carbon material.

In the preparation method of the arylcyano/aralkynyl porous carbon material, in the step (1), the structural general formula of the arylcyano resin monomer is as follows:

the structural general formula of the aromatic alkynyl resin monomer is as follows:

in the preparation method of the aromatic cyano/aromatic alkynyl porous carbon material, in the step (1), when the resin matrix consists of at least two resin monomers, the resin monomers are uniformly mixed by grinding or solution blending and the like, and then the uniformly mixed resin monomers and the reinforcing component are mixed. And during curing, the melting point of the highest melting point monomer in the resin monomers is taken as the melting temperature T of the resin matrix_m。

In the preparation method of the aromatic cyano/aromatic alkynyl porous carbon material, in the step (1), the resin matrix and the reinforcing component are blended mainly by a mechanical blending manner, for example, the blending may be at least one of mechanical grinding, dry ball milling, wet ball milling, or mechanical chemical millstone milling. The preferred implementation is as follows: firstly, the resin matrix and the reinforcing component are blended by ultrasonic dispersion, mechanical stirring and wet ball milling in sequence. Researches show that the rotating speed and the ball milling time in the wet ball milling process have great influence on the grinding and dispersion conditions of the components, the high-temperature stability and the lubricating property of the final composite material can be influenced when the rotating speed is too high or the ball milling time is too long, the preferred range of the rotating speed and the ball milling time is 240-260 r/min, and the ball milling time is 5-7 hours. The selection of the ball ratio and the grinding balls in the wet ball milling process can refer to the conventional selection matched in the field.

In the preparation method of the arylcyano/aralkynyl porous carbon material, in the step (2), the blend is pressed and molded under the pressure of 10-210 MPa, and the molding pressure is kept for 1-10 min.

In the preparation method of the aromatic cyano/aromatic alkynyl porous carbon material, the mass ratio of the resin matrix to the reinforcing component is preferably 1: 0.05 to 0.5.

The aromatic cyano group/aromatic alkynyl porous carbon material provided by the invention is a porous carbon material prepared by the method.

The invention provides a method for preparing a porous carbon material with excellent thermal stability, mechanical strength, electrical conductivity and electromagnetic shielding performance by using an aromatic cyano/aromatic alkynyl resin monomer with excellent high-temperature stability in thermosetting resin as a carbonization precursor, realizing good dispersion of a nano filler (a reinforcing component) in the aromatic cyano resin by using a powder metallurgy process and carrying out high-temperature carbonization. The bending strength of the prepared porous carbon material reaches 300MPa at room temperature, and the compression strength reaches 180MPa, which shows that the prepared porous carbon material has good mechanical properties; the electromagnetic shielding performance of the material in the x wave band reaches 55dB, which shows that the porous carbon material prepared by the invention has excellent electromagnetic shielding performance. The porous carbon material can be observed to have an excellent pore structure and a high degree of graphitization by SEM.

The aromatic cyano/aromatic alkynyl porous carbon material and the preparation method thereof have the following beneficial effects:

(1) the method takes an aromatic cyano resin monomer or/and an aromatic alkynyl resin monomer and a reinforcing component as raw materials, and the raw materials are sintered and formed through a powder metallurgy process and then carbonized to obtain a porous carbon material with excellent performance; the compact cross-linked network and the benzene ring structure enable the porous carbon to have excellent mechanical strength, meanwhile, the porous structure enables the porous carbon to have excellent adsorption performance, and the enhancing component is doped to improve the graphitization degree of the porous carbon and enhance the conductivity and the electromagnetic shielding performance of the porous carbon.

(2) The powder metallurgy process adopted by the invention can ensure that the reinforced component does not generate segregation in the resin matrix, and forms physical or chemical 'lap joint' with the middle of the resin matrix at high temperature, thereby being more beneficial to the optimization of the pore diameter structure; the oxygen-containing functional groups are decomposed in the carbonization process, so that the carbon material after high-temperature carbonization has lower oxygen content and is beneficial to improving the conductivity.

(3) The porous carbon material prepared by the invention can avoid the shrinkage of the precursor resin due to the added reinforcing component, so that the appearance size of the precursor resin can be basically maintained, and the porous carbon material has good shape retention and designability of shape.

(4) The method has mature and simple process, can realize curing and carbonization in the same heating equipment, and is easy for large-scale production.

Drawings

FIG. 1 is a three-point bending property curve of an aromatic cyano porous carbon material prepared in example 1 of the present invention.

FIG. 2 is a graph showing the compressive property of the aromatic cyano porous carbon material prepared in example 1 of the present invention.

FIG. 3 is a graph showing the electromagnetic shielding performance of the aromatic cyano porous carbon material prepared in example 1 of the present invention.

FIG. 4 is an SEM photograph of a cyano-aromatic porous carbon material prepared in example 1 of the present invention.

Detailed Description

The technical solutions of the present invention are described in detail below with reference to the accompanying drawings, and it is obvious that the described embodiments are only some embodiments of the present invention, but not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, belong to the present invention.

The arylcyano resin monomers used in the examples were prepared with reference to the following methods:

an arylcyano resin monomer of formula A

Prepared with reference to the following data: xiao H, Zhou T, Shi M, et al. A moving-positioning method installed by powder feeder for thermal positioning resins with a narrow processing window A case study on bio-based irradiation conditioning treatment [ J ]. Chemical Engineering Journal, 2020, 398: 125442.

Arylcyano resin monomers of formula B2

Prepared with reference to the following data: bio-adenine-branched molecular design approach-phase extension [ J ] Journal of Materials, 2020, 55(1): 140-.

Aromatic cyano resin monomer of structural formula B1 and B3

Prepared with reference to the following method: p- (o) -phenylenediamine (2.7g, 24mmol), 6-chloropurine (8.50g, 55mmol), DMF 25 mL and n-pentanol 25 mL were added sequentially to a 250 mL three-necked round-bottomed flask. The mixture is heated to 80 ℃ under the protection of nitrogen and fully stirred for reaction for 6 hours. After the reaction, the reaction mixture was cooled to room temperature, and the reaction mixture was poured into a beaker containing 500 ml of deionized water and washed with stirring. While adjusting the pH to 6 with a saturated aqueous solution of potassium carbonate. After the precipitate was stirred and washed for 30 minutes, it was filtered by vacuum circulation. And (4) continuously stirring and washing the filter cake obtained by suction filtration with 300 ml of deionized water for 30 minutes, carrying out vacuum circulation suction filtration to obtain a filter cake, and repeating the operation twice. The purity of the washed sample was monitored during the washing by Thin Layer Chromatography (TLC). And finally drying the filter cake after suction filtration for 10 hours at the temperature of 100 ℃ in vacuum to obtain the product p- (o) -phenylenediamine adenine. Then p- (o) phenylenediamine adenine (3.44g, 10mmol), 4-nitrophthalonitrile (3.80g, 22mmol) were added sequentially in a 250 ml three-necked round bottom flask, and anhydrous potassium carbonate (3.04g, 22mmol) and 70 ml DMSO were well ground. The reaction was carried out under nitrogen with heating to 50 ℃ and stirring thoroughly for 10 hours. After the reaction, the reaction mixture system maintained at 50 ℃ was directly filtered by vacuum filtration through a Buchner funnel. The resulting filter cake was washed in a beaker containing 300 ml of deionized water with stirring for 30 minutes. The washing was repeated three times or more until the filtrate obtained by the suction filtration was neutral as measured with a pH paper. Washing the final filter cake once with 200 ml tetrahydrofuran solvent, and drying the final filter cake in vacuum at 100 deg.c for 10 hr to obtain final product arylcyano resin monomer of structural formulas B1 and B3.

Aromatic cyano resin monomer with structural formula C1-C3

Prepared with reference to the following method: 100mmol of p- (o/m) -phthalaldehyde, 220mmol of DAMN and 300 ml of DMAc are sequentially added into a 500 ml single-neck round-bottom flask, stirred for 10 minutes at room temperature, then 60d of concentrated sulfuric acid is added dropwise, and the reaction is fully stirred for 1 hour at room temperature. After the reaction is finished, pouring the reaction mixed system into a beaker filled with 500 ml of acetonitrile, stirring and washing for 30 minutes, and performing suction filtration by using vacuum circulation. And (3) continuously stirring and washing the filter cake obtained by suction filtration with 500 ml of ethanol for 30 minutes, carrying out vacuum circulation suction filtration to obtain a filter cake, and repeating the operation for three times. The purity of the washed sample was monitored during the washing by Thin Layer Chromatography (TLC). And finally drying the filter cake after suction filtration for 10 hours at the temperature of 100 ℃ in vacuum to obtain the product Schiff base. Finally, 84mmol of Schiff base, 201.46mmol of nicotinamide and 350ml of DMF are sequentially added into a 1000 ml three-neck round-bottom flask to be fully dissolved, 171.43mmol of NCS is added, and the mixture is heated to 40 ℃ and fully stirred for reaction for 3 hours. After the reaction, the reaction mixture system was poured into a beaker containing 3000 ml of deionized water, stirred and washed for 30 minutes, and then filtered by vacuum circulation. And (4) continuously stirring and washing the filter cake obtained by suction filtration with 2000 ml of deionized water for 30 minutes, carrying out vacuum circulation suction filtration to obtain a filter cake, and repeating the operation twice. The purity of the washed sample was monitored during the washing by Thin Layer Chromatography (TLC). And finally drying the filter cake after suction filtration for 10 hours at the temperature of 100 ℃ in vacuum to obtain the product of the aromatic cyano resin monomer with the structural formula of C1 (C2/C3).

Aromatic cyano resin monomer of structural formula D1-D3

Prepared with reference to the following method: 100mmol of p- (o/m) -oxybenzaldehyde, 220mmol of DAMN and 300 ml of DMAc were sequentially added to a 500 ml single-neck round-bottom flask, and after stirring at room temperature for 10 minutes, 60d of concentrated sulfuric acid was added dropwise and the reaction was stirred well at room temperature for 1 hour. After the reaction is finished, pouring the reaction mixed system into a beaker filled with 500 ml of acetonitrile, stirring and washing for 30 minutes, and performing suction filtration by using vacuum circulation. And (3) continuously stirring and washing the filter cake obtained by suction filtration with 500 ml of ethanol for 30 minutes, carrying out vacuum circulation suction filtration to obtain a filter cake, and repeating the operation for three times. The purity of the washed sample was monitored during the washing by Thin Layer Chromatography (TLC). And finally drying the filter cake after suction filtration for 10 hours at the temperature of 100 ℃ in vacuum to obtain the product Schiff base. Finally, 84mmol of Schiff base, 201.46mmol of nicotinamide and 350ml of DMF are sequentially added into a 1000 ml three-neck round-bottom flask to be fully dissolved, 171.43mmol of NCS is added, and the mixture is heated to 40 ℃ and fully stirred for reaction for 3 hours. After the reaction, the reaction mixture system was poured into a beaker containing 3000 ml of deionized water, stirred and washed for 30 minutes, and then filtered by vacuum circulation. And (4) continuously stirring and washing the filter cake obtained by suction filtration with 2000 ml of deionized water for 30 minutes, carrying out vacuum circulation suction filtration to obtain a filter cake, and repeating the operation twice. The purity of the washed sample was monitored during the washing by Thin Layer Chromatography (TLC). And finally drying the filter cake after suction filtration for 10 hours at the temperature of 100 ℃ in vacuum to obtain the product of the aromatic cyano resin monomer with the structural formula D1 (D2/D3).

Aromatic cyano resin monomer of structural formula E1-E9

Prepared with reference to the following method: to a 1000 mL four-necked round-bottomed flask were added p- (m/o) fluorobenzaldehyde (63.5g, 512mmol), p- (m/o) benzenediol (30.8g, 280mmol), potassium carbonate (96.7g, 700mmol) and 400 mL of DMF in this order. After pumping the system for 10 times, heating to 155 ℃ under the protection of flowing nitrogen, and fully stirring for reaction for 7 hours. After the reaction is finished, the reaction mixture is cooled to room temperature, poured into a beaker filled with 2500 ml of deionized water, stirred and washed for 30 minutes, and then is subjected to vacuum circulation suction filtration. And (3) continuously stirring and washing the filter cake obtained by suction filtration with 2500 ml of deionized water for 30 minutes, carrying out vacuum circulation suction filtration to obtain a filter cake, and repeating the operation twice. The purity of the washed sample was monitored during the washing by Thin Layer Chromatography (TLC). And finally drying the filter cake after suction filtration for 10 hours at the temperature of 80 ℃ in vacuum to obtain the product phenylene bis (oxy) benzaldehyde. Then, in a 500 ml single neck round bottom flask were added successively phenylene bis (oxy) benzaldehyde (31.83g, 100mmol), DAMN (23.78g, 220mmol) and 300 ml of DMAc, and after stirring at room temperature for 10 minutes, 60d of concentrated sulfuric acid was added dropwise, and the reaction was stirred well at room temperature for 1 hour. After the reaction is finished, pouring the reaction mixed system into a beaker filled with 500 ml of acetonitrile, stirring and washing for 30 minutes, and performing suction filtration by using vacuum circulation. And (3) continuously stirring and washing the filter cake obtained by suction filtration with 500 ml of ethanol for 30 minutes, carrying out vacuum circulation suction filtration to obtain a filter cake, and repeating the operation for three times. The purity of the washed sample was monitored during the washing by Thin Layer Chromatography (TLC). And finally drying the filter cake after suction filtration for 10 hours at the temperature of 100 ℃ in vacuum to obtain the product Schiff base. Finally, Schiff base ((41.78g, 84mmol), nicotinamide (24.60g, 201.46mmol) and 350ml of DMF are sequentially added into a 1000 ml three-neck round-bottom flask to be fully dissolved, then NCS (22.89g, 171.43mmol) is added, the mixture is heated to 40 ℃ and fully stirred to react for 3 hours, after the reaction is finished, the reaction mixture system is poured into a beaker filled with 3000 ml of deionized water to be stirred and washed for 30 minutes, vacuum circulation suction filtration is carried out, the filter cake obtained after suction filtration is continuously stirred and washed for 30 minutes by 2000 ml of deionized water, the filter cake is obtained by vacuum circulation suction filtration, the operation is repeated twice, the purity of the washed sample is monitored by a Thin Layer Chromatography (TLC) method in the washing process, and the filter cake obtained after final suction filtration is dried for 10 hours at the vacuum 100 ℃ to obtain the aromatic cyano resin monomer with the structural formula E1 (E2-E9).

Aromatic cyano resin monomer with structural formula F1-F3

Prepared with reference to the following data: synthesis and properties of high temperature polymeric polymers based on o, m, p-dihydrobenzine isometers [ J ]. Rsc Advances, 2015, 5(98): 80749-80755.

Aromatic cyano resin monomer with structural formula G1-G3

Prepared with reference to the following data: chen X, Liu J, Xi Z, et al. Synthesis and thermal properties of High temperature phenolic resins cured with self-catalytic amino-containing phenolic compositions [ J ]. High Performance Polymers, 2016:0954008316673419.

Aromatic cyano resin monomer with structural formula H1-H3

Prepared with reference to the following data: chen H, Xin H, Lu J, et al.Synthesis and Properties of poly (dimethylsilylene-ethylene-phenyloxyphenylene-ethylene) [ J ] High Performance Polymers, 2016: 0954008316655862.

Example 1

The resin matrix used in this example was an arylcyano resin monomer of formula a.

The reinforcing component used in this example was Graphene Oxide (GO).

In the embodiment, the aromatic cyano porous carbon material is prepared from the raw materials according to the following steps:

(1) uniformly blending the resin matrix and the reinforcing component; the method comprises the following steps:

(11) adding 0.3g of resin matrix and 0.0225g of graphene oxide into 10mL of ethanol, and performing ultrasonic dispersion for 1h at room temperature;

(12) mechanically stirring the obtained dispersion liquid according to 100 revolutions per minute for 1 h;

(13) further grinding a product obtained by mechanical stirring for 6 hours by using a wet ball milling mode, wherein the specific parameters are as follows: the rotating speed is 250 r/min, the ball material ratio is 10:1, the diameter of the grinding ball is 10 mm: the mass ratio of the 5mm balls is 1: 1;

(14) filtering a product obtained by ball milling, and vacuum-drying a filter cake at 80 ℃ for 10 hours to obtain a blend;

(2) keeping the pressure of the obtained blend at 210MPa for 3min, and performing compression molding;

(3) curing the blend after pressure forming in a nitrogen atmosphere according to the following temperature gradient:

keeping the temperature at 300 ℃ for 4 h; keeping the temperature at 375 ℃ for 4 h;

(4) heating the cured product to 800 ℃ at the heating rate of 2 ℃/min under the inert gas atmosphere, preserving heat and carbonizing, and preserving heat for 3 h;

and after the carbonization is finished, cooling the obtained product to room temperature along with the furnace to obtain the aromatic cyano porous carbon material.

The mechanical property analysis of the aromatic cyano porous carbon material prepared in this example is shown in fig. 1 and 2. As can be seen from the figure, the tensile strength (i.e. the bending stress in FIG. 1) reaches 300MPa and the compressive strength reaches 180MPa at room temperature, which indicates that the porous carbon material prepared by the present example has good mechanical properties.

The electromagnetic shielding performance of the aromatic cyano porous carbon material prepared in this example was analyzed, and the analysis result is shown in fig. 3. As can be seen from the figure, the electromagnetic shielding performance of the material in the x wave band reaches 50dB, which shows that the porous carbon material prepared by the embodiment has excellent electromagnetic shielding performance.

The morphology analysis of the aromatic cyano porous carbon material prepared in this example is shown in fig. 4. As can be seen from the figure, the material has an excellent pore structure and a high degree of graphitization.

Example 2

The resin matrix used in this example was an arylcyano resin monomer of formula B1.

The reinforcing component used in this example was Graphene Oxide (GO).

(11) adding 0.3g of resin matrix and 0.015g of graphene oxide into a ceramic mortar for grinding for 30 min;

(12) and further grinding the product obtained by grinding for 6h by using a dry ball milling mode, wherein the specific parameters are as follows: the rotating speed is 250 r/min, the ball material ratio is 10:1, the diameter of the grinding ball is 10 mm: the mass ratio of the 5mm balls is 1: 1;

(13) further carrying out vacuum drying on the product obtained by ball milling at 80 ℃ for 10h to obtain a blend;

(2) keeping the pressure of the obtained blend at 210MPa for 2min, and performing compression molding;

keeping the temperature at 300 ℃ for 2 h; keeping the temperature at 375 ℃ for 6 h;

(4) heating the cured product to 1100 ℃ at a heating rate of 10 ℃/min under the inert gas atmosphere, preserving heat and carbonizing, and preserving heat for 3 h;

Example 3

The resin matrix used in this example was an arylcyano resin monomer of formula B2.

The reinforcing component used in this example was Graphene Oxide (GO).

(11) adding 0.3g of resin matrix and 0.15g of graphene oxide into 10mL of ethanol, and performing ultrasonic dispersion for 1h at room temperature;

(2) keeping the pressure of the obtained blend at 70MPa for 3min, and performing compression molding;

keeping the temperature at 300 ℃ for 6 h; keeping the temperature at 375 ℃ for 2 h;

(4) heating the cured product to 800 ℃ at the heating rate of 15 ℃/min under the inert gas atmosphere, preserving heat and carbonizing, and preserving heat for 1 h;

Example 4

The resin matrix used in this example was an arylcyano resin monomer of formula B3.

The reinforcing component used in this example was Carbon Nanotubes (CNTs).

(11) adding 0.3g of resin matrix and 0.09g of carbon nano tube into 10mL of ethanol, and performing ultrasonic dispersion for 1h at room temperature;

(12) mechanically stirring the obtained dispersion liquid at 250 revolutions per minute for 1 h;

(14) further carrying out vacuum drying on the product obtained by ball milling at 80 ℃ for 10h to obtain a blend;

(2) keeping the pressure of the obtained blend at 10MPa for 3min, and performing compression molding;

keeping the temperature at 300 ℃ for 5 h; keeping the temperature at 375 ℃ for 5 h;

(4) heating the cured product to 500 ℃ at the heating rate of 2 ℃/min under the inert gas atmosphere, preserving heat and carbonizing, and preserving heat for 1 h;

Example 5

The resin matrix used in this example was an arylcyano resin monomer of formula C1.

The reinforcing component used in this example was Carbon Nanotubes (CNTs).

(11) adding 0.15g of resin matrix and 0.3g of carbon nano tube into 10mL of ethanol, and performing ultrasonic dispersion for 1h at room temperature;

Example 6

The resin matrix used in this example was an arylcyano resin monomer of formula C2.

The reinforcing component used in this example was Carbon Nanotubes (CNTs).

(11) adding 3.0g of resin matrix and 0.03g of carbon nano tube into a mortar for grinding for 30 min;

(4) heating the cured product to 800 ℃ at the heating rate of 10 ℃/min under the inert gas atmosphere, preserving heat and carbonizing, and preserving heat for 0.5 h;

Example 7

The resin matrix used in this example was an arylcyano resin monomer of formula C3.

The reinforcing component used in this example was glass fiber.

(11) adding 0.3g of resin matrix and 0.0225g of glass fiber into 10mL of ethanol, and performing ultrasonic dispersion for 1h at room temperature;

(14) further carrying out vacuum drying on the product obtained by ball milling at 10 ℃ for 10 hours to obtain a blend;

(2) keeping the pressure of the obtained blend at 10MPa for 15min, and performing compression molding;

(4) heating the cured product to 800 ℃ at the heating rate of 2 ℃/min under the inert gas atmosphere, preserving heat and carbonizing, and preserving heat for 0.5 h;

Example 8

The resin matrix used in this example was the arylcyano resin monomer of formula D1.

The reinforcing component used in this example was glass fiber.

(11) adding 0.15g of resin matrix and 0.3g of glass fiber into 10mL of ethanol, and performing ultrasonic dispersion for 1h at room temperature;

(4) heating the cured product to 800 ℃ at a heating rate of 10 ℃/min under the inert gas atmosphere, preserving heat and carbonizing, and preserving heat for 3 h;

Example 9

The resin matrix used in this example was the arylcyano resin monomer of formula D2.

The reinforcing component used in this example was glass fiber.

(11) adding 3.0g of resin matrix and 0.03g of glass fiber into 10mL of ethanol, and performing ultrasonic dispersion for 1h at room temperature;

keeping the temperature at 300 ℃ for 4 h; keeping the temperature at 375 ℃ for 6 h;

(4) heating the cured product to 1100 ℃ at a heating rate of 15 ℃/min under the inert gas atmosphere, preserving heat and carbonizing, and preserving heat for 3 h;

Example 10

The resin matrix used in this example was the arylcyano resin monomer of formula D3.

The reinforcing component used in this example was Graphene Oxide (GO).

keeping the temperature at 300 ℃ for 6 h; keeping the temperature at 375 ℃ for 4 h;

(4) heating the cured product to 1100 ℃ at a heating rate of 10 ℃/min under the inert gas atmosphere, preserving heat and carbonizing, and preserving heat for 1 h;

Example 11

The resin matrix used in this example was an arylcyano resin monomer of formula E1.

The reinforcing component used in this example was Graphene Oxide (GO).

(11) adding 0.15g of resin matrix and 0.3g of graphene oxide into 10mL of ethanol, and performing ultrasonic dispersion for 1h at room temperature;

Example 12

The resin matrix used in this example was an arylcyano resin monomer of formula E2.

The reinforcing component used in this example was Graphene Oxide (GO).

(11) adding 3.0g of resin matrix and 0.03g of graphene oxide into a mortar for grinding for 30 min;

Example 13

The resin matrix used in this example was an arylcyano resin monomer of formula E3.

The reinforcing component used in this example was Graphene Oxide (GO).

(4) heating the cured product to 800 ℃ at the heating rate of 10 ℃/min under the inert gas atmosphere, preserving heat and carbonizing, and preserving heat for 1.5 h;

Example 14

The resin matrix used in this example was an arylcyano resin monomer of formula E4.

The reinforcing component used in this example was Carbon Nanotubes (CNTs).

(4) heating the cured product to 800 ℃ at the heating rate of 2 ℃/min under the inert gas atmosphere, preserving heat and carbonizing, and preserving heat for 1 h;

Example 15

The resin matrix used in this example was an arylcyano resin monomer of formula E5.

The reinforcing component used in this example was Carbon Nanotubes (CNTs).

(11) adding 3.0g of resin matrix and 0.03g of carbon nano tube into 10mL of ethanol, and performing ultrasonic dispersion for 1h at room temperature;

(4) heating the cured product to 800 ℃ at the heating rate of 15 ℃/min under the inert gas atmosphere, preserving heat and carbonizing, and preserving heat for 3 h;

Example 16

The resin matrix used in this example was an arylcyano resin monomer of formula E6.

The reinforcing component used in this example was glass fiber.

Example 17

The resin matrix used in this example was an arylcyano resin monomer of formula E7.

The reinforcing component used in this example was glass fiber.

Example 18

The resin matrix used in this example was an arylcyano resin monomer of formula E8.

The reinforcing component used in this example was glass fiber.

(11) 3.0g of resin matrix and 0.03g of glass fiber were added to a ceramic mortar and ground for 30min

Example 19

The resin matrix used in this example was an arylcyano resin monomer of formula E9.

The reinforcing component used in this example was Graphene Oxide (GO).

(4) heating the cured product to 800 ℃ at a heating rate of 10 ℃/min under the inert gas atmosphere, preserving heat and carbonizing, and preserving heat for 1 h;

Example 20

The resin matrix used in this example was an arylcyano resin monomer of formula F1.

The reinforcing component used in this example was Graphene Oxide (GO).

Example 21

The resin matrix used in this example was an arylcyano resin monomer of formula F2.

The reinforcing component used in this example was Graphene Oxide (GO).

(11) adding 3.0g of resin matrix and 0.03g of graphene oxide into 10mL of ethanol, and performing ultrasonic dispersion for 1h at room temperature;

Example 22

The resin matrix used in this example was an arylcyano resin monomer of formula F3.

The reinforcing component used in this example was Carbon Nanotubes (CNTs).

(11) adding 0.3g of resin matrix and 0.0225g of carbon nano tube into 10mL of ethanol, and performing ultrasonic dispersion for 1h at room temperature;

(4) heating the cured product to 500 ℃ at the heating rate of 2 ℃/min under the inert gas atmosphere, preserving heat and carbonizing, and preserving heat for 1.5 h;

Example 23

The resin matrix used in this example was an arylcyano resin monomer of formula G1.

The reinforcing component used in this example was Carbon Nanotubes (CNTs).

Example 24

The resin matrix used in this example was an arylcyano resin monomer of formula G2.

The reinforcing component used in this example was Carbon Nanotubes (CNTs).

(11) 3.0g of the resin matrix and 0.03g of the carbon nanotubes were added to a ceramic mortar and ground for 30min

Example 25

The resin matrix used in this example was an arylcyano resin monomer of formula G3.

The reinforcing component used in this example was glass fiber.

Example 26

The resin matrix used in this example was an arylalkynyl resin monomer of formula H1.

The reinforcing component used in this example was glass fiber.

In the embodiment, the aryl alkynyl porous carbon material is prepared from the raw materials according to the following steps:

and after carbonization, cooling the obtained product to room temperature along with the furnace to obtain the aryne-based porous carbon material.

Example 27

The resin matrix used in this example was an arylalkynyl resin monomer of formula H2.

The reinforcing component used in this example was glass fiber.

Example 28

The resin matrix used in this example was an arylalkynyl resin monomer of formula H3.

The reinforcing component used in this example was Graphene Oxide (GO).

(11) grinding 0.3g of resin matrix and 0.0225g of graphene oxide by using a strong chemical grinding disc for 1 h;

(14) the obtained product is further dried in vacuum at 80 ℃ for 10h to obtain a blend;

Example 29

The enhancement component used in this example was MXene [ ACS nano, 2020, DOI:10.1021/acsnano.0c03391 ].

(11) adding 0.15g of resin matrix and 0.3g of MXene into 10mL of ethanol, and ultrasonically dispersing for 1h at room temperature;

Example 30

The resin matrix used in this example is a resin monomer of formula (a + C1) ground at a mass ratio of 1:1 for 30 min.

The reinforcing component used in this example was Graphene Oxide (GO).

Example 31

The resin matrix used in this example is a resin monomer of formula (a + H3) ground at a mass ratio of 1:1 for 30 min.

The reinforcing component used in this example was Graphene Oxide (GO).

and after carbonization, cooling the obtained product to room temperature along with the furnace to obtain the arylcyano/arylalkynyl porous carbon material.

Claims

1. A preparation method of an arylcyano/aralkynyl porous carbon material is characterized by comprising the following steps:

(1) uniformly mixing a resin matrix and a reinforcing component to form a blend, wherein the mass ratio of the resin matrix to the reinforcing component in the blend is 1: (0.01-2);

the resin matrix is composed of at least one resin monomer; the resin monomer is an aromatic cyano resin monomer or/and an aromatic alkynyl resin monomer; the reinforcing component is one of graphene oxide, carbon nano tubes, glass fibers and transition metal carbon/nitride;

(2) pressing and forming the blend;

T_m＜T≤T_mkeeping the temperature for 3-5 h at +50 ℃;

T_m+50℃＜T≤T_mkeeping the temperature for 3-5 h at 200 ℃;

in the formula, T_mIs the melting temperature of the resin matrix;

2. The method for producing an arylcyano/aralkynyl porous carbon material according to claim 1, characterized in that: in the step (1), the structural general formula of the aromatic cyano resin monomer is as follows:

3. the method for producing an arylcyano/aralkynyl porous carbon material according to claim 1, characterized in that: in the step (1), when the resin matrix is composed of at least two resin monomers, the resin monomers are uniformly mixed by grinding, melting or solution mixing, and then the uniformly mixed resin monomers are mixed with the reinforcing component.

4. The method for producing an arylcyano/aralkynyl porous carbon material according to claim 3, characterized in that when the resin matrix is composed of at least two resin monomers, the melting point of the highest melting point monomer among the resin monomers is taken as the melting temperature T of the resin matrix_m。

5. The method for producing an arylcyano/aralkynyl porous carbon material as claimed in any one of claims 1 to 4, wherein in the step (1), the mixing manner of the resin base and the reinforcing component is a mechanical mixing manner.

6. The method for preparing an arylcyano/aralkynyl porous carbon material according to claim 5, characterized in that the mechanical blending manner is mechanical milling, dry ball milling, wet ball milling or mechanochemical millstone milling.

7. The method for producing an arylcyano/aralkynyl porous carbon material as claimed in any one of claims 1 to 4, wherein the blend is press-molded under a pressure of 10 to 210 MPa.

8. The method for producing an arylcyano/aralkynyl porous carbon material as claimed in any one of claims 1 to 4, wherein the mass ratio of the resin base to the reinforcing component is 1: (0.05-0.5).

9. An arylcyano/aralkynyl porous carbon material, characterized in that the arylcyano/aralkynyl porous carbon material is prepared by the preparation method according to any one of claims 1 to 8.