CN112499615A - Nano polymer ring, nano carbon ring and preparation method thereof - Google Patents

Nano polymer ring, nano carbon ring and preparation method thereof Download PDF

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CN112499615A
CN112499615A CN202011383440.1A CN202011383440A CN112499615A CN 112499615 A CN112499615 A CN 112499615A CN 202011383440 A CN202011383440 A CN 202011383440A CN 112499615 A CN112499615 A CN 112499615A
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CN112499615B (en
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李文翠
侯璐
陆安慧
张玉
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Dalian University of Technology
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    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B32/00—Carbon; Compounds thereof
    • C01B32/15—Nano-sized carbon materials
    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
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    • C08G14/00—Condensation polymers of aldehydes or ketones with two or more other monomers covered by at least two of the groups C08G8/00 - C08G12/00
    • C08G14/02—Condensation polymers of aldehydes or ketones with two or more other monomers covered by at least two of the groups C08G8/00 - C08G12/00 of aldehydes
    • C08G14/04—Condensation polymers of aldehydes or ketones with two or more other monomers covered by at least two of the groups C08G8/00 - C08G12/00 of aldehydes with phenols
    • C08G14/06—Condensation polymers of aldehydes or ketones with two or more other monomers covered by at least two of the groups C08G8/00 - C08G12/00 of aldehydes with phenols and monomers containing hydrogen attached to nitrogen

Abstract

The invention provides a nano polymer ring, a nano carbon ring and a preparation method thereof. The method comprises the steps of taking long-chain fatty alcohol as a phase change material, taking a surfactant, phenol, aldehyde and organic amine as raw materials, taking water as a solvent, carrying out phase transformation induced molecular directional self-assembly and polymerization to obtain a nano polymer ring, and carbonizing to obtain the nano carbon ring. The diameter of the nano polymer ring is 120-1100nm, and the diameter of the cross-section circle is 30-300 nm. The diameter of the carbon nano-ring is 100-1000nm, and the diameter of the cross-section circle is 20-280 nm. The invention relates to a method for preparing a nano polymer ring and a carbon ring based on phase inversion induced molecular oriented self-assembly. By changing the proportion of the long-chain fatty alcohol phase-change material to the phenol, the diameters of the cross-section circles of the polymer ring and the carbon ring can be changed, and the regulation and control of the annular structure are realized, which is difficult to achieve by other methods.

Description

Nano polymer ring, nano carbon ring and preparation method thereof
Technical Field
The invention relates to controllable preparation of a nano polymer ring and a nano carbon ring, in particular to a nano polymer ring and a nano carbon ring formed by oriented self-assembly based on phase inversion induction and preparation methods thereof.
Background
The porous nanocarbon material generally has physical and chemical properties such as rich pore channels, high specific surface area, high electric conductivity and thermal conductivity, good structural stability and the like, so the porous nanocarbon material is widely applied to the fields of catalysis, energy storage, adsorption, separation and the like. The morphology and structural characteristics of carbon materials can significantly affect their properties, for example, the electrochemical properties of carbon fibers are strongly related primarily to their high aspect ratio and small radial dimensions. The relatively rare nano carbon material with the annular structure has unique physical and chemical properties such as magnetic resistance which is negatively related to temperature at low temperature, unique electromechanical effect and magnetic response related to curvature due to the special appearance and structural characteristics, so the nano carbon material has important application value in the fields of biosensors, electromagnetic devices, energy storage and the like. In addition, the ring structure can be used as a building unit for assembling a complex superstructure. Although the cyclic nanocarbon material shows huge application potential and market prospect, how to accurately synthesize the cyclic nanocarbon material by molecular self-assembly in a solution has not been reported.
Amphiphilic block copolymers have abundant self-assembly behavior in solution and are often used to synthesize spherical, cylindrical, vesicular, or other complex nanostructures. The main idea of preparing the ring-shaped micelle is to use the columnar micelle formed by self-assembly of the block copolymer as a secondary unit and induce the tail ends of the columnar micelle to be mutually connected to form a ring-shaped structure. The method provides driving force required by ring formation by treating the columnar micelle and inducing the hydrophobic cores to attract each other or the ions of the block copolymer to complex, and finally promotes the formation of the annular nano structure.
However, the existing method for forming polymer rings by self-assembly of rod-shaped micelles has great limitations, and because of the step of forming polymer rings by inducing a rod-shaped precursor, products often coexist with the precursor, the uniformity is not high, the size distribution is wide, and thus a ring structure with uniform size is difficult to obtain; moreover, the polymer cyclic micelle reported in the prior art has no residual carbon content in the pyrolysis process and cannot be converted into a cyclic porous carbon material.
Disclosure of Invention
The invention aims to provide a nano polymer ring and a carbon ring formed by directed self-assembly based on phase inversion induction and preparation methods thereof.
The technical scheme of the invention is as follows:
a phase inversion induction based directional self-assembly nano polymer ring and a nano carbon ring are prepared by taking long-chain fatty alcohol as a phase change material, taking a surfactant, phenol, aldehyde and organic amine as raw materials, taking water as a solvent, performing phase inversion induction molecular directional self-assembly and polymerization to obtain a nano polymer ring, and carbonizing to obtain the nano carbon ring. The diameter of the nano polymer ring is 120-1100nm, and the diameter of the cross-section circle is 30-300 nm. The diameter of the carbon nano-ring is 100-1000nm, and the diameter of the cross-section circle is 20-280 nm. .
A method for preparing a directional self-assembly nano polymer ring and a nano carbon ring based on phase inversion induction comprises the following steps of taking long-chain fatty alcohol as a phase change material, taking a surfactant, phenol, aldehyde and organic amine as raw materials, taking water as a solvent, preparing the polymer ring with regular appearance and adjustable cross-section circle diameter through low-temperature polymerization, and further performing carbonization and pyrolysis to obtain the nano carbon ring, wherein the method comprises the following steps:
adding a long-chain fatty alcohol phase-change material into an aqueous solution of a surfactant, and violently stirring at a high temperature to obtain a semitransparent white solution, wherein the mass ratio of the long-chain fatty alcohol phase-change material to the surfactant is 1:10-1: 2;
secondly, standing the obtained semitransparent white emulsion at a low temperature to obtain white colloidal solution;
thirdly, sequentially adding water, aldehyde, white colloidal solution and organic amine into the phenol aqueous solution according to a proportion, stirring in a water bath for 4-24 hours, filtering, washing and drying the product to obtain a colloidal polymer sheet; wherein the molar ratio of the phenol, the aldehyde, the organic amine and the surfactant is 1:1-3:0.1-1:0.001-0.04, and the mass ratio of the phenol to the water is 1:200-1: 3000;
putting the colloid polymer sheet into a carbonization furnace, and carbonizing under the protection of inert gas to obtain a nano carbon ring; the carbonization method comprises the steps of increasing the temperature from room temperature to 400 ℃ at a speed of 1-3 ℃/min under the protection of inert gas, and carrying out volatilization of the long-chain fatty alcohol phase-change material at constant temperature for 120 min; then raising the temperature to 500-;
the surfactant is polyoxyethylene-polyoxypropylene-polyoxyethylene triblock copolymer, sorbitan monooleate polyoxyethylene ether (Tween 80), sorbitan monooleate (span-80) and polyvinylpyrrolidone; the polyoxyethylene-polyoxypropylene-polyoxyethylene triblock copolymer F127 is preferred.
The long-chain fatty alcohol phase-change material is preferably straight-chain fatty alcohol CnH2n+1OH(n＝10-30)。
The stirring temperature is 50-100 ℃, the standing temperature is 0-50 ℃, and the standing time is 1-200 h.
The phenol is phenol, resorcinol, phloroglucinol or bisphenol A; resorcinol is preferred.
The aldehyde is benzaldehyde, glyoxal, butyraldehyde, glutaraldehyde or 37 wt.% formaldehyde, preferably 37 wt.% formaldehyde.
The organic amine is ethylenediamine, n-propylamine, p-aniline, hexamethylenediamine or aniline, and preferably n-propylamine.
The inert gas is argon or nitrogen.
The basic principle of the invention is that:
(1) the polymer ring and carbon ring are synthesized based on a phase inversion induced directed self-assembly process. The hydrophobic long-chain fatty alcohol phase change material is fully dispersed in a surfactant solution, and fatty alcohol and surfactant micelles can form mixed micelles in an aqueous solution through micelle interaction. In the low-temperature standing process, the phase change of the long-chain fatty alcohol induces the micelle to deform and directionally self-assemble to form the annular micelle. The polymer ring and the carbon ring with uniform size and regular appearance can be obtained by coating and carbonizing the soft template with a polymer.
(2) The polymer ring is carbonized to obtain the carbon ring. During the carbonization of the polymer ring, the inner template is decomposed and volatilized to leave an annular cavity. Due to the thermal stability and structural stability of the polymer component, the carbon ring perfectly maintains an annular structure, and has the characteristics of a microporous structure and high specific surface area.
(3) The diameters of the cross sections of the polymer ring and the carbon ring are adjustable. By changing the proportion of the long-chain fatty alcohol phase-change material to the resorcinol, carbon rings with different cross-section circle diameters can be obtained. The use amount of resorcinol is increased, so that the polymerization rate is increased, and the polymerization products are increased, so that a polymer ring with a larger diameter of a cross-sectional circle can be obtained, and a carbon ring with a larger diameter of the cross-sectional circle can be obtained.
Compared with the prior art, the invention has the beneficial effects of providing the colloidal polymer ring and the carbon ring prepared by phase inversion induced oriented self-assembly and the preparation methods thereof. By changing the proportion of the long-chain fatty alcohol phase-change material to the phenol, the diameters of the cross-section circles of the polymer ring and the carbon ring can be changed, and the regulation and control of the annular structure are realized, which is difficult to achieve by other methods. The method has simple process, does not need the additional step of inducing the self-assembly of the rod-shaped micelle to form a ring structure, so that the prepared polymer has regular ring shape and uniform size, and has high carbon residue rate and good ring shape retention after carbonization.
Drawings
FIG. 1 is a scanning electron microscope of the nano-polymer ring prepared in example 5 of the present invention, wherein a is 11000 times magnified, and b is 100000 times magnified.
Fig. 2 is a scanning electron microscope of the nanocarbon ring prepared in example 6 of the present invention, wherein the magnification is 11000 times, and the magnification is 100000 times.
Detailed Description
The following non-limiting examples are presented to enable those of ordinary skill in the art to more fully understand the present invention and are not intended to limit the invention in any way.
The sources of the raw materials and the equipment used by the nano polymer ring and the carbon ring of the invention are shown in Table 1
Table 1 materials and equipment sources used in the invention
Figure BDA0002810285040000041
Figure BDA0002810285040000051
Figure BDA0002810285040000061
Example 1
400mg of the surfactant F127 is weighed out and dissolved in 40mL of deionized water with stirring for 1 h. The aqueous solution of F127 was warmed to 90 ℃ and then 150mg dodecanol was added and stirred rapidly for 2h to give a translucent white emulsion. The obtained white emulsion is placed at 20 ℃ and kept stand for 120h to obtain white colloidal solution. Then, 440mg of resorcinol is weighed and placed in a 500mL round-bottom flask, 360mL of deionized water is added, after the resorcinol is fully dissolved, 584 μ L of formaldehyde solution (37 wt%) is sequentially added, the white colloidal solution and 60mg of n-propylamine are stirred and reacted for 1h to obtain a white colloidal solution, and the obtained white colloidal solution is heated to 70 ℃ and stirred for 6 h. After the reaction is finished, centrifuging the reactant at 8000r/min for 5min, washing with deionized water, and drying the product to obtain the monodisperse nano polymer ring. The diameter of the polymer ring obtained in the example is 686 +/-96 nm, and the diameter of the cross-sectional circle is 123 +/-15 nm.
Example 2
Placing the nano polymer ring prepared in the example 1 in a carbonization furnace for carbonization, raising the temperature from room temperature to 400 ℃ at a speed of 3 ℃/min under the protection of argon, and keeping the temperature for 120 min; then the temperature is raised from 400 ℃ to 600 ℃ of the final carbonization temperature at the temperature raising rate of 5 ℃/min, the temperature is kept for 120min, and the obtained nano carbon ring with the maintained shape is obtained, and the BET specific surface area is 802cm3G, total pore volume 0.28cm3The concentration of the pore diameter is distributed at 0.5 nm. The diameter of the nano-carbon obtained in the embodiment is 592 +/-67 nm, and the diameter of the cross-sectional circle is 108 +/-10 nm.
Example 3
200mg of the surfactant F127 was weighed, 20mL of deionized water was added, and the mixture was dissolved at 20 ℃ for 1 hour with stirring. The aqueous solution of F127 was warmed to 80 ℃ and then 100mg tetradecanol was added and stirred rapidly for 3h to give a translucent white emulsion. The obtained white emulsion is placed at 30 ℃ and kept stand for 96h to obtain white colloidal solution. 440mg of resorcinol is weighed and placed in a 500mL round-bottom flask, 380mL of deionized water is added, 584 μ L of formaldehyde solution (37 wt%) is sequentially added after the resorcinol is fully dissolved, the white colloidal solution and 60mg of n-propylamine are stirred and reacted for 0.5h to obtain a white colloidal solution, and the obtained white colloidal solution is heated to 90 ℃ and stirred for 4 h. After the reaction is finished, centrifuging the reactant at 8000r/min for 5min, washing with deionized water, and drying the product to obtain the monodisperse nano polymer ring. Raising the temperature from room temperature to 400 ℃ at the speed of 2 ℃/min under the protection of argon, and keeping the temperature for 120 min; then the temperature is increased from 400 ℃ to 700 ℃ at the heating rate of 3 ℃/min, and the temperature is kept for 120min to obtain the nano carbon ring. The diameter of the polymer ring obtained in the embodiment is 602 +/-101 nm, the diameter of the cross-sectional circle is 142 +/-20 nm, the diameter of the carbonized carbon ring is 589 +/-87 nm, and the diameter of the cross-sectional circle is 130 +/-11 nm.
Example 4
200mg of the surfactant F127 was weighed, 20mL of deionized water was added, and the mixture was dissolved at 20 ℃ for 1 hour with stirring. The aqueous solution of F127 was warmed to 80 ℃ and then 100mg tetradecanol was added and stirred rapidly for 3h to give a translucent white emulsion. The obtained white emulsion is placed at 30 ℃ and kept stand for 96h to obtain white colloidal solution. 440mg of resorcinol is weighed and placed in a 500mL round-bottom flask, 180mL of deionized water is added, after the resorcinol is fully dissolved, 584 μ L of formaldehyde solution (37 wt%) is sequentially added, the white colloidal solution and 58mg of hexamethylenediamine are stirred and reacted for 0.5h to obtain a white colloidal solution, and the obtained white colloidal solution is heated to 90 ℃ and stirred for 4 h. After the reaction is finished, centrifuging the reactant at 8000r/min for 5min, washing with deionized water, and drying the product to obtain the monodisperse nano polymer ring. Raising the temperature from room temperature to 400 ℃ at the speed of 2 ℃/min under the protection of argon, and keeping the temperature for 120 min; then the temperature is increased from 400 ℃ to 700 ℃ at the heating rate of 3 ℃/min, and the temperature is kept for 120min to obtain the nano carbon ring. The diameter of the polymer ring obtained in the embodiment is 623 +/-108 nm, the diameter of the cross-sectional circle is 182 +/-23 nm, the diameter of the carbonized carbon ring is 598 +/-89 nm, and the diameter of the cross-sectional circle is 162 +/-14 nm.
Example 5
100mg of the surfactant F127 was weighed, 10mL of deionized water was added, and the mixture was dissolved at 40 ℃ for 1 hour with stirring. The aqueous solution of F127 was warmed to 80 ℃ and then 40mg of octadecanol were added and stirred rapidly at 80 ℃ for 3h to give a translucent white emulsion. The obtained white emulsion is placed at 28 ℃ and kept stand for 120h to obtain white colloidal solution. Then, 440mg of resorcinol is weighed and placed in a 500mL round-bottom flask, 390mL of deionized water is added, after the resorcinol is fully dissolved, 584 μ L of formaldehyde solution (37 wt%) is sequentially added, the white colloidal solution and 60mg of n-propylamine are stirred and reacted for 0.5h to obtain a white colloidal solution, and the obtained white colloidal solution is heated to 70 ℃ and stirred for 4 h. After the reaction is finished, centrifuging the reactant at 8000r/min for 5min, washing with deionized water, and drying the product to obtain the monodisperse nano polymer ring. The diameter of the obtained polymer ring is 782 +/-83 nm, the diameter of the cross-sectional circle is 187 +/-12 nm, and a scanning electron microscope is shown in FIG. 1.
Example 6
Placing the nano polymer ring prepared in the example 5 in a carbonization furnace for carbonization, raising the temperature from room temperature to 400 ℃ at a speed of 3 ℃/min under the protection of argon, and keeping the temperature for 120 min; then the temperature is raised from 400 ℃ to 600 ℃ at the temperature raising rate of 5 ℃/min, the temperature is kept for 120min, and the obtained nano carbon ring with the maintained shape is obtained, wherein the BET specific surface area is 772cm3G, total pore volume 0.22cm3The concentration of the pore diameter is distributed at 0.5 nm. The diameter of the nano-carbon obtained in the embodiment is 640 +/-67 nm, the diameter of the cross-sectional circle is 155 +/-10 nm, and a scanning electron microscope is shown in FIG. 2.
Example 7
100mg of the surfactant F127 was weighed, 10mL of deionized water was added, and the mixture was dissolved at 40 ℃ for 1 hour with stirring. The aqueous solution of F127 was warmed to 85 ℃ and then 50mg of cetyl alcohol was added and stirred rapidly for 3h to give a translucent white emulsion. The obtained white emulsion is placed at 25 ℃ and kept stand for 120h to obtain white colloidal solution. 440mg of resorcinol is weighed and placed in a 500mL round-bottom flask, 390mL of deionized water is added, 584 μ L of formaldehyde solution (37 wt%) is sequentially added after the resorcinol is fully dissolved, the white colloidal solution and 60mg of n-propylamine are stirred and reacted for 0.5h to obtain a white colloidal solution, and the obtained white colloidal solution is heated to 70 ℃ and stirred for 10 h. After the reaction is finished, centrifuging the reactant at 8000r/min for 5min, washing with deionized water, and drying the product to obtain the monodisperse nano polymer ring. Raising the temperature from room temperature to 400 ℃ at a speed of 3 ℃/min under the protection of argon, and keeping the temperature for 120 min; then the temperature is raised from 400 ℃ to 600 ℃ of the final carbonization temperature at the temperature raising rate of 5 ℃/min, and the temperature is kept for 120min to obtain the nano carbon ring. The diameter of the polymer ring obtained in the embodiment is 892 +/-203 nm, the diameter of the cross-sectional circle is 180 +/-32 nm, the diameter of the carbonized carbon ring is 840 +/-178 nm, and the diameter of the cross-sectional circle is 159 +/-20 nm.
Example 8
200mg of the surfactant F127 was weighed, 10mL of deionized water was added, and the mixture was dissolved at 40 ℃ for 1 hour with stirring. The aqueous solution of F127 was warmed to 85 ℃ and then 50mg of cetyl alcohol was added and stirred rapidly for 3h to give a translucent white emulsion. The obtained white emulsion is placed in a water bath at 25 ℃ for 120h to obtain a white colloidal solution. 440mg of resorcinol is weighed and placed in a 500mL round-bottom flask, 390mL of deionized water is added, 584 μ L of formaldehyde solution (37 wt%) is sequentially added after the resorcinol is fully dissolved, the white colloidal solution and 60mg of n-propylamine are stirred and reacted for 0.5h to obtain a white colloidal solution, and the obtained white colloidal solution is heated to 70 ℃ and stirred for 10 h. After the reaction is finished, centrifuging the reactant at 8000r/min for 5min, washing with deionized water, and drying the product to obtain the monodisperse nano polymer ring. Raising the temperature from room temperature to 400 ℃ at a speed of 3 ℃/min under the protection of argon, and keeping the temperature for 120 min; then the temperature is raised from 400 ℃ to 600 ℃ of the final carbonization temperature at the temperature raising rate of 5 ℃/min, and the temperature is kept for 120min to obtain the nano carbon ring. The diameter of the polymer ring obtained in the embodiment is 881 +/-186 nm, the diameter of the cross-section circle is 172 +/-36 nm, the diameter of the carbonized carbon ring is 821 +/-152 nm, and the diameter of the cross-section circle is 154 +/-30 nm.
Example 9
500mg of the surfactant F127 was weighed, 40mL of deionized water was added, and the mixture was dissolved at 30 ℃ for 1 hour with stirring. The aqueous solution of F127 was warmed to 70 ℃ and then 200mg of eicosanol was added and stirred rapidly for 5h to give a translucent white emulsion. The obtained white emulsion is placed at 10 ℃ and kept stand for 72h to obtain white colloidal solution. And further weighing 220mg of resorcinol, putting the resorcinol in a 500mL round-bottom flask, adding 360mL of deionized water, after the resorcinol is fully dissolved, sequentially adding 292 mu L of formaldehyde solution (37 wt%), the white colloidal solution and 30mg of n-propylamine, stirring and reacting for 2 hours to obtain a white colloidal solution, heating the obtained white colloidal solution to 80 ℃, and stirring and treating for 6 hours. After the reaction is finished, centrifuging the reactant at 8000r/min for 5min, washing with deionized water, and drying the product to obtain the monodisperse nano polymer ring. Raising the temperature from room temperature to 400 ℃ at the speed of 2 ℃/min under the protection of argon, and keeping the temperature for 120 min; then the temperature is increased from 400 ℃ to 800 ℃ at the temperature increase rate of 5 ℃/min, and the temperature is kept for 120min to obtain the nano carbon ring. The diameter of the polymer ring obtained in the embodiment is 303 +/-88 nm, the diameter of the cross-sectional circle is 189 +/-20 nm, the diameter of the carbonized carbon ring is 286 +/-78 nm, and the diameter of the cross-sectional circle is 168 +/-15 nm.
Example 10
500mg of the surfactant F127 was weighed, 40mL of deionized water was added, and the mixture was dissolved at 30 ℃ for 1 hour with stirring. The aqueous solution of F127 was warmed to 70 ℃ and then 100mg of eicosanol was added and stirred rapidly for 5h to give a translucent white emulsion. The obtained white emulsion is placed at 20 ℃ and kept stand for 72h to obtain white colloidal solution. And further weighing 220mg of resorcinol, putting the resorcinol in a 500mL round-bottom flask, adding 360mL of deionized water, after the resorcinol is fully dissolved, sequentially adding 292 mu L of formaldehyde solution (37 wt%), the white colloidal solution and 30mg of n-propylamine, stirring and reacting for 2 hours to obtain a white colloidal solution, heating the obtained white colloidal solution to 80 ℃, and stirring and treating for 6 hours. After the reaction is finished, centrifuging the reactant at 8000r/min for 5min, washing with deionized water, and drying the product to obtain the monodisperse nano polymer ring. Raising the temperature from room temperature to 400 ℃ at the speed of 2 ℃/min under the protection of argon, and keeping the temperature for 120 min; then the temperature is increased from 400 ℃ to 800 ℃ at the temperature increase rate of 5 ℃/min, and the temperature is kept for 120min to obtain the nano carbon ring. The diameter of the polymer ring obtained in the embodiment is 286 +/-82 nm, the diameter of the cross-section circle is 122 +/-18 nm, the diameter of the carbonized carbon ring is 252 +/-63 nm, and the diameter of the cross-section circle is 114 +/-12 nm.

Claims (9)

1. A nanometer polymer ring, nanometer carbon ring and its preparation method, characterized by, regard long-chain fatty alcohol as the phase change material, surfactant active, phenol, aldehyde and organic amine as raw materials, water is the solvent, induce the molecule to orient the self-assembly, polymerize and get the nanometer polymer ring through phase inversion, get the nanometer carbon ring after charring; the diameter of the nano polymer ring is 120-1100nm, and the diameter of the cross section circle is 30-300 nm; the diameter of the carbon nano-ring is 100-1000nm, and the diameter of the cross-section circle is 20-280 nm.
2. A method for preparing polymer ring and nanometer carbon ring comprises the steps of taking long-chain fatty alcohol as a phase-change material, taking surfactant, phenol, aldehyde and organic amine as raw materials, taking water as a solvent, preparing the polymer ring with regular appearance and adjustable cross-section circle diameter through low-temperature polymerization, and further carbonizing and pyrolyzing the polymer ring to obtain the nanometer carbon ring, wherein the method comprises the following steps:
adding a long-chain fatty alcohol phase-change material into an aqueous solution of a surfactant, and violently stirring at a high temperature to obtain a semitransparent white solution, wherein the mass ratio of the long-chain fatty alcohol phase-change material to the surfactant is 1:10-1: 2;
secondly, standing the obtained semitransparent white emulsion at low temperature to obtain white colloidal solution;
thirdly, sequentially adding water, aldehyde, white colloidal solution and organic amine into the phenol aqueous solution according to a proportion, stirring in a water bath for 4-24 hours, filtering, washing and drying the product to obtain a colloidal polymer sheet; wherein the molar ratio of the phenol, the aldehyde, the organic amine and the surfactant is 1:1-3:0.1-1:0.001-0.04, and the mass ratio of the phenol to the water is 1:200-1: 3000;
putting the colloid polymer sheet into a carbonization furnace, and carbonizing under the protection of inert gas to obtain a nano carbon ring; the carbonization method comprises the steps of increasing the temperature from room temperature to 400 ℃ at a speed of 1-3 ℃/min under the protection of inert gas, and carrying out volatilization of the long-chain fatty alcohol phase-change material at constant temperature for 120 min; then raising the temperature to 500-1200 ℃ at the final carbonization temperature of 1-5 ℃/min, and keeping the temperature for 60-240min to obtain the nano carbon ring with maintained shape.
3. The method for preparing a nano polymer ring or a nano carbon ring according to claim 2, wherein the surfactant is polyoxyethylene-polyoxypropylene-polyoxyethylene triblock copolymer, sorbitan monooleate polyoxyethylene ether, sorbitol triglyceride or polyvinylpyrrolidone.
4. The method for preparing a nano polymer ring or a nano carbon ring according to claim 2 or 3, wherein the long-chain fatty alcohol phase-change material is a straight-chain fatty alcohol CnH2n+1OH，n＝10-30。
5. The method for preparing polymer rings and nanocarbon rings according to claim 4, wherein the stirring temperature is 50-100 ℃, the standing temperature is 0-50 ℃, and the standing time is 1-200 h.
6. The method for preparing nano polymer ring or nano carbon ring according to claim 2, 3 or 5, wherein the phenol is phenol, resorcinol, phloroglucinol or bisphenol A; resorcinol is preferred.
7. The method for preparing nano polymer rings and nano carbon rings according to claim 6, wherein the aldehyde is benzaldehyde, glyoxal, butyraldehyde, glutaraldehyde or 37 wt.% formaldehyde.
8. The method for preparing a nano polymer ring or a nano carbon ring according to claim 2, 3, 5 or 7, wherein the organic amine is ethylenediamine, n-propylamine, p-aniline, hexamethylenediamine or aniline.
9. The method for preparing a nano polymer ring or a nano carbon ring according to claim 8, wherein the inert gas is argon or nitrogen.
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