Asymmetric structure polymer, carbon microspheres and preparation method thereof

Abstract

The application discloses asymmetric structure polymer, carbon microspheres and a preparation method thereof, and belongs to the technical field of nanometer materials. The asymmetric structure polymer is a snowman-shaped particle; the snowman-shaped particle comprises a hollow phenolic resin sphere with a porous cavity and a phenolic resin protrusion grown on the surface of the hollow phenolic resin sphere. The preparation method of the asymmetric structure polymer is simple in technology, does not need large equipment, and asymmetric structure polymer microspheres are synthesized by one-pot method through adding a mixed solution of an etching agent and a surfactant. The micro-nano structure of the prepared asymmetric structure polymer is regular in morphology and uniform in size. The polymer with different morphologies can be obtained by adjusting the amount of the surfactant.

Description

TECHNICAL FIELD

[0001] The application relates to an asymmetric structure polymer, a carbon microsphere and a preparation method thereof, and belongs to the technical field of nanomaterials. BACKGROUND

[0002] Asymmetric structure nanomaterials have attracted great interest of researchers on the basis of the advantages of traditional symmetric structure nanomaterials due to their unique asymmetric structure and surface anisotropy. Each part of the asymmetric structure nanoparticles can be selectively modified and independently function, realizing function coordination without mutual interference, and thus has wide application prospects in many fields such as catalysis, energy conversion and storage, material science and biomedical engineering.

[0003] At present, main methods for synthesizing asymmetric polymer microspheres are interfacial assembly strategy, soft / hard template method and selective etching strategy. However, the above methods are complex in process, and the synthesized materials are not uniform in morphology and size. Therefore, it has been a hotspot and difficulty to synthesize uniform and controllable asymmetric nanoparticles by a simple synthesis method. SUMMARY

[0004] To solve the foregoing technical problems, the application provides a technical scheme for constructing an asymmetric structure polymer, and an asymmetric structure is obtained by adding a surfactant to an etchant, thereby solving the problems of non-uniform particle size and difficulty in controlling the degree of asymmetry, and the method is one-pot synthesis, simple in operation and high in yield.

[0005] The application adopts the following technical scheme:

[0006] According to a first aspect of the application, an asymmetric structure polymer is provided, and the asymmetric structure polymer is a snowman-shaped particle.

[0007] The snowman-shaped particle comprises a hollow phenolic resin sphere with a porous cavity and a phenolic resin protrusion grown on the surface of the hollow phenolic resin sphere.

[0008] Optionally, the longitudinal length of the asymmetric structure polymer is 320-620 nm.

[0009] Optionally, the longitudinal length of the phenolic resin material is selected from any value or a range value between any two values in 320 nm, 420 nm, 520 nm and 620 nm.

[0010] Optionally, the transverse length of the asymmetric structure polymer is 320-720 nm.

[0011] Optionally, the lateral length of the phenolic resin material is selected from any value or a range between any two values of 320 nm, 420 nm, 520 nm, 620 nm, 720 nm.

[0012] According to another aspect of the present application, a preparation method of the asymmetric structure polymer is provided, comprising the following steps:

[0013] S1, a mixture containing a phenolic compound, an aldehyde compound, a catalyst, and a solvent is reacted I to obtain a system containing polymer I;

[0014] S2, a mixed solution containing a surfactant and an etchant is added to the system containing polymer I, and reacted II to obtain the asymmetric structure polymer.

[0015] Optionally, the surfactant is selected from at least one of fluorocarbon surfactant, sodium dodecyl sulfate, sodium dodecyl benzene sulfonate, sodium laurate, cetyltrimethylammonium bromide, sodium oleate, Pluronic F127, P123, P108, F68, and dicetyl dimethyl ammonium bromide.

[0016] Optionally, the concentration of the surfactant in the mixed solution is 0.1-30 g / L.

[0017] Optionally, the concentration of the surfactant in the mixed solution is selected from any value or a range between any two values of 0.1 g / L, 0.15 g / L, 0.2 g / L, 0.5 g / L, 1 g / L, 5 g / L, 10 g / L, 20 g / L, and 30 g / L.

[0018] Optionally, the etchant is selected from at least one of methanol, ethanol, acetone, N,N-dimethylformamide, tetrahydrofuran, dichloroethane, ethylene oxide, and dimethyl sulfoxide.

[0019] Optionally, the volume ratio of the etchant to the solvent is 0.3-6:1.

[0020] Optionally, the volume ratio of the etchant to the solvent is selected from any value or a range between any two values of 0.3:1, 0.5:1, 0.75:1, 1:1, 2:1, 3:1, 4:1, 5:1, and 6:1.

[0021] Optionally, the phenolic compound is selected from at least one of 2-aminophenol, 3-aminophenol, 4-aminophenol, 3-aminophenol, 4-amino-3-fluorothiophenol, resorcinol, hydroquinone, and pyrogallol.

[0022] Optionally, the aldehyde compound is selected from at least one of formaldehyde, glyoxal, and butanedial.

[0023] Optionally, the concentration of the phenolic compound in the mixture is 2-50 g / L.

[0024] Optionally, the concentration of the phenolic compound in the mixture is selected from any value or a range between any two values of 2 g / L, 5 g / L, 10 g / L, 20 g / L, 30 g / L, 40 g / L, 50 g / L.

[0025] Optionally, the molar ratio of the phenolic compound to the aldehyde compound in the mixture is 0.15-2:1.

[0026] Optionally, the molar ratio of the phenolic compound to the aldehyde compound in the mixture is selected from any value or a range between any two values of 0.15:1, 0.25:1, 0.5:1, 1:1, 1.5:1, 2:1.

[0027] Optionally, the catalyst is selected from at least one of ammonia water, ammonium persulfate, sodium hydroxide, potassium hydroxide.

[0028] Optionally, the concentration of the catalyst in the mixture is 0.1-10 μL / mL.

[0029] Optionally, the concentration of the catalyst in the mixture is selected from any value or a range between any two values of 0.1 μL / mL, 0.5 μL / mL, 1 μL / mL, 2 μL / mL, 3 μL / mL, 4 μL / mL, 5 μL / mL, 6 μL / mL, 7 μL / mL, 8 μL / mL, 9 μL / mL, 10 μL / mL.

[0030] Optionally, the solvent is selected from at least one of methanol, ethanol, water, tetrahydrofuran.

[0031] Optionally, the conditions of the reaction I include: being carried out under the action of rotation providing shear force, the reaction temperature is 0-100 °C, the reaction time is 1-60 min, and the rotation speed is 0-800 rpm.

[0032] Optionally, in the conditions of the reaction I, the reaction temperature is selected from any value or a range between any two values of 0 °C, 10 °C, 20 °C, 30 °C, 40 °C, 50 °C, 60 °C, 70 °C, 80 °C, 90 °C, 100 °C.

[0033] Optionally, in the conditions of the reaction I, the reaction time is selected from any value or a range between any two values of 1 min, 2 min, 5 min, 10 min, 20 min, 30 min, 40 min, 50 min, 60 min.

[0034] Optionally, in the reaction I, the rotation speed is selected from any value or a range between any two values of 0 rpm, 100 rpm, 200 rpm, 300 rpm, 400 rpm, 500 rpm, 600 rpm, 700 rpm, 800 rpm.

[0035] Optionally, the reaction II is carried out under rotation to provide shear force, the reaction temperature is 0-100 °C, the reaction time is 0.5-96 h, and the rotation speed is 0-800 rpm.

[0036] Optionally, in the reaction II, the reaction temperature is selected from any value or a range between any two values of 0 °C, 10 °C, 20 °C, 30 °C, 40 °C, 50 °C, 60 °C, 70 °C, 80 °C, 90 °C, 100 °C.

[0037] Optionally, in the reaction II, the reaction time is selected from any value or a range between any two values of 0.5 h, 2 h, 4 h, 6 h, 8 h, 10 h, 12 h, 24 h, 36 h, 48 h, 60 h, 72 h, 84 h, 96 h.

[0038] Optionally, in the reaction II, the rotation speed is selected from any value or a range between any two values of 0 rpm, 100 rpm, 200 rpm, 300 rpm, 400 rpm, 500 rpm, 600 rpm, 700 rpm, 800 rpm.

[0039] According to another aspect of the present application, a carbon material is also provided, which is obtained by calcining the asymmetric structure polymer or the asymmetric structure polymer obtained according to any of the above preparation methods.

[0040] Optionally, the carbon material is a snowman-shaped particle.

[0041] The snowman-shaped particle comprises a hollow carbon ball having a porous cavity and a carbon protrusion grown on the surface of the hollow carbon ball.

[0042] Optionally, the particle size of the carbon material is 100-800 nm.

[0043] Optionally, the pore size of the carbon material is 0.1-20 nm.

[0044] Optionally, the specific surface area of the carbon material is 10-1000 m 2 / g.

[0045] Optionally, the conditions of the calcination include: being carried out under an inactive atmosphere, the temperature of the calcination is 300-900 °C, and the time of the calcination is 1-8 h.

[0046] Optionally, in the conditions of the calcination, the inactive atmosphere is selected from at least one of nitrogen, argon, and helium.

[0047] Optionally, in the conditions of the calcination, the temperature of the calcination is selected from any one of 300 °C, 400 °C, 500 °C, 600 °C, 700 °C, 800 °C, 900 °C or a range value between any two of them.

[0048] Optionally, in the conditions of the calcination, the time of the calcination is selected from any one of 1 h, 2 h, 3 h, 4 h, 5 h, 6 h, 7 h, 8 h or a range value between any two of them.

[0049] Optionally, the calcination is carried out at a temperature increasing rate of 1-10 °C / min to the required temperature of the calcination, and then the temperature is kept constant.

[0050] The beneficial effects of the present application include:

[0051] 1. The asymmetric structure polymer provided by the present application is a phenolic resin material, and both the asymmetric structure polymer and the carbon material obtained by calcining the asymmetric structure polymer have asymmetric snowman-like structures.

[0052] 2. The preparation method of the asymmetric structure polymer provided by the present application is simple in technology and does not require large equipment. The asymmetric structure polymer microspheres are synthesized by one-pot method through adding a mixed solution of etching agent and surfactant. The micro-nano structure of the prepared asymmetric structure polymer is regular in morphology and uniform in size. Different morphologies of the polymer can be obtained by adjusting the amount of the surfactant. BRIEF DESCRIPTION OF DRAWINGS

[0053] Figure 1 SEM and TEM images of the phenolic resin prepared under the conditions of Example 1 of the present application after etching with the addition of surfactant.

[0054] Figure 2 Infrared spectrum of the phenolic resin prepared under the conditions of Example 1 of the present application.

[0055] Figure 3 Thermogravimetric curve of the phenolic resin prepared under the conditions of Example 1 of the present application.

[0056] Figure 4 SEM and TEM images of the phenolic resin prepared in Comparative Example 1 of the present application without etching with the addition of surfactant.

[0057] Figure 5SEM and TEM images of the phenolic resin prepared under the conditions of Example 3 of the present application.

[0058] Figure 6 TEM images of the asymmetrically structured carbon microspheres prepared under the conditions of Example 6 of the present application, wherein a, b images are TEM images of the asymmetrically structured carbon microspheres obtained after carbonization of Example 1 and Comparative Example 1. DETAILED DESCRIPTION

[0059] The present application will be described in detail below with reference to Examples, but the present application is not limited to these Examples.

[0060] Unless otherwise specified, the raw materials in the Examples of the present application are purchased through commercial channels.

[0061] Unless otherwise specified, the test methods are all conventional methods, and the instrument settings are all recommended settings of the manufacturers.

[0062] Scanning electron microscope analysis (SEM) is performed using a Japanese Hitachi S-4800 instrument; transmission electron microscope analysis (TEM) is performed using a Japanese Hitachi Hitachi 7800; infrared spectrum analysis is performed using a Nexus-6700 Fourier transform infrared spectrometer; and thermal gravimetric analysis is performed using a German Netzsch STA449 FJupiter.

[0063] Example 1

[0064] 0.2 g of 3-aminophenol is dissolved in 30 mL of water, and after ultrasonic dissolution for 5 min, 0.2 mL of formaldehyde and 0.2 mL of ammonia water are added, and the mixture is stirred at 30 °C for 30 min. A mixed solution of 40 mL of ethanol and 0.2 g of fluorocarbon surfactant (FC4) is added to the above system, and the mixture is stirred for 120 min. The precipitate is collected by centrifugation, washed with water three times, and dried in a vacuum freeze dryer for 12 h to obtain asymmetrically structured polymer microspheres, i.e., asymmetrically micro-nano structured phenolic resin.

[0065] Figure 1 The a, b images are scanning electron microscope and transmission electron microscope images of the asymmetrically micro-nano structured phenolic resin prepared under the conditions of Example 1 of the present application. As can be seen from the images, the phenolic resin has an asymmetric structure, consisting of a hollow spherical shape with a larger diameter and a solid spherical shape with a smaller diameter. The particle size is about 362 nm, the shell thickness is about 100 nm, and the surface of the phenolic resin is smooth.

[0066] Figure 2 is an infrared spectrum image of the asymmetrically micro-nano structured phenolic resin prepared under the conditions of Example 1. The absorption band at 3362 cm -1 belongs to O-H stretching vibration, the absorption band at 1624 cm -1the absorption peak at 1588 cm -1 the band observed at 1588 cm -1 belongs to (Ar)C-H stretching vibration.

[0067] Figure 3 The thermogravimetric curve of the asymmetric micro-nano structured phenolic resin prepared under the conditions of Example 1 is shown in FIG. 4. It can be seen that the phenolic resin can be converted into carbon material under an inert atmosphere, and the carbon residue rate is 38.3%.

[0068] Comparative Example 1

[0069] Dissolve 0.2 g of 3-aminophenol in 30 mL of water, and after dissolving under ultrasonic for 5 min, add 0.2 mL of formaldehyde and 0.2 mL of ammonia water. Stir at 30°C for 30 min, add 40 mL of ethanol and 0.1 g of fluorocarbon surfactant (FC4) to the above system, stir for 120 min, centrifugal collect the precipitate, wash with water for three times, and dry in a vacuum freeze dryer for 12 h to obtain the polymer microspheres.

[0070] Figure 4 The scanning electron microscope image and the transmission electron microscope image of the polymer microspheres prepared under the conditions of Comparative Example 1 are shown in FIG. 3. It can be seen from the figure that the nano material has regular morphology, uniform size, and the spherical particle size is 473 nm, which is a spherical multi-level hollow structure rather than an asymmetric structure.

[0071] Example 2

[0072] Dissolve 0.2 g of 3-aminophenol in 30 mL of water, and after dissolving under ultrasonic for 5 min, add 0.2 mL of formaldehyde and 0.2 mL of ammonia water. Stir at 30°C for 30 min, add 40 mL of ethanol and 0.1 g of fluorocarbon surfactant (FC4) to the above system, stir for 120 min, centrifugal collect the precipitate, wash with water for three times, and dry in a vacuum freeze dryer for 12 h to obtain the polymer microspheres.

[0073] Example 3

[0074] Dissolve 0.2 g of 3-aminophenol in 30 mL of water, and after dissolving under ultrasonic for 5 min, add 0.2 mL of formaldehyde and 0.2 mL of ammonia water. Stir at 30°C for 30 min, add 40 mL of ethanol and 0.1 g of fluorocarbon surfactant (FC4) to the above system, stir for 120 min, centrifugal collect the precipitate, wash with water for three times, and dry in a vacuum freeze dryer for 12 h to obtain the polymer microspheres.

[0075] Figure 5 a and Figure 5b is a scanning electron microscope image and a transmission electron microscope image of the asymmetric structure polymer microspheres prepared under the conditions of Example 3, and it can be seen from the images that the nano-material has a regular morphology, and the solid part of the asymmetric structure is larger than that of Example 1, and the particle size is 410 nm.

[0076] Example 4

[0077] 0.2 g of 3-aminophenol was dissolved in 30 mL of water, and after ultrasonic dissolution for 5 min, 0.2 mL of formaldehyde and 0.2 mL of ammonia water were added, and stirred at 30 °C for 30 min. A mixed solution of 40 mL of ethanol and 1.0 g of fluorocarbon surfactant (FC4) was added to the above system, and stirred for 120 min. The precipitate was collected by centrifugation, washed with water three times, and dried in a vacuum freeze dryer for 12 h to obtain asymmetric structure polymer microspheres.

[0078] Example 5

[0079] 0.2 g of 3-aminophenol was dissolved in 30 mL of water, and after ultrasonic dissolution for 5 min, 0.2 mL of formaldehyde and 0.2 mL of ammonia water were added, and stirred at 30 °C for 30 min. A mixed solution of 40 mL of ethanol and 2.0 g of fluorocarbon surfactant (FC4) was added to the above system, and stirred for 120 min. The precipitate was collected by centrifugation, washed with water three times, and dried in a vacuum freeze dryer for 12 h to obtain asymmetric structure polymer microspheres.

[0080] Example 6

[0081] The micro-nano structured phenolic resin prepared under the conditions of Comparative Example 1 and Example 1 was carbonized at 800 °C under a nitrogen atmosphere at a temperature increase rate of 3 °C / min for 2 h, and finally naturally cooled to room temperature to obtain the carbon material.

[0082] Figure 6 a and b are transmission electron microscope images of the carbon material after carbonization of Comparative Example 1 and Example 1 prepared under the conditions of Example 6, and it can be seen from the images that the morphology does not change before and after carbonization.

[0083] The above is only a few embodiments of the present application, and does not limit the present application in any form. Although the present application discloses the above preferred embodiments, it is not intended to limit the present application. Any skilled person in the art can make some changes or modifications to the above disclosed technical content without departing from the scope of the technical solution of the present application, and such changes or modifications are equivalent to equivalent embodiments, and are within the scope of the technical solution.

Claims

1. An asymmetrically structured polymer, characterized by, The asymmetric structure polymer is a snowman-shaped particle; The snowman-shaped particle comprises a hollow phenolic resin sphere with a porous cavity and a solid phenolic resin protrusion grown on the surface of the hollow phenolic resin sphere; the longitudinal length of the asymmetric structure polymer is 320-420 nm; The transverse length of the asymmetric structure polymer is 320-420 nm.

2. The method for preparing the asymmetric polymer according to claim 1, characterized in that, The method comprises the following steps: S1, a mixture containing a phenolic compound, an aldehyde compound, a catalyst, and solvent water is subjected to reaction I under the action of rotation to provide shear force, to obtain a system containing polymer I; S2, a mixed solution containing a surfactant and an etchant is added to the system containing polymer I, and reaction II is carried out under the action of rotation to provide shear force, to obtain the asymmetric structure polymer; the concentration of the surfactant in the mixed solution is in the range of 5-20 g / L, and the volume ratio of the etchant to solvent water is in the range of 1:1 to 4:1; The surfactant is fluorocarbon surfactant FC4; The etchant is ethanol.

3. The preparation method according to claim 2, characterized in that, The phenolic compound is at least one selected from 2-aminophenol, 3-aminophenol, 4-aminophenol, 3-aminothiophenol, 4-amino-3-fluorothiophenol, resorcinol, hydroquinone, and pyrogallol; The aldehyde compound is at least one selected from formaldehyde, glyoxal, and butanedial.

4. The preparation method according to claim 2, characterized in that, The catalyst is at least one selected from ammonia, ammonium persulfate, sodium hydroxide, and potassium hydroxide.

5. The preparation method according to claim 2, characterized in that, The conditions of the reaction I include: the reaction temperature is 0-100 °C, the reaction time is 1-60 min, and the rotation speed is 0-800 rpm.

6. The preparation method according to claim 2, characterized in that, The conditions of the reaction II include: the reaction temperature is 0-100 °C, the reaction time is 0.5-96 h, and the rotation speed is 0-800 rpm.

7. A carbon material, characterized by, The carbon material is obtained by heating the asymmetric structure polymer of claim 1 to the required temperature at a heating rate of 1-10 °C / min, and then keeping the temperature; The carbon material is a snowman-shaped particle; The snowman-shaped particle comprises a hollow carbon sphere with a porous cavity and a carbon protrusion grown on the surface of the hollow carbon sphere.

8. The carbon material according to claim 7, characterized by The specific surface area of the carbon material is 10-1000 m 2 / g; The pore size of the carbon material is 0.1-20 nm.

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