Polymer with asymmetric structure, carbon microsphere and preparation method thereof

Abstract

The invention discloses an asymmetric structure polymer, a carbon microsphere and a preparation method thereof, and belongs to the technical field of nano materials. The polymer with the asymmetric structure is snowman-shaped particles; the snowman-shaped particles comprise hollow phenolic resin spheres with porous cavities and phenolic resin bulges grown on the surfaces of the hollow phenolic resin spheres. According to the preparation method of the polymer with the asymmetric structure, the technology is simple, large equipment is not needed, the polymer microspheres with the asymmetric structure are synthesized by adding the mixed solution of the etching agent and the surfactant through a one-pot method, and the prepared polymer with the asymmetric structure is regular in micro-nano structure morphology and uniform in size. Polymers with different morphologies can be obtained by adjusting the use amount of the surfactant.

Description

Technical Field

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

[0002] On the basis of inheriting the advantages of traditional symmetric structure nanomaterials, asymmetric structure nanomaterials have attracted great interest from researchers due to their unique asymmetric structure and surface anisotropy. Each part of the asymmetric structure nanoparticles can be selectively modified and play an independent role, achieving coordinated functions without mutual interference. Therefore, they have broad application prospects in many fields such as catalysis, energy conversion and storage, materials science and biomedical engineering.

[0003] Currently, the main methods for synthesizing asymmetric polymer microspheres are interface assembly strategy, soft / hard template method and selective etching strategy. However, the above methods have complex processes, and the synthesized materials have uneven morphology and size. Therefore, synthesizing uniform and controllable asymmetric nanoparticles by a simple synthesis method has always been a research hotspot and difficulty. Summary of the Invention

[0004] To solve the foregoing technical problems, the present application provides a technical solution for constructing an asymmetric structure polymer. An asymmetric structure is obtained by adding a surfactant to an etchant, which solves the limitations such as uneven particle size and difficult-to-control asymmetry degree in the prior art. At the same time, this method is a one-pot synthesis with simple operation method and high yield.

[0005] The present application adopts the following technical solutions: According to the first aspect of the present application, an asymmetric structure polymer is provided, and the asymmetric structure polymer is a snowman-shaped particle; The snowman-shaped particle includes a hollow phenolic resin sphere having a porous cavity and phenolic resin protrusions growing on the surface of the hollow phenolic resin sphere.

[0006] Optionally, the longitudinal length of the asymmetric structure polymer is 320 - 620 nm.

[0007] Optionally, the longitudinal length of the phenolic resin material is selected from any value of 320 nm, 420 nm, 520 nm, 620 nm or the range value between any two values.

[0008] Optionally, the transverse length of the asymmetric structure polymer is 320 - 720 nm.

[0009] Optionally, the transverse length of the phenolic resin material is selected from any value of 320 nm, 420 nm, 520 nm, 620 nm, 720 nm or the range value between any two values.

[0010] According to another aspect of the present application, a method for preparing the above-mentioned asymmetric structure polymer is provided, including the following steps: S1. React a mixture of a phenolic compound, an aldehyde compound, a catalyst, and a solvent in Reaction I to obtain a system containing Polymer I; S2. Add a mixed solution containing a surfactant and an etchant to the system containing Polymer I, and carry out Reaction II to obtain the asymmetric structure polymer.

[0011] Optionally, the surfactant is selected from at least one of fluorocarbon surfactants, sodium dodecyl sulfate, sodium dodecylbenzenesulfonate, sodium laurate, cetyltrimethylammonium bromide, sodium oleate, Pluronic F127, P123, P108, F68, and didodecyldimethylammonium bromide.

[0012] Optionally, the concentration of the surfactant in the mixed solution is 0.1 - 30 g / L.

[0013] Optionally, the concentration of the surfactant in the mixed solution is selected from any value 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, 30 g / L or a range value between any two values.

[0014] Optionally, the etchant is selected from at least one of methanol, ethanol, acetone, N,N-dimethylformamide, tetrahydrofuran, dichloroethane, ethylene oxide, and dimethyl sulfoxide.

[0015] Optionally, the volume ratio of the etchant to the solvent is 0.3 - 6:1.

[0016] Optionally, the volume ratio of the etchant to the solvent is selected from any value of 0.3:1, 0.5:1, 0.75:1, 1:1, 2:1, 3:1, 4:1, 5:1, 6:1 or a range value between any two values.

[0017] Optionally, the phenolic compound is selected from at least one of 2-aminophenol, 3-aminophenol, 4-aminophenol, 3-aminobenzenethiol, 4-amino-3-fluorobenzenethiol, resorcinol, hydroquinone, and phloroglucinol.

[0018] Optionally, the aldehyde compound is selected from at least one of formaldehyde, glyoxal, and succinaldehyde.

[0019] Optionally, the concentration of the phenolic compound in the mixture is 2 - 50 g / L.

[0020] Optionally, the concentration of the phenolic compound in the mixture is selected from any value among 2 g / L, 5 g / L, 10 g / L, 20 g / L, 30 g / L, 40 g / L, 50 g / L or a range value between any two values.

[0021] Optionally, the molar ratio of the phenolic compound to the aldehyde compound in the mixture is 0.15 - 2:1.

[0022] Optionally, the molar ratio of the phenolic compound to the aldehyde compound in the mixture is selected from any value among 0.15:1, 0.25:1, 0.5:1, 1:1, 1.5:1, 2:1 or a range value between any two values.

[0023] Optionally, the catalyst is selected from at least one of ammonia water, ammonium persulfate, sodium hydroxide, and potassium hydroxide.

[0024] Optionally, the concentration of the catalyst in the mixture is 0.1 - 10 μL / mL.

[0025] Optionally, the concentration of the catalyst in the mixture is selected from any value among 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 or a range value between any two values.

[0026] Optionally, the solvent is selected from at least one of methanol, ethanol, water, and tetrahydrofuran. Optionally, the conditions for Reaction I include: being carried out under the action of rotation to provide shear force, with a reaction temperature of 0 - 100 °C, a reaction time of 1 - 60 min, and a rotation speed of 0 - 800 rpm.

[0027] Optionally, in the conditions for Reaction I, the reaction temperature is selected from any value among 0 °C, 10 °C, 20 °C, 30 °C, 40 °C, 50 °C, 60 °C, 70 °C, 80 °C, 90 °C, 100 °C or a range value between any two values.

[0028] Optionally, in the conditions for Reaction I, the reaction time is selected from any value among 1 min, 2 min, 5 min, 10 min, 20 min, 30 min, 40 min, 50 min, 60 min or a range value between any two values.

[0029] Optionally, in the conditions of Reaction I, the rotation speed is selected from any value of 0 rpm, 100 rpm, 200 rpm, 300 rpm, 400 rpm, 500 rpm, 600 rpm, 700 rpm, 800 rpm or a range value between any two values.

[0030] Optionally, the conditions of Reaction II include: being carried out under the action of 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.

[0031] Optionally, in the conditions of Reaction II, the reaction temperature is selected from any value of 0 °C, 10 °C, 20 °C, 30 °C, 40 °C, 50 °C, 60 °C, 70 °C, 80 °C, 90 °C, 100 °C or a range value between any two values.

[0032] Optionally, in the conditions of Reaction II, the reaction time is selected from any value 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 or a range value between any two values.

[0033] Optionally, in the conditions of Reaction II, the rotation speed is selected from any value of 0 rpm, 100 rpm, 200 rpm, 300 rpm, 400 rpm, 500 rpm, 600 rpm, 700 rpm, 800 rpm or a range value between any two values.

[0034] According to another aspect of the present application, a carbon material is further provided, and the carbon material is obtained by calcining the above asymmetric structure polymer or the asymmetric structure polymer obtained by the preparation method according to any one of the above.

[0035] Optionally, the carbon material is snowman-shaped particles; The snowman-shaped particles include a hollow carbon sphere having a porous cavity and carbon protrusions growing on the surface of the hollow carbon sphere.

[0036] Optionally, the particle size of the carbon material is 100~800 nm.

[0037] Optionally, the pore size of the carbon material is 0.1~20 nm.

[0038] Optionally, the specific surface area of the carbon material is 10~1000 m 2 / g.

[0039] Optionally, the conditions for the roasting include: being carried out in an inert atmosphere, with the roasting temperature being 300 - 900 °C and the roasting time being 1 - 8 h.

[0040] Optionally, among the conditions for the roasting, the inert atmosphere is selected from at least one of nitrogen, argon, and helium.

[0041] Optionally, among the conditions for the roasting, the roasting temperature is selected from any value or the range value between any two values among 300 °C, 400 °C, 500 °C, 600 °C, 700 °C, 800 °C, and 900 °C.

[0042] Optionally, among the conditions for the roasting, the roasting time is selected from any value or the range value between any two values among 1 h, 2 h, 3 h, 4 h, 5 h, 6 h, 7 h, and 8 h.

[0043] Optionally, the roasting is carried out by raising the temperature to the required roasting temperature at a heating rate of 1 - 10 °C / min, and then holding the temperature.

[0044] The beneficial effects of this application include: 1. The asymmetric - structure polymer provided by this application is a phenolic - resin material, and both the asymmetric - structure polymer and the carbon material obtained by roasting it have an asymmetric snowman - like structure.

[0045] 2. The preparation method of the asymmetric - structure polymer provided by this application is simple in technology and does not require large - scale equipment. By adding a mixed solution of an etching agent and a surfactant, the asymmetric - structure polymer microspheres are synthesized by a one - pot method. The micro - nano structure morphology of the prepared asymmetric - structure polymer is regular and the size is uniform. Different morphologies of the polymer can be obtained by adjusting the dosage of the surfactant. Description of the Drawings

[0046] Figure 1 SEM and TEM images of the phenolic resin after being etched with a surfactant prepared under the conditions of Example 1 of this application.

[0047] Figure 2 Infrared spectrum diagram of the phenolic resin prepared under the conditions of Example 1 of this application.

[0048] Figure 3 Thermogravimetric curve of the phenolic resin prepared under the conditions of Example 1 of this application.

[0049] Figure 4 SEM and TEM images of the phenolic resin without being etched with a surfactant prepared in Comparative Example 1 of this application.

[0050] Figure 5 SEM and TEM images of the phenolic resin prepared under the conditions of Example 3 of this application.

[0051] Figure 6 This is the TEM image of the asymmetric-structured carbon microspheres prepared under the conditions of Example 6 of this application. Among them, Figures a and b are the TEM images of the asymmetric-structured carbon microspheres obtained after carbonization in Example 1 and Comparative Example 1. Detailed implementation manners

[0052] The present application will be described in detail below with reference to the embodiments, but the present application is not limited to these embodiments.

[0053] Unless otherwise specified, the raw materials in the embodiments of the present application are all purchased through commercial channels.

[0054] Unless otherwise specified, the test methods are all conventional methods, and the instrument settings are all the settings recommended by the manufacturers.

[0055] Scanning electron microscope analysis (SEM) was carried out using a Hitachi S-4800 instrument from Japan; transmission electron microscope analysis (TEM) was carried out using a Hitachi 7800 from Japan; infrared spectrum analysis was carried out using a Nexus-6700 Fourier transform infrared spectrometer; thermogravimetric analysis was carried out using a Netzsch STA449 F Jupiter from Germany.

[0056] Example 1 Dissolve 0.2 g of 3-aminophenol in 30 mL of water. After ultrasonic dissolution for 5 min, add 0.2 mL of formaldehyde and 0.2 mL of ammonia water. Stir at 30 °C for 30 min. Add a mixed solution of 40 mL of ethanol and 0.2 g of fluorocarbon surfactant (FC4) to the above system, stir for 120 min, centrifuge to collect the precipitate, wash it three times with water, and dry it in a vacuum freeze dryer for 12 h to obtain asymmetric-structured polymer microspheres, that is, asymmetric micro-nano structured phenolic resin.

[0057] Figure 1 Figures a and b in it are the scanning electron microscope and transmission electron microscope images of the asymmetric micro-nano structured phenolic resin prepared under the conditions of Example 1 of this application. It can be seen from the figure that the phenolic resin has an asymmetric structure and is composed of a hollow sphere with a larger diameter and a solid sphere 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.

[0058] Figure 2 This is the infrared spectrum image of the asymmetric micro-nano structured phenolic resin prepared under the conditions of Example 1. The absorption band at 3362 cm -1 is attributed to the O-H stretching vibration, and the absorption peak at 1624 cm -1 is attributed to the stretching of C=C in the aromatic ring. At 1588 cm -1The bands observed at [1394 cm] can be attributed to the stretching vibration of Ar-NH2. -1 It is attributed to the stretching vibration of (Ar)C-H.

[0059] Figure 3 The thermogravimetric curve of the asymmetric micro-nano structured phenolic resin prepared under the conditions of Example 1 is shown. It can be seen that in an inert atmosphere, the phenolic resin can be converted into a carbon material, and the residual carbon rate is 38.3%.

[0060] Comparative Example 1 Dissolve 0.2 g of 3-aminophenol in 30 mL of water. After ultrasonic dissolution for 5 min, add 0.2 mL of formaldehyde and 0.2 mL of ammonia water. Stir at 30 °C for 30 min. Then add 40 mL of ethanol to the above system, stir for 120 min, centrifuge to collect the precipitate, wash it three times with water, and dry it in a vacuum freeze dryer for 12 h to obtain polymer microspheres.

[0061] Figure 4 These are the scanning electron microscope image and transmission electron microscope image of the polymer microspheres prepared under the conditions of Comparative Example 1 of this application. It can be seen from the figure that the morphology of this nanomaterial is regular, the size is uniform, the size of the spherical particles is 473 nm, and it is a spherical multi-level hollow structure rather than an asymmetric structure.

[0062] Example 2 Dissolve 0.2 g of 3-aminophenol in 30 mL of water. After ultrasonic dissolution for 5 min, add 0.2 mL of formaldehyde and 0.2 mL of ammonia water. Stir at 30 °C for 30 min. Then add a mixed solution of 40 mL of ethanol and 0.1 g of fluorocarbon surfactant (FC4) to the above system, stir for 120 min, centrifuge to collect the precipitate, wash it three times with water, and dry it in a vacuum freeze dryer for 12 h to obtain polymer microspheres.

[0063] Example 3 Dissolve 0.2 g of 3-aminophenol in 30 mL of water. After ultrasonic dissolution for 5 min, add 0.2 mL of formaldehyde and 0.2 mL of ammonia water. Stir at 30 °C for 30 min. Then add a mixed solution of 40 mL of ethanol and 0.5 g of fluorocarbon surfactant (FC4) to the above system, stir for 120 min, centrifuge to collect the precipitate, wash it three times with water, and dry it in a vacuum freeze dryer for 12 h to obtain asymmetric structured polymer microspheres.

[0064] Figure 5 a and Figure 5Figure b shows the SEM and TEM images of the asymmetric-structured polymer microspheres prepared under the conditions of Example 3 of this application. It can be seen from the figure that the morphology of this nanomaterial is regular. Compared with Example 1, the solid part of the asymmetric structure becomes larger, and the particle size is 410 nm.

[0065] Example 4 Dissolve 0.2 g of 3-aminophenol in 30 mL of water. After ultrasonic dissolution for 5 min, add 0.2 mL of formaldehyde and 0.2 mL of ammonia water. Stir at 30 °C for 30 min. Then add a mixed solution of 40 mL of ethanol and 1.0 g of fluorocarbon surfactant (FC4) to the above system. Stir for 120 min, centrifuge to collect the precipitate, wash it three times with water, and dry it in a vacuum freeze dryer for 12 h to obtain asymmetric-structured polymer microspheres.

[0066] Example 5 Dissolve 0.2 g of 3-aminophenol in 30 mL of water. After ultrasonic dissolution for 5 min, add 0.2 mL of formaldehyde and 0.2 mL of ammonia water. Stir at 30 °C for 30 min. Then add a mixed solution of 40 mL of ethanol and 2.0 g of fluorocarbon surfactant (FC4) to the above system. Stir for 120 min, centrifuge to collect the precipitate, wash it three times with water, and dry it in a vacuum freeze dryer for 12 h to obtain asymmetric-structured polymer microspheres.

[0067] Example 6 Heat the micro-nano structured phenolic resin prepared under the conditions of Comparative Example 1 and Example 1 to 800 °C at a rate of 3 °C / min and carbonize it for 2 h in a nitrogen atmosphere, and finally cool it to room temperature naturally to obtain the carbon material.

[0068] Figure 6 Figures a and b show the TEM images of the carbon materials obtained by carbonizing Comparative Example 1 and Example 1 under the conditions of Example 6 of this application. It can be seen from the figure that the morphology has not changed before and after carbonization.

[0069] The above are only several embodiments of this application and do not impose any form of limitation on this application. Although this application is disclosed with preferred embodiments as above, it is not intended to limit this application. Any person skilled in the art, without departing from the scope of the technical solution of this application, makes some changes or modifications using the technical content disclosed above, which are all equivalent to equivalent implementation cases and fall within the scope of the technical solution.

Claims

1. An asymmetric structure polymer, characterized in that, The asymmetric structure polymer is a snowman-shaped particle; The snowman-shaped particle includes a hollow phenolic resin sphere having a porous cavity and a phenolic resin protrusion growing on the surface of the hollow phenolic resin sphere.

2. The asymmetric structure polymer according to claim 1, characterized in that, The longitudinal length of the asymmetric structure polymer is 320-620 nm; The transverse length of the asymmetric structure polymer is 320-720 nm.

3. The preparation method of the asymmetric structure polymer according to claim 1 or 2, characterized in that, It includes the following steps: S1. React a mixture of a phenolic compound, an aldehyde compound, a catalyst, and a solvent in Reaction I to obtain a system containing Polymer I; S2. Add a mixed solution containing a surfactant and an etchant to the system containing Polymer I and react in Reaction II to obtain the asymmetric structure polymer.

4. The preparation method according to claim 3, characterized in that, The surfactant is selected from at least one of fluorocarbon surfactants, sodium dodecyl sulfate, sodium dodecylbenzenesulfonate, sodium laurate, cetyltrimethylammonium bromide, sodium oleate, Pluronic F127, P123, P108, F68, and didodecyldimethylammonium bromide; The concentration of the surfactant in the mixed solution is 0.1-30 g / L; The etchant is selected from at least one of methanol, ethanol, acetone, N,N-dimethylformamide, tetrahydrofuran, dichloroethane, ethylene oxide, and dimethyl sulfoxide; The volume ratio of the etchant to the solvent is 0.3-6:

1.

5. The preparation method according to claim 3, characterized in that, The phenolic compound is selected from at least one of 2-aminophenol, 3-aminophenol, 4-aminophenol, 3-aminobenzenethiol, 4-amino-3-fluorobenzenethiol, resorcinol, hydroquinone, and phloroglucinol; The aldehyde compound is selected from at least one of formaldehyde, glyoxal, and succinaldehyde.

6. The preparation method according to claim 3, characterized in that, The catalyst is selected from at least one of ammonia water, ammonium persulfate, sodium hydroxide, and potassium hydroxide.

7. The preparation method according to claim 3, characterized in that, The conditions of Reaction I include: being carried out under the action of shear force provided by rotation, with a reaction temperature of 0-100 °C, a reaction time of 1-60 min, and a rotation speed of 0-800 rpm.

8. The preparation method according to claim 3, characterized in that, The conditions of Reaction II include: being carried out under the action of shear force provided by rotation, with a reaction temperature of 0-100 °C, a reaction time of 0.5-96 h, and a rotation speed of 0-800 rpm.

9. A carbon material, characterized in that, The carbon material is obtained by calcining the asymmetric structure polymer described in Claim 1 or 2.

10. The carbon material according to claim 9, wherein The carbon material is a snowman-shaped particle; The snowman-shaped particle includes a hollow carbon sphere having a porous cavity and a carbon protrusion growing on the surface of the hollow carbon sphere.

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