CN105273188B - It is copolymerized the self-catalysis preparation method of benzoxazine colophony high score bulbec and the self-catalysis preparation method of resin based carbon balls - Google Patents

It is copolymerized the self-catalysis preparation method of benzoxazine colophony high score bulbec and the self-catalysis preparation method of resin based carbon balls Download PDF

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CN105273188B
CN105273188B CN201510821748.2A CN201510821748A CN105273188B CN 105273188 B CN105273188 B CN 105273188B CN 201510821748 A CN201510821748 A CN 201510821748A CN 105273188 B CN105273188 B CN 105273188B
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benzoxazine
present
resin
copolymerization
high score
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CN105273188A (en
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徐国宝
赵建明
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Changzhou Institute of Energy Storage Materials & Devices
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Changchun Institute of Applied Chemistry of CAS
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Abstract

The present invention provides a kind of self-catalysis preparation method for being copolymerized benzoxazine colophony high score bulbec, belongs to technical field of polymer.This method dissolves m-aminophenol and formaldehyde under conditions of extra catalyst is not utilized in a solvent, obtains being copolymerized benzoxazine colophony high score bulbec after polymerisation；The solvent is the mixed solution of water and alcohol compound.The present invention also provides a kind of self-catalysis preparation method for being copolymerized benzoxazine colophony based carbon balls, and this method obtains corresponding charcoal ball after obtained copolymerization benzoxazine colophony high score bulbec is calcined.The copolymerization benzoxazine colophony high score bulbec and charcoal ball that the present invention obtains have very high monodispersity, and the size of resin balls can be adjusted on a large scale, be advantageous to its application.And method preparation copolymerization benzoxazine colophony high score bulbec provided by the invention has high concentration in unit reaction system.

Description

It is copolymerized the self-catalysis preparation method and resin base charcoal of benzoxazine-resin high score bulbec The self-catalysis preparation method of ball
Technical field
The invention belongs to technical field of polymer, and in particular to a kind of to be copolymerized urging certainly for benzoxazine-resin high score bulbec Change preparation method and the self-catalysis preparation method of resin based carbon balls.
Background technology
In the last few years, molecular level design turned into study hotspot, including silica with controllable preparation monodisperse colloid ball Ball, high score bulbec, charcoal ball and their composite balls etc., are primarily due to them and have a wide range of applications, such as：Colloidal catalytic, Photonic crystal, drug delivery, bio-sensing, energy storage and template etc..The application of these colloidal spheres and their size, knot Structure and composition are closely related.Charcoal ball is different from most of high score bulbecs and silica spheres, and they have big specific surface area, height Thermodynamic stability (in inert environments) and strong anti acid alkali performance, we can use charcoal ball in severe reaction environment. However, controlledly synthesis high quality monodisperse colloid charcoal ball is designed on molecular level still has challenge very much.
Scientist has found, based on hydrolytic-polymeric reaction mechanism, the building-up process of resorcinol-formaldehyde organosol gels with Inorganic oxide, particularly silica, collosol and gel it is much like.Due to the resorcinol being synthesized by this method Carboxaldehyde radicals organic aerogel and xerogel have excellent thermodynamic stability, and we can lead to as charcoal material precursor Cross carbonization process and change into corresponding charcoal aerosol and xerogel.In addition, we, which can adjust reaction condition and obtain, has species Abundant nanostructured and high polymer material and its corresponding Carbon Materials of composition.Therefore, we can be as needed, from molecule Controllable design synthesizes these materials in level.Recently, it is similar to silane to associate the structure of resorcinol formaldehyde presoma, and The collosol and gel building-up process of resorcinol formaldehyde resin is again close with silica spheres, and people are successfully utilized with preparing dioxy The similar approach of SiClx ball method prepare monodispersed resorcinol formaldehyde resin high score bulbec (Angew.Chem., Int.Ed.2011,50,5947-5951.).However, in the course of the polymerization process, ammoniacal liquor may obtain not only as catalyst The surface of resorcinol-formaldehyde resin ball and corresponding charcoal ball is rougher, and monodispersity is relatively low, is unfavorable for resin balls and charcoal ball Using.Based on benzoxazine chemistry, there is document report to be condensed system by the Mannich of resorcinol, formaldehyde and 1,6- hexamethylene diamine A kind of standby new highly homogeneous Polybenzoxazine base resin high molecular nanometer sphere (J.Am.Chem.Soc.2011,133, 15304-15307.), they adjust the pattern of ball with block copolymer F127 in preparation process, are obtained by adjusting synthesis temperature Resin balls and corresponding charcoal ball, but this method obtains resin balls and the particle size section of charcoal ball is smaller, particle diameter can Modulability is smaller, and the production concentration of gained unit volume is smaller, also, surfactant has been used during preparation, makes Obtain synthesis step and post-process cumbersome.
The content of the invention
It is an object of the invention to provide a kind of self-catalysis preparation method for being copolymerized benzoxazine-resin high score bulbec and altogether The self-catalysis preparation method of Polybenzoxazine-resin based carbon balls, this method prepare copolymerization benzoxazine-resin high score bulbec and Charcoal ball has the monodispersity of height, and preparation process does not have to catalyst, surfactant, template and functional additive.
The present invention provides a kind of self-catalysis preparation method for being copolymerized benzoxazine-resin high score bulbec, comprises the following steps：
M-aminophenol and formaldehyde are dissolved in a solvent, obtain being copolymerized benzoxazine-resin macromolecule after polymerisation Ball；
The solvent is the mixed solution of water and alcohol compound.
Preferably, the alcohol compound is the one or more in methanol, ethanol, isopropanol and ethylene glycol.
Preferably, described alcohol compound is ethanol.
Preferably, described solution temperature is 3 DEG C~70 DEG C.
Preferably, the mol ratio of described m-aminophenol and formaldehyde is 1：(1.5~5).
Preferably, the concentration of described m-aminophenol is 5mmol/L~320mmol/L.
Preferably, the concentration of described formaldehyde is 7.5mmol/L~1600mmol/L.
Preferably, the temperature of described polymerisation is 50 DEG C~200 DEG C, time of polymerisation for 0.1 hour~ 50 hours.
The present invention provides a kind of self-catalysis preparation method for being copolymerized benzoxazine-resin based carbon balls, comprises the following steps：
The copolymerization benzoxazine that preparation method described in above-mentioned technical proposal is obtained-resin high score bulbec is calcined, Obtain being copolymerized benzoxazine-resin based carbon balls.
Preferably, the temperature of described calcining is 500 DEG C~1300 DEG C, and the time of calcining is 2 hours~12 hours.
Beneficial effects of the present invention
The present invention provides a kind of self-catalysis preparation method for being copolymerized benzoxazine-resin high score bulbec, and this method is not having Under conditions of extra catalyst, m-aminophenol and formaldehyde are dissolved in a solvent, obtain being copolymerized benzo after polymerisation Oxazine-resin high score bulbec；The solvent is the mixed solution of water and alcohol compound.The present invention is by formaldehyde and m-aminophenol Micella is formed in a solvent, and in micella, the amino of m-aminophenol is not only reacted by Mannich participates in polymerization, urges simultaneously Change m-aminophenol and polymerisation occurs for formaldehyde, so as to obtain being copolymerized benzoxazine-resin high score bulbec；In course of reaction In, the amino of m-aminophenol can be distributed in the surface of micella, form positive charge, and electrostatic repulsion makes the surface band of micella There is identical electric charge, so that mutually exclusive between micella, it is suppressed that the bonding between micella, obtained copolymerization Ben Bing Evil Piperazine-resin macromolecule ball has very high monodispersity, and the size of resin balls can be adjusted on a large scale, be advantageous to its application. And method provided by the invention prepare copolymerization benzoxazine-resin high score bulbec have in unit reaction system it is high dense Degree.
The present invention also provides a kind of self-catalysis preparation method for being copolymerized benzoxazine-resin based carbon balls, and this method will obtain Copolymerization benzoxazine-resin high score bulbec obtain corresponding charcoal ball after being calcined, charcoal ball provided by the invention also has very High monodispersity, three-dimensional periodic arrangement is kept, its size can be adjusted on a large scale, be advantageous to its application.
Brief description of the drawings
Fig. 1 is the scanning electron microscope (SEM) photograph of copolymerization benzoxazine-resin high score bulbec prepared by the embodiment of the present invention 1；
Fig. 2 is the particle diameter statistical chart for copolymerization benzoxazine-resin high score bulbec that the embodiment of the present invention 1 obtains；
Fig. 3 is the scanning electron microscope (SEM) photograph for copolymerization benzoxazine-resin based carbon balls that the embodiment of the present invention 21 obtains；
Fig. 4 is the cyclic voltammetry curve for the charcoal ball electrode that the embodiment of the present invention 21 obtains；
Fig. 5 is the charging and discharging curve for the charcoal ball electrode that the embodiment of the present invention 21 obtains；
Fig. 6 is the Ragone curves for the charcoal ball electrode that the embodiment of the present invention 21 obtains；
Fig. 7 is the stable circulation linearity curve for the charcoal ball electrode that the embodiment of the present invention 21 obtains；
Fig. 8 is the scanning electron microscope (SEM) photograph for copolymerization benzoxazine-resin high score bulbec that the embodiment of the present invention 2 obtains；
Fig. 9 is the scanning electron microscope (SEM) photograph for copolymerization benzoxazine-resin high score bulbec that the embodiment of the present invention 3 obtains；
Figure 10 is the scanning electron microscope (SEM) photograph for copolymerization benzoxazine-resin high score bulbec that the embodiment of the present invention 4 obtains；
Figure 11 is the scanning electron microscope (SEM) photograph for copolymerization benzoxazine-resin high score bulbec that the embodiment of the present invention 5 obtains；
Figure 12 is the scanning electron microscope (SEM) photograph for copolymerization benzoxazine-resin high score bulbec that the embodiment of the present invention 6 obtains；
Figure 13 is the scanning electron microscope (SEM) photograph for copolymerization benzoxazine-resin high score bulbec that the embodiment of the present invention 7 obtains；
Figure 14 is the scanning electron microscope (SEM) photograph for copolymerization benzoxazine-resin high score bulbec that the embodiment of the present invention 8 obtains；
Figure 15 is the scanning electron microscope (SEM) photograph for copolymerization benzoxazine-resin high score bulbec that the embodiment of the present invention 9 obtains；
Figure 16 is the scanning electron microscope (SEM) photograph for copolymerization benzoxazine-resin high score bulbec that the embodiment of the present invention 10 obtains；
Figure 17 is the scanning electron microscope (SEM) photograph for copolymerization benzoxazine-resin high score bulbec that the embodiment of the present invention 11 obtains；
Figure 18 is the scanning electron microscope (SEM) photograph for copolymerization benzoxazine-resin high score bulbec that the embodiment of the present invention 12 obtains.
Embodiment
The present invention provides a kind of self-catalysis preparation method for being copolymerized benzoxazine-resin high score bulbec, comprises the following steps：
M-aminophenol and formaldehyde are dissolved in a solvent, obtain being copolymerized benzoxazine-resin macromolecule after polymerisation Ball；
The solvent is the mixed solution of water and alcohol compound.
The present invention first dissolves m-aminophenol and formaldehyde in a solvent, obtains mixed solution, the process is without outer Add catalyst.The order that the present invention dissolves in a solvent to m-aminophenol and formaldehyde does not have special limitation, using this area The technical scheme of phenolic resin is prepared known to technical staff.M-aminophenol is preferably first added to solvent by the present invention In, formaldehyde is then added thereto, obtains mixed solution.After the formaldehyde adds, m-aminophenol and formaldehyde shape in a solvent Into micella, in the micella, the amino catalysis formaldehyde and m-aminophenol of the m-aminophenol carry out polymerisation, and Amino in m-aminophenol also assists in polymerisation by Mannich reactions, obtains being copolymerized benzoxazine-resin macromolecule Ball.In order that raw material fully dissolves and mixed, the present invention is preferably carried out the after m-aminophenol is added in solvent One stirring and dissolving；After adding formaldehyde thereto, mixed solution is obtained, the mixed solution that preferred pair of the present invention obtains carries out second and stirred Mix.
In the present invention, the solvent is the mixed solution of water and alcohol compound, preferably water and alcohol compound Mixed solution, the alcohol compound are preferably the one or more in methanol, ethanol, isopropanol and ethylene glycol, more preferably Ethanol, the present invention do not have special limit to the ratio of the mixed solution reclaimed water and alcohol compound of the water and alcohol compound System, can make m-aminophenol and formaldehyde dissolve and produce micella；The present invention is to the m-aminophenol and the ratio of formaldehyde Example is without special limitation, using phenolic compound in phenolic aldehyde polymerization process well known to those skilled in the art and formaldehyde Ratio；In the present invention, the mol ratio of described m-aminophenol and formaldehyde is preferably 1：(1.5~5), the formaldehyde The mass ratio of volume and the m-aminophenol is preferably (15~968) μ L:(9.17~586.64) mg, more preferably (60~ 242)μL:(36.67~180) mg.The concentration of described m-aminophenol is preferably 5mmol/L~320mmol/L, described first The concentration of aldehyde is preferably 7.5mmol/L~1600mmol/L.
The temperature of first stirring is preferably 3 DEG C~70 DEG C, more preferably 10 DEG C~70 DEG C, most preferably 20 DEG C~70 ℃；The present invention does not have special limitation to the time of the first stirring, and the m-aminophenol is dissolved, in the present invention, The time of first stirring is preferably 5 minutes~15 minutes；The time of second stirring is preferably 0.1 hour~24 small When, more preferably 1 hour~15 hours, most preferably 2 hours~5 hours；Second stirring is with the described first stirring in phase Carried out at same temperature.
After obtaining the mixed solution of m-aminophenol and formaldehyde, in the mixed solution, in the amino of m-aminophenol Under autocatalysis, with the formaldehyde polymerisation occurs for the m-aminophenol, obtains being copolymerized benzoxazine-resin macromolecule Ball.The present invention does not have special limitation to the condition of the m-aminophenol and formaldehyde reaction, ripe using those skilled in the art The technical scheme of the preparation for the phenolic resin known.In the present invention, the temperature of the polymerisation is preferably 50 DEG C~200 DEG C, more preferably 80 DEG C~150 DEG C, when reaction temperature is higher than 110 DEG C, the present invention is preferably by the mixed solution in hydro-thermal bar Hydro-thermal reaction is carried out under part, obtains being copolymerized benzoxazine-resin high score bulbec.The present invention can also be directly to the mixed solution Carry out the 3rd stirring, you can obtain being copolymerized benzoxazine-resin high score bulbec, without carrying out water-heat process.The present invention is to described The method of stirring does not have special limitation, using the technical scheme of stirring well known to those skilled in the art.In the present invention In, the time of the polymerisation is preferably 0.1 hour~50 hours, and more preferably 1 hour~40 hours, more preferably 2 is small When~30 hours.
During the polymerisation, the formaldehyde and m-aminophenol form micella in a solvent, in the glue Shu Zhong, the amino in m-aminophenol react as catalyst autocatalytic polymerization, so as to obtain being copolymerized benzoxazine-resin high score Bulbec；During the course of the reaction, the amino as the m-aminophenol for playing catalytic action can also be distributed in the surface of micella so that Micellar surface carries same electric charge, so that repulsive interaction between micella be present, it is suppressed that the bonding between micella, obtain Copolymerization benzoxazine-resin macromolecule ball has very high monodispersity, and its size has good controllability, is advantageous to it Using.
After the completion of the polymerisation, the present invention is preferably post-processed obtained reaction solution, obtains being copolymerized Ben Bing Evil Piperazine-resin high score bulbec, detailed process are as follows：
Obtained reaction solution is carried out separation of solid and liquid by the present invention, is then cleaned obtained solid, clear by what is obtained Solid after washing is dried, and obtains being copolymerized benzoxazine-resin high score bulbec.The present invention does not have to the method for the separation of solid and liquid There is special limitation, it is in the present invention, described solid using the technical scheme of separation of solid and liquid well known to those skilled in the art Liquid separation is preferably to centrifuge, and the present invention does not have special limitation to the parameter setting of the centrifugation, using those skilled in the art The technical scheme of well known centrifugation.In the present invention, the speed of the centrifugation is 5000rpm~12000rpm, more preferably For 7000rpm~9000rpm, the time of the centrifugation is preferably 1 minute~20 minutes, more preferably 3 minutes~10 minutes.This Invention does not have special limitation to the method for the cleaning, and the technical scheme using cleaning well known to those skilled in the art is Can.In the present invention, the cleaning is preferably to be cleaned with water, and the number of the cleaning is preferably 2 times~5 times.The present invention is to institute Stating dry method does not have special limitation, using the technical scheme of drying well known to those skilled in the art.In this hair In bright, the temperature of the drying is preferably 60 DEG C~120 DEG C, and more preferably 70 DEG C~90 DEG C, the time of the drying is preferably 4 Hour~24 hours, more preferably 6 hours~15 hours.
Obtain after being copolymerized benzoxazine-resin high score bulbec, the present invention is to the copolymerization benzoxazine-resin high score bulbec It is scanned electron-microscope scanning analysis, the results showed that, copolymerization benzoxazine-resin macromolecule ball provided by the invention has very high Monodispersity, and the size of resin balls can be in a wide range of interior regulation.
The present invention provides a kind of method that self-catalysis prepares copolymerization benzoxazine-resin high score bulbec, in m-aminophenol Amino self-catalysis m-aminophenol and formaldehyde polymerisation in, formaldehyde and m-aminophenol form micella in a solvent, In micella, polymerisation occurs for the amino of m-aminophenol catalysis m-aminophenol and formaldehyde, so as to obtain being copolymerized benzoxazine- Resin high score bulbec；During the course of the reaction, the amino of part m-aminophenol can also be distributed in the surface of micella, make micella table Face carries identical electric charge, and electrostatic repulsion inhibits the bonding between micella, so as to get copolymerization benzoxazine-resin it is high Molecular ball has very high monodispersity, and the size of resin balls can be adjusted on a large scale, be advantageous to its application.
The present invention provides a kind of self-catalysis preparation method for being copolymerized benzoxazine-resin based carbon balls, comprises the following steps：
The copolymerization benzoxazine that preparation method described in above-mentioned technical proposal is obtained-resin high score bulbec is calcined, and is obtained To copolymerization benzoxazine-resin based carbon balls.
Obtain after being copolymerized benzoxazine-resin high score bulbec, the present invention is copolymerized benzoxazine-resin high score bulbec by described Calcined, the copolymerization benzoxazine-resin high score bulbec is carbonized, so as to obtain charcoal ball.The present invention is to the calcining Method there is no special limitation, using the technical scheme of calcining well known to those skilled in the art.The present invention preferably will Obtained copolymerization benzoxazine-resin high score bulbec is placed in tube furnace, is calcined, obtains charcoal ball, in the present invention, The temperature of the calcining is preferably 500 DEG C~1300 DEG C, more preferably 550 DEG C~1100 DEG C, most preferably 700 DEG C~1000 ℃；The time of the calcining is preferably 2 hours~12 hours, more preferably 4 hours~8 hours.
Obtain after being copolymerized benzoxazine-resin based carbon balls, the present invention enters obtained copolymerization benzoxazine-resin based carbon balls Row ESEM scanning analysis, the results showed that, copolymerization benzoxazine-resin based carbon balls provided by the invention have very high single point Property is dissipated, keeps the arrangement architecture of three-dimensional periodic, the size of obtained copolymerization benzoxazine-resin based carbon balls can be a wide range of interior Regulation.
The copolymerization benzoxazine that the present invention obtains preparation method described in above-mentioned technical proposal-resin high score bulbec carries out charcoal Charcoal ball is obtained after change, therefore copolymerization benzoxazine-resin based carbon balls prepared by the present invention also have very high monodispersity, ball The adjustable section of particle diameter is big, is advantageous to its application.
Copolymerization benzoxazine-resin based carbon balls that the present invention obtains can use the electrode material of double layer capacitor, specifically Process is as follows：
The present invention is prepared into the electrode of double layer capacitor by benzoxazine-resin based carbon balls are copolymerized.The present invention is to described The preparation method of charcoal ball electrode does not have special limitation, using the electricity well known to those skilled in the art for preparing double layer capacitor The technical scheme of pole.
The capacitive property of charcoal ball electrode of the present invention to obtaining is tested, and detailed process is as follows：
The present invention carries out capacitive property test experiments, obtains cyclic voltammetric song using the charcoal ball electrode as working electrode Line, constant current charge-discharge curve, charge and discharge cycles curve and electrochemical impedance spectroscopy, and filled according to the constant current under different densities Discharge curve, the curve of energy density and saturation effect is calculated, the results showed that.As a result show, the present invention will obtain The electrode of double layer capacitor that is prepared into of copolymerization benzoxazine-resin based carbon balls, there is excellent capacitive property.
It is high to copolymerization benzoxazine-resin provided by the invention with reference to embodiments in order to further illustrate the present invention Molecular ball, corresponding charcoal ball and preparation method thereof are described in detail, but can not be interpreted as them to protect model to the present invention The restriction enclosed.
Embodiment 1
73.33mg m-aminophenols are added in the mixed solution of 8.4mL water and 8.4mL methanol, stirred at 30 DEG C After dissolving 10 minutes, 121 μ L formaldehyde are added thereto, after stirring 1 hour, the temperature of water-bath are increased to 75 DEG C, continues stirring 4 Hour.Obtained reaction product is centrifuged 5 minutes under 8000rpm rotating speeds, by the solid washing after obtained centrifugation twice, Dried 12 hours at 80 DEG C, obtain being copolymerized benzoxazine-resin high score bulbec.
The present invention is scanned electron-microscope scanning analysis to obtained copolymerization benzoxazine-resin high score bulbec, as a result such as Fig. 1 Shown, Fig. 1 is the scanning electron microscope (SEM) photograph of copolymerization benzoxazine-resin high score bulbec prepared by the embodiment of the present invention 1, can be with by Fig. 1 Find out, phenolic resin ball prepared by the present invention has very high monodispersity.Obtained scanning electron microscope (SEM) photograph is carried out grain by the present invention Footpath counts, as a result as shown in Fig. 2 the particle diameter for copolymerization benzoxazine-resin high score bulbec that Fig. 2, which is the embodiment of the present invention 1, to be obtained Statistical chart, as seen from Figure 2, the particle diameter distribution of copolymerization benzoxazine-resin high score bulbec prepared by the present invention are very narrow, single point It is fine to dissipate property.The particle diameter of copolymerization benzoxazine-resin high score bulbec manufactured in the present embodiment is 617nm.
Embodiment 2
73.33mg m-aminophenols are added in the mixed solution of 8.4mL water and 8.4mL methanol, stirred at 20 DEG C After dissolving 10 minutes, 121 μ L formaldehyde are added thereto, after stirring 1 hour, the temperature of water-bath are increased to 75 DEG C, continues stirring 4 Hour.Obtained reaction product is centrifuged 5 minutes under 8000rpm rotating speeds, after the centrifugation washing twice of obtained product, 80 Dried 12 hours at DEG C, obtain being copolymerized benzoxazine-resin high score bulbec.
The present invention is scanned electron-microscope scanning analysis to obtained copolymerization benzoxazine-resin high score bulbec, as a result such as Fig. 8 Shown, Fig. 8 is the scanning electron microscope (SEM) photograph of copolymerization benzoxazine-resin high score bulbec prepared by the embodiment of the present invention 2, can be with by Fig. 8 Find out, phenolic resin ball prepared by the present invention has very high monodispersity.Copolymerization benzoxazine-resin manufactured in the present embodiment The particle diameter of high score bulbec is 613nm.
Embodiment 3
73.33mg m-aminophenols are added in the mixed solution of 8.4mL water and 8.4mL methanol, stirred at 10 DEG C After dissolving 10 minutes, 121 μ L formaldehyde are added thereto, after stirring 1 hour, the temperature of water-bath are increased to 75 DEG C, continues stirring 4 Hour.Obtained reaction product is centrifuged 5 minutes under 8000rpm rotating speeds, after the centrifugation washing twice of obtained product, 80 Dried 12 hours at DEG C, obtain being copolymerized benzoxazine-resin high score bulbec.
The present invention is scanned electron-microscope scanning analysis to obtained copolymerization benzoxazine-resin high score bulbec, as a result such as Fig. 9 Shown, Fig. 9 is the scanning electron microscope (SEM) photograph of copolymerization benzoxazine-resin high score bulbec prepared by the embodiment of the present invention 3, can be with by Fig. 9 Find out, phenolic resin ball prepared by the present invention has very high monodispersity.Copolymerization benzoxazine-tree prepared by the present embodiment 3 The particle diameter of fat high score bulbec is 605nm.
Embodiment 4
73.33mg m-aminophenols are added in the mixed solution of 8.4mL water and 8.4mL methanol, stirred at 40 DEG C After dissolving 10 minutes, 121 μ L formaldehyde are added thereto, after stirring 1 hour, the temperature of water-bath are increased to 75 DEG C, continues stirring 4 Hour.Obtained reaction product is centrifuged 5 minutes under 8000rpm rotating speeds, after the centrifugation washing twice of obtained product, 80 Dried 12 hours at DEG C, obtain being copolymerized benzoxazine-resin high score bulbec.
The present invention is scanned electron-microscope scanning analysis to obtained copolymerization benzoxazine-resin high score bulbec, as a result as schemed Shown in 10, Figure 10 is the scanning electron microscope (SEM) photograph of copolymerization benzoxazine-resin high score bulbec prepared by the embodiment of the present invention 4, by Figure 10 As can be seen that phenolic resin ball prepared by the present invention has very high monodispersity.Copolymerization Ben Bing Evil prepared by the present embodiment 4 The particle diameter of piperazine-resin high score bulbec is 627nm.
Embodiment 5
73.33mg m-aminophenols are added in the mixed solution of 8.4mL water and 8.4mL methanol, stirred at 50 DEG C After dissolving 10 minutes, 121 μ L formaldehyde are added thereto, after stirring 1 hour, the temperature of water-bath are increased to 75 DEG C, continues stirring 4 Hour.Obtained reaction product is centrifuged 5 minutes under 8000rpm rotating speeds, after the centrifugation washing twice of obtained product, 80 Dried 12 hours at DEG C, obtain being copolymerized benzoxazine-resin high score bulbec.
The present invention is scanned electron-microscope scanning analysis to obtained copolymerization benzoxazine-resin high score bulbec, as a result as schemed Shown in 11, Figure 11 is the scanning electron microscope (SEM) photograph of copolymerization benzoxazine-resin high score bulbec prepared by the embodiment of the present invention 5, by Figure 11 As can be seen that phenolic resin ball prepared by the present invention has very high monodispersity.Copolymerization Ben Bing Evil prepared by the present embodiment 5 The particle diameter of piperazine-resin high score bulbec is 599nm.
Embodiment 6
73.33mg m-aminophenols are added in the mixed solution of 8.4mL water and 8.4mL methanol, stirred at 60 DEG C After dissolving 10 minutes, 121 μ L formaldehyde are added thereto, after stirring 1 hour, the temperature of water-bath are increased to 75 DEG C, continues stirring 4 Hour.Obtained reaction product is centrifuged 5 minutes under 8000rpm rotating speeds, after the centrifugation washing twice of obtained product, 80 Dried 12 hours at DEG C, obtain being copolymerized benzoxazine-resin high score bulbec.
The present invention is scanned electron-microscope scanning analysis to obtained copolymerization benzoxazine-resin high score bulbec, as a result as schemed Shown in 12, Fig. 6 is the scanning electron microscope (SEM) photograph of copolymerization benzoxazine-resin high score bulbec prepared by the embodiment of the present invention 12, by Figure 12 As can be seen that phenolic resin ball prepared by the present invention has very high monodispersity.Copolymerization Ben Bing Evil prepared by the present embodiment 6 The particle diameter of piperazine-resin high score bulbec is 577nm.
Embodiment 7
36.67mg m-aminophenols are added in the mixed solution of 8.4mL water and 8.4mL methanol, stirred at 30 DEG C After dissolving 10 minutes, 60 μ L formaldehyde are added thereto, after stirring 1 hour, the temperature of water-bath are increased to 75 DEG C, continues stirring 4 Hour.Obtained reaction product is centrifuged 5 minutes under 8000rpm rotating speeds, after the centrifugation washing twice of obtained product, 80 Dried 12 hours at DEG C, obtain being copolymerized benzoxazine-resin high score bulbec.
The present invention is scanned electron-microscope scanning analysis to obtained copolymerization benzoxazine-resin high score bulbec, as a result as schemed Shown in 13, Figure 13 is the scanning electron microscope (SEM) photograph of copolymerization benzoxazine-resin high score bulbec prepared by the embodiment of the present invention 7, by Figure 13 As can be seen that phenolic resin ball prepared by the present invention has very high monodispersity.Copolymerization Ben Bing Evil prepared by the present embodiment 7 The particle diameter of piperazine-resin high score bulbec is 507nm.
Embodiment 8
45.83mg m-aminophenols are added in the mixed solution of 8.4mL water and 8.4mL methanol, stirred at 30 DEG C After dissolving 10 minutes, 76 μ L formaldehyde are added thereto, after stirring 1 hour, the temperature of water-bath are increased to 75 DEG C, continues stirring 4 Hour.Obtained reaction product is centrifuged 5 minutes under 8000rpm rotating speeds, after the centrifugation washing twice of obtained product, 80 Dried 12 hours at DEG C, obtain being copolymerized benzoxazine-resin high score bulbec.
The present invention is scanned electron-microscope scanning analysis to obtained copolymerization benzoxazine-resin high score bulbec, as a result as schemed Shown in 14, Figure 14 is the scanning electron microscope (SEM) photograph of copolymerization benzoxazine-resin high score bulbec prepared by the embodiment of the present invention 8, by Figure 14 As can be seen that phenolic resin ball prepared by the present invention has very high monodispersity.Copolymerization Ben Bing Evil prepared by the present embodiment 8 The particle diameter of piperazine-resin high score bulbec is 570nm.
Embodiment 9
55.00mg m-aminophenols are added in the mixed solution of 8.4mL water and 8.4mL methanol, stirred at 30 DEG C After dissolving 10 minutes, 91 μ L formaldehyde are added thereto, after stirring 1 hour, the temperature of water-bath are increased to 75 DEG C, continues stirring 4 Hour.Obtained reaction product is centrifuged 5 minutes under 8000rpm rotating speeds, after the centrifugation washing twice of obtained product, 80 Dried 12 hours at DEG C, obtain being copolymerized benzoxazine-resin high score bulbec.
The present invention is scanned electron-microscope scanning analysis to obtained copolymerization benzoxazine-resin high score bulbec, as a result as schemed Shown in 15, Figure 15 is the scanning electron microscope (SEM) photograph of copolymerization benzoxazine-resin high score bulbec prepared by the embodiment of the present invention 9, by Figure 15 As can be seen that phenolic resin ball prepared by the present invention has very high monodispersity.Copolymerization Ben Bing Evil prepared by the present embodiment 9 The particle diameter of piperazine-resin high score bulbec is 604nm.
Embodiment 10
91.66mg m-aminophenols are added in the mixed solution of 8.4mL water and 8.4mL methanol, stirred at 30 DEG C After dissolving 10 minutes, 151 μ L formaldehyde are added thereto, after stirring 1 hour, the temperature of water-bath are increased to 75 DEG C, continues stirring 4 Hour.Obtained reaction product is centrifuged 5 minutes under 8000rpm rotating speeds, after the centrifugation washing twice of obtained product, 80 Dried 12 hours at DEG C, obtain being copolymerized benzoxazine-resin high score bulbec.
The present invention is scanned electron-microscope scanning analysis to obtained copolymerization benzoxazine-resin high score bulbec, as a result as schemed Shown in 16, Figure 16 is the scanning electron microscope (SEM) photograph of copolymerization benzoxazine-resin high score bulbec prepared by the embodiment of the present invention 10, by Figure 16 As can be seen that phenolic resin ball prepared by the present invention has very high monodispersity.Copolymerization Ben Bing Evil prepared by the present embodiment 10 The particle diameter of piperazine-resin high score bulbec is 640nm.
Embodiment 11
110mg m-aminophenols are added in the mixed solution of 8.4mL water and 8.4mL methanol, stirred at 30 DEG C molten Solution adds 182 μ L formaldehyde thereto after 10 minutes, and after stirring 1 hour, the temperature of water-bath is increased into 75 DEG C, and it is small to continue stirring 4 When.Obtained reaction product is centrifuged 5 minutes under 8000rpm rotating speeds, after the centrifugation washing twice of obtained product, at 80 DEG C Lower drying 12 hours, obtain being copolymerized benzoxazine-resin high score bulbec.
The present invention is scanned electron-microscope scanning analysis to obtained copolymerization benzoxazine-resin high score bulbec, as a result as schemed Shown in 17, Figure 17 is the scanning electron microscope (SEM) photograph of copolymerization benzoxazine-resin high score bulbec prepared by the embodiment of the present invention 11, by Figure 17 As can be seen that phenolic resin ball prepared by the present invention has very high monodispersity.Copolymerization Ben Bing Evil prepared by the present embodiment 11 The particle diameter of piperazine-resin high score bulbec is 651nm.
Embodiment 12
146.67mg m-aminophenols are added in the mixed solution of 8.4mL water and 8.4mL methanol, stirred at 30 DEG C After dissolving 10 minutes, 242 μ L formaldehyde are added thereto, after stirring 1 hour, the temperature of water-bath are increased to 75 DEG C, continues stirring 4 Hour.Obtained reaction product is centrifuged 5 minutes under 8000rpm rotating speeds, after the centrifugation washing twice of obtained product, 80 Dried 12 hours at DEG C, obtain being copolymerized benzoxazine-resin high score bulbec.
The present invention is scanned electron-microscope scanning analysis to obtained copolymerization benzoxazine-resin high score bulbec, as a result as schemed Shown in 18, Figure 18 is the scanning electron microscope (SEM) photograph of copolymerization benzoxazine-resin high score bulbec prepared by the embodiment of the present invention 12, by Figure 18 As can be seen that phenolic resin ball prepared by the present invention has very high monodispersity.Copolymerization Ben Bing Evil prepared by the present embodiment 12 The particle diameter of piperazine-resin high score bulbec is 703nm.
Embodiment 13
293.32mg m-aminophenols are added in the mixed solution of 8.4mL water and 8.4mL methanol, stirred at 30 DEG C After dissolving 10 minutes, 484 μ L formaldehyde are added thereto, after stirring 1 hour, the temperature of water-bath are increased to 75 DEG C, continues to stir 0.1 hour.Obtained reaction product is centrifuged 3 minutes under 5000rpm rotating speeds, after the centrifugation washing twice of obtained product, Dried 4 hours at 120 DEG C, obtain being copolymerized benzoxazine-resin high score bulbec.
Copolymerization benzoxazine-resin high score bulbec that the present invention obtains to embodiment 13 is scanned electron-microscope scanning analysis, As a result show, phenolic resin ball prepared by the present invention has higher monodispersity.Copolymerization Ben Bing Evil prepared by the present embodiment 13 The particle diameter of piperazine-resin high score bulbec is 914nm.
Embodiment 14
586.64mg m-aminophenols are added in the mixed solution of 8.4mL water and 8.4mL methanol, stirred at 30 DEG C After dissolving 10 minutes, 968 μ L formaldehyde are added thereto, after stirring 1 hour, the temperature of water-bath are increased to 75 DEG C, continues to stir 0.1 hour.Obtained reaction product is centrifuged 1 minute under 5000rpm rotating speeds, after the centrifugation washing twice of obtained product, Dried 4 hours at 120 DEG C, obtain being copolymerized benzoxazine-resin high score bulbec.
Copolymerization benzoxazine-resin high score bulbec that the present invention obtains to embodiment 14 is scanned electron-microscope scanning analysis, As a result show, phenolic resin ball prepared by the present invention has higher monodispersity.Copolymerization Ben Bing Evil prepared by the present embodiment 14 The particle diameter of piperazine-resin high score bulbec is 1030nm.
Embodiment 15
9.17mg m-aminophenols are added in the mixed solution of 8.4mL water and 8.4mL methanol, stirred at 30 DEG C molten Solution adds 15 μ L formaldehyde thereto after 5 minutes, and after stirring 24 hours, the temperature of water-bath is increased into 90 DEG C, and it is small to continue stirring 50 When.Obtained reaction product is centrifuged 20 minutes under 12000rpm rotating speeds, after the centrifugation washing twice of obtained product, 50 Dried 12 hours at DEG C, obtain being copolymerized benzoxazine-resin high score bulbec.
Copolymerization benzoxazine-resin high score bulbec that the present invention obtains to embodiment 15 is scanned electron-microscope scanning analysis, As a result show, phenolic resin ball prepared by the present invention has higher monodispersity.Copolymerization Ben Bing Evil prepared by the present embodiment 15 The particle diameter of piperazine-resin high score bulbec is 375nm.
Embodiment 16
13.75mg m-aminophenols are added in the mixed solution of 8.4mL water and 8.4mL methanol, stirred at 30 DEG C After dissolving 10 minutes, 23 μ L formaldehyde are added thereto, after stirring 1 hour, the temperature of water-bath are increased to 75 DEG C, continues stirring 4 Hour.Obtained reaction product is centrifuged 5 minutes under 10000rpm rotating speeds, after the centrifugation washing twice of obtained product, Dried 4 hours at 100 DEG C, obtain being copolymerized benzoxazine-resin high score bulbec.
Copolymerization benzoxazine-resin high score bulbec that the present invention obtains to embodiment 16 is scanned electron-microscope scanning analysis, As a result show, phenolic resin ball prepared by the present invention has higher monodispersity.Copolymerization Ben Bing Evil prepared by the present embodiment 16 The particle diameter of piperazine-resin high score bulbec is 416nm.
Embodiment 17
18.33mg m-aminophenols are added in the mixed solution of 8.4mL water and 8.4mL methanol, stirred at 30 DEG C After dissolving 10 minutes, 30 μ L formaldehyde are added thereto, after stirring 1 hour, the temperature of water-bath are increased to 75 DEG C, continues stirring 4 Hour.Obtained reaction product is centrifuged 5 minutes under 10000rpm rotating speeds, after the centrifugation washing twice of obtained product, Dried 12 hours at 80 DEG C, obtain being copolymerized benzoxazine-resin high score bulbec.
Copolymerization benzoxazine-resin high score bulbec that the present invention obtains to embodiment 17 is scanned electron-microscope scanning analysis, As a result show, phenolic resin ball prepared by the present invention has higher monodispersity.Copolymerization Ben Bing Evil prepared by the present embodiment 17 The particle diameter of piperazine-resin high score bulbec is 436nm.
Embodiment 18
27.50mg m-aminophenols are added in the mixed solution of 8.4mL water and 8.4mL methanol, stirred at 30 DEG C After dissolving 10 minutes, 45 μ L formaldehyde are added thereto, after stirring 1 hour, the temperature of water-bath are increased to 75 DEG C, continues stirring 4 Hour.Obtained reaction product is centrifuged 5 minutes under 8000rpm rotating speeds, after the centrifugation washing twice of obtained product, 80 Dried 12 hours at DEG C, obtain being copolymerized benzoxazine-resin high score bulbec.
Copolymerization benzoxazine-resin high score bulbec that the present invention obtains to embodiment 18 is scanned electron-microscope scanning analysis, As a result show, phenolic resin ball prepared by the present invention has higher monodispersity.Copolymerization Ben Bing Evil prepared by the present embodiment 18 The particle diameter of piperazine-resin high score bulbec is 473nm.
Embodiment 19
73.33mg m-aminophenols are added in the mixed solution of 8.4mL water and 8.4mL methanol, stirred at 30 DEG C After dissolving 10 minutes, 91 μ L formaldehyde are added thereto, after stirring 1 hour, the temperature of water-bath are increased to 75 DEG C, continues stirring 4 Hour.Obtained reaction product is centrifuged 10 minutes under 5000rpm rotating speeds, after the centrifugation washing twice of obtained product, Dried 24 hours at 60 DEG C, obtain being copolymerized benzoxazine-resin high score bulbec.
Copolymerization benzoxazine-resin high score bulbec that the present invention obtains to embodiment 19 is scanned electron-microscope scanning analysis, As a result show, phenolic resin ball prepared by the present invention has higher monodispersity.Copolymerization Ben Bing Evil prepared by the present embodiment 17 The particle diameter of piperazine-resin high score bulbec is 606nm.
Embodiment 20
73.33mg m-aminophenols are added in the mixed solution of 8.4mL water and 8.4mL methanol, stirred at 30 DEG C After dissolving 10 minutes, 242 μ L formaldehyde are added thereto, after stirring 1 hour, the temperature of water-bath are increased to 75 DEG C, continues stirring 4 Hour.Obtained reaction product is centrifuged 5 minutes under 8000rpm rotating speeds, after the centrifugation washing twice of obtained product, Dried 4 hours at 120 DEG C, obtain being copolymerized benzoxazine-resin high score bulbec.
Copolymerization benzoxazine-resin high score bulbec that the present invention obtains to embodiment 20 is scanned electron-microscope scanning analysis, As a result show, phenolic resin ball prepared by the present invention has higher monodispersity.Copolymerization Ben Bing Evil prepared by the present embodiment 18 The particle diameter of piperazine-resin high score bulbec is 643nm.
Comparative example 1
73.33mg m-aminophenols are added in the mixed solution of 8.4mL water and 8.4mL methanol, at 0 DEG C, (temperature is not Stirring and dissolving adds 121 μ L formaldehyde thereto after 10 minutes under together), and after stirring 1 hour, the temperature of water-bath is increased into 75 DEG C, Continue stirring 4 hours.Obtained reaction product is centrifuged 5 minutes under 12000rpm rotating speeds, obtained product is centrifuged and washed After twice, dried 12 hours at 80 DEG C, obtain being copolymerized benzoxazine-resin high score bulbec.
Obtained copolymerization benzoxazine-resin high score bulbec is scanned electron-microscope scanning analysis by the present invention, the results showed that, The Size Distribution for copolymerization benzoxazine-resin high score bulbec that this comparative example obtains is wider, and monodispersity is poor.
Embodiment 21
Embodiment 1 is obtained being copolymerized benzoxazine-resin high score bulbec and calcined 4 hours in tube furnace at 900 DEG C, is obtained To copolymerization benzoxazine-resin based carbon balls.
Obtained copolymerization benzoxazine-resin based carbon balls are scanned electron-microscope scanning analysis by the present invention, as a result such as Fig. 3 institutes Show, Fig. 3 is the scanning electron microscope (SEM) photograph of copolymerization benzoxazine-resin based carbon balls prepared by the embodiment of the present invention 21, can be seen by Fig. 3 Go out, charcoal ball uniform particle sizes prepared by the present invention, there is very high monodispersity.
Obtain after being copolymerized benzoxazine-resin based carbon balls, the electrode of double layer capacitor is prepared into it, it follows that Copolymerization benzoxazine-resin based carbon balls provided by the invention may be used as the electrode material of double layer capacitor.The present invention is to obtaining The charcoal ball electrode arrived carries out cyclic voltammetric sign, as a result as shown in figure 4, Fig. 4 is the copolymerization benzo that the embodiment of the present invention 21 obtains The cyclic voltammetry curve of electrode prepared by oxazine-resin based carbon balls, as seen from Figure 4, charcoal ball electrode tool prepared by the present invention There is high rate capability；The present invention carries out constant current charge-discharge sign to obtained charcoal ball electrode, as a result such as Fig. 5, as a result shows Electrode has high capacitor performance and good rate response, the energy density that is calculated by constant current charge-discharge data and Power density curve, as a result as Fig. 6, display charcoal ball electrode have higher energy density and power density；The present invention is to obtaining Charcoal ball electrode carry out cycle performance sign, as a result such as Fig. 7, illustrate that charcoal ball electrode has performance stably.
Embodiment 22
Embodiment 2 is obtained being copolymerized benzoxazine-resin high score bulbec and calcined 4 hours in tube furnace at 900 DEG C, is obtained To copolymerization benzoxazine-resin based carbon balls.
Copolymerization benzoxazine-resin based carbon balls that the present invention obtains embodiment 22 are scanned electron-microscope scanning analysis, knot Fruit shows charcoal ball uniform particle sizes prepared by the present invention, there is very high monodispersity.
Obtain after being copolymerized benzoxazine-resin based carbon balls, the electrode of double layer capacitor is prepared into it, it follows that Copolymerization benzoxazine-resin based carbon balls provided by the invention may be used as the electrode material of double layer capacitor.The present invention is to obtaining The charcoal ball electrode arrived carries out cyclic voltammetric sign, and charcoal ball electrode prepared by the present invention has high rate capability；The present invention is to obtaining The charcoal ball electrode arrived carries out constant current charge-discharge sign, and charcoal ball electrode has high capacitor performance and good rate response, The energy density and power density curve being calculated by constant current charge-discharge data, it is higher as a result to show that charcoal ball electrode has Energy density and power density；The present invention carries out cycle performance sign to obtained charcoal ball electrode, as a result illustrates that charcoal ball electrode has There is stable performance.
Embodiment 23
Embodiment 3 is obtained being copolymerized after benzoxazine-resin high score bulbec and calcined 4 hours in tube furnace at 900 DEG C, Obtain being copolymerized benzoxazine-resin based carbon balls.
Copolymerization benzoxazine-resin based carbon balls that the present invention obtains embodiment 23 are scanned electron-microscope scanning analysis, knot Fruit shows copolymerization benzoxazine-resin based carbon balls uniform particle sizes prepared by the present invention, there is very high monodispersity.
Obtain after being copolymerized benzoxazine-resin based carbon balls, the electrode of double layer capacitor is prepared into it, it follows that Copolymerization benzoxazine-resin based carbon balls provided by the invention may be used as the electrode material of double layer capacitor.The present invention is to obtaining The charcoal ball electrode arrived carries out cyclic voltammetric sign, and charcoal ball electrode prepared by the present invention has high rate capability；The present invention is to obtaining The charcoal ball electrode arrived carries out constant current charge-discharge sign, and charcoal ball electrode has high capacitor performance and good rate response, The energy density and power density curve being calculated by constant current charge-discharge data, it is higher as a result to show that charcoal ball electrode has Energy density and power density；The present invention carries out cycle performance sign to obtained charcoal ball electrode, and it is steady to illustrate that charcoal ball electrode has Fixed performance.
Embodiment 24
Embodiment 4 is obtained being copolymerized benzoxazine-resin high score bulbec and calcined 4 hours in tube furnace at 900 DEG C, is obtained To copolymerization benzoxazine-resin based carbon balls.
Copolymerization benzoxazine-resin based carbon balls that the present invention obtains embodiment 24 are scanned electron-microscope scanning analysis, knot Fruit shows copolymerization benzoxazine-resin based carbon balls uniform particle sizes prepared by the present invention, there is higher monodispersity.
Obtain after being copolymerized benzoxazine-resin based carbon balls, the electrode of double layer capacitor is prepared into it, it follows that Copolymerization benzoxazine-resin based carbon balls provided by the invention may be used as the electrode material of double layer capacitor.The present invention is to obtaining The charcoal ball electrode arrived carries out cyclic voltammetric sign, and charcoal ball electrode prepared by the present invention has high rate capability；The present invention is to obtaining The charcoal ball electrode arrived carries out constant current charge-discharge sign, and charcoal ball electrode has high capacitor performance and good rate response, The energy density and power density curve being calculated by constant current charge-discharge data, it is higher as a result to show that charcoal ball electrode has Energy density and power density；The present invention carries out cycle performance sign to obtained charcoal ball electrode, and it is steady to illustrate that charcoal ball electrode has Fixed performance.
Embodiment 25
Embodiment 5 is obtained being copolymerized benzoxazine-resin high score bulbec and calcined 4 hours in tube furnace at 900 DEG C, is obtained To copolymerization benzoxazine-resin based carbon balls.
Copolymerization benzoxazine-resin based carbon balls that the present invention obtains embodiment 25 are scanned electron-microscope scanning analysis, knot Fruit shows copolymerization benzoxazine-resin based carbon balls uniform particle sizes prepared by the present invention, there is very high monodispersity.
Obtain after being copolymerized benzoxazine-resin based carbon balls, the electrode of double layer capacitor is prepared into it, it follows that Copolymerization benzoxazine-resin based carbon balls provided by the invention may be used as the electrode material of double layer capacitor.The present invention is to obtaining The charcoal ball electrode arrived carries out cyclic voltammetric sign, and charcoal ball electrode prepared by the present invention has high rate capability；The present invention is to obtaining The charcoal ball electrode arrived carries out constant current charge-discharge sign, and charcoal ball electrode has high capacitor performance and good rate response, The energy density and power density curve being calculated by constant current charge-discharge data, it is very high as a result to show that charcoal ball electrode has Energy density and power density；The present invention carries out cycle performance sign to obtained charcoal ball electrode, and it is steady to illustrate that charcoal ball electrode has Fixed performance.
Embodiment 26
Embodiment 6 is obtained being copolymerized benzoxazine-resin high score bulbec and calcined 4 hours in tube furnace at 900 DEG C, is obtained To copolymerization benzoxazine-resin based carbon balls.
Copolymerization benzoxazine-resin based carbon balls of embodiment 26 are scanned electron-microscope scanning analysis by the present invention, as a result table Bright, prepared by present invention copolymerization benzoxazine-resin based carbon balls uniform particle sizes, have very high monodispersity.
After obtaining charcoal ball, the electrode of double layer capacitor is prepared into it, it follows that charcoal ball provided by the invention can be with Electrode material as double layer capacitor.The present invention carries out cyclic voltammetric sign to obtained charcoal ball electrode, prepared by the present invention Charcoal ball electrode there is high rate capability；The present invention carries out constant current charge-discharge sign, charcoal ball electricity to obtained charcoal ball electrode Have high capacitor performance and good rate response, the energy density and work(being calculated by constant current charge-discharge data Rate density curve, as a result show that charcoal ball electrode has higher energy density and power density；The present invention is electric to obtained charcoal ball Pole carries out cycle performance sign, illustrates that charcoal ball electrode has stable performance.
Embodiment 27
Embodiment 7 is obtained being copolymerized benzoxazine-resin high score bulbec and calcined 4 hours in tube furnace at 900 DEG C, is obtained To copolymerization benzoxazine-resin based carbon balls.
Copolymerization benzoxazine-resin based carbon balls that the present invention obtains embodiment 27 are scanned electron-microscope scanning analysis, knot Fruit shows copolymerization benzoxazine-resin based carbon balls uniform particle sizes prepared by the present invention, there is very high monodispersity.
Obtain after being copolymerized benzoxazine-resin based carbon balls, the electrode of double layer capacitor is prepared into it, it follows that Copolymerization benzoxazine-resin based carbon balls provided by the invention may be used as the electrode material of double layer capacitor.The present invention is to obtaining The charcoal ball electrode arrived carries out cyclic voltammetric sign, and charcoal ball electrode prepared by the present invention has high rate capability；The present invention is to obtaining The charcoal ball electrode arrived carries out constant current charge-discharge sign, and charcoal ball electrode has high capacitor performance and good rate response, The energy density and power density curve being calculated by constant current charge-discharge data, it is higher as a result to show that charcoal ball electrode has Energy density and power density；The present invention carries out cycle performance sign to obtained charcoal ball electrode, and it is steady to illustrate that charcoal ball electrode has Fixed performance.
Embodiment 28
Embodiment 8 is obtained being copolymerized benzoxazine-resin high score bulbec and calcined 4 hours in tube furnace at 900 DEG C, is obtained To copolymerization benzoxazine-resin based carbon balls.
Copolymerization benzoxazine-resin based carbon balls that the present invention obtains embodiment 28 are scanned electron-microscope scanning analysis, knot Fruit shows copolymerization benzoxazine-resin based carbon balls uniform particle sizes prepared by the present invention, there is very high monodispersity.
Obtain after being copolymerized benzoxazine-resin based carbon balls, the electrode of double layer capacitor is prepared into it, it follows that Copolymerization benzoxazine-resin based carbon balls provided by the invention may be used as the electrode material of double layer capacitor.The present invention is to obtaining The charcoal ball electrode arrived carries out cyclic voltammetric sign, and charcoal ball electrode prepared by the present invention has high rate capability；The present invention is to obtaining The charcoal ball electrode arrived carries out constant current charge-discharge sign, and charcoal ball electrode has high capacitor performance and good rate response, The energy density and power density curve being calculated by constant current charge-discharge data, it is higher as a result to show that charcoal ball electrode has Energy density and power density；The present invention carries out cycle performance sign to obtained charcoal ball electrode, and it is steady to illustrate that charcoal ball electrode has Fixed performance.
Embodiment 29
Embodiment 9 is obtained being copolymerized benzoxazine-resin high score bulbec and calcined 4 hours in tube furnace at 900 DEG C, is obtained To copolymerization benzoxazine-resin based carbon balls.
Copolymerization benzoxazine-resin based carbon balls that the present invention obtains embodiment 29 are scanned electron-microscope scanning analysis, knot Fruit shows copolymerization benzoxazine-resin based carbon balls uniform particle sizes prepared by the present invention, there is very high monodispersity.
Obtain after being copolymerized benzoxazine-resin based carbon balls, the electrode of double layer capacitor is prepared into it, it follows that Copolymerization benzoxazine-resin based carbon balls provided by the invention may be used as the electrode material of double layer capacitor.The present invention is to obtaining The charcoal ball electrode arrived carries out cyclic voltammetric sign, and charcoal ball electrode prepared by the present invention has high rate capability；The present invention is to obtaining The charcoal ball electrode arrived carries out constant current charge-discharge sign, and charcoal ball electrode has high capacitor performance and good rate response, The energy density and power density curve being calculated by constant current charge-discharge data, it is higher as a result to show that charcoal ball electrode has Energy density and power density；The present invention carries out cycle performance sign to obtained charcoal ball electrode, and it is steady to illustrate that charcoal ball electrode has Fixed performance.
Embodiment 30
Embodiment 10 is obtained being copolymerized benzoxazine-resin high score bulbec and calcined 4 hours in tube furnace at 900 DEG C, Obtain being copolymerized benzoxazine-resin based carbon balls.
Copolymerization benzoxazine-resin based carbon balls that the present invention obtains embodiment 30 are scanned electron-microscope scanning analysis, knot Fruit shows copolymerization benzoxazine-resin based carbon balls uniform particle sizes prepared by the present invention, there is very high monodispersity.
Obtain after being copolymerized benzoxazine-resin based carbon balls, the electrode of double layer capacitor is prepared into it, it follows that Copolymerization benzoxazine-resin based carbon balls provided by the invention may be used as the electrode material of double layer capacitor.The present invention is to obtaining The charcoal ball electrode arrived carries out cyclic voltammetric sign, and charcoal ball electrode prepared by the present invention has high rate capability；The present invention is to obtaining The charcoal ball electrode arrived carries out constant current charge-discharge sign, and charcoal ball electrode has high capacitor performance and good rate response, The energy density and power density curve being calculated by constant current charge-discharge data, it is higher as a result to show that charcoal ball electrode has Energy density and power density；The present invention carries out cycle performance sign to obtained charcoal ball electrode, and it is steady to illustrate that charcoal ball electrode has Fixed performance.
Embodiment 31
Embodiment 11 is obtained being copolymerized benzoxazine-resin high score bulbec and calcined 4 hours in tube furnace at 900 DEG C, Obtain being copolymerized benzoxazine-resin based carbon balls.
Copolymerization benzoxazine-resin based carbon balls that the present invention obtains embodiment 31 are scanned electron-microscope scanning analysis, knot Fruit shows copolymerization benzoxazine-resin based carbon balls uniform particle sizes prepared by the present invention, there is very high monodispersity.
Obtain after being copolymerized benzoxazine-resin based carbon balls, the electrode of double layer capacitor is prepared into it, it follows that Copolymerization benzoxazine-resin based carbon balls provided by the invention may be used as the electrode material of double layer capacitor.The present invention is to obtaining The charcoal ball electrode arrived carries out cyclic voltammetric sign, and charcoal ball electrode prepared by the present invention has high rate capability；The present invention is to obtaining The charcoal ball electrode arrived carries out constant current charge-discharge sign, and charcoal ball electrode has high capacitor performance and good rate response, The energy density and power density curve being calculated by constant current charge-discharge data, it is higher as a result to show that charcoal ball electrode has Energy density and power density；The present invention carries out cycle performance sign to obtained charcoal ball electrode, and it is steady to illustrate that charcoal ball electrode has Fixed performance.
Embodiment 32
Embodiment 12 is obtained being copolymerized benzoxazine-resin high score bulbec and calcined 4 hours in tube furnace at 900 DEG C, Obtain being copolymerized benzoxazine-resin based carbon balls.
Copolymerization benzoxazine-resin based carbon balls that the present invention obtains embodiment 32 are scanned electron-microscope scanning analysis, knot Fruit shows copolymerization benzoxazine-resin based carbon balls uniform particle sizes prepared by the present invention, there is very high monodispersity.
Obtain after being copolymerized benzoxazine-resin based carbon balls, the electrode of double layer capacitor is prepared into it, it follows that Copolymerization benzoxazine-resin based carbon balls provided by the invention may be used as the electrode material of double layer capacitor.The present invention is to obtaining The charcoal ball electrode arrived carries out cyclic voltammetric sign, and charcoal ball electrode prepared by the present invention has high rate capability；The present invention is to obtaining The charcoal ball electrode arrived carries out constant current charge-discharge sign, and charcoal ball electrode has high capacitor performance and good rate response, The energy density and power density curve being calculated by constant current charge-discharge data, it is higher as a result to show that charcoal ball electrode has Energy density and power density；The present invention carries out cycle performance sign to obtained charcoal ball electrode, and it is steady to illustrate that charcoal ball electrode has Fixed performance.
Embodiment 33
Embodiment 13 is obtained being copolymerized benzoxazine-resin high score bulbec and calcined 4 hours in tube furnace at 1300 DEG C, Obtain being copolymerized benzoxazine-resin based carbon balls.
Obtained copolymerization benzoxazine-resin based carbon balls are scanned electron-microscope scanning analysis, knot by the embodiment of the present invention 33 Fruit shows copolymerization benzoxazine-resin based carbon balls uniform particle sizes prepared by the present invention, there is higher monodispersity.
Obtain after being copolymerized benzoxazine-resin based carbon balls, the electrode of double layer capacitor is prepared into it, it follows that Copolymerization benzoxazine-resin based carbon balls provided by the invention may be used as the electrode material of double layer capacitor.The present invention is to obtaining The charcoal ball electrode arrived carries out cyclic voltammetric sign, and charcoal ball electrode prepared by the present invention has high rate capability；The present invention is to obtaining The charcoal ball electrode arrived carries out constant current charge-discharge sign, and charcoal ball electrode has high capacitor performance and good rate response, The energy density and power density curve being calculated by constant current charge-discharge data, it is higher as a result to show that charcoal ball electrode has Energy density and power density；The present invention carries out cycle performance sign to obtained charcoal ball electrode, and it is steady to illustrate that charcoal ball electrode has Fixed performance.
Embodiment 34
Embodiment 14 is obtained being copolymerized benzoxazine-resin high score bulbec and calcined 4 hours in tube furnace at 1300 DEG C, Obtain being copolymerized benzoxazine-resin based carbon balls.
Copolymerization benzoxazine-resin based carbon balls that the present invention obtains embodiment 34 are scanned electron-microscope scanning analysis, knot Fruit shows copolymerization benzoxazine-resin based carbon balls uniform particle sizes prepared by the present invention, there is higher monodispersity.
Obtain after being copolymerized benzoxazine-resin based carbon balls, the electrode of double layer capacitor is prepared into it, it follows that Copolymerization benzoxazine-resin based carbon balls provided by the invention may be used as the electrode material of double layer capacitor.The present invention is to obtaining The charcoal ball electrode arrived carries out cyclic voltammetric sign, and charcoal ball electrode prepared by the present invention has high rate capability；The present invention is to obtaining The charcoal ball electrode arrived carries out constant current charge-discharge sign, and charcoal ball electrode has high capacitor performance and good rate response, The energy density and power density curve being calculated by constant current charge-discharge data, it is higher as a result to show that charcoal ball electrode has Energy density and power density；The present invention carries out cycle performance sign to obtained charcoal ball electrode, and it is steady to illustrate that charcoal ball electrode has Fixed performance.
Embodiment 35
Embodiment 15 is obtained being copolymerized benzoxazine-resin high score bulbec and calcined 4 hours in tube furnace at 550 DEG C, Obtain being copolymerized benzoxazine-resin based carbon balls.
Copolymerization benzoxazine-resin based carbon balls that the present invention obtains embodiment 35 are scanned electron-microscope scanning analysis, knot Fruit shows copolymerization benzoxazine-resin based carbon balls uniform particle sizes prepared by the present invention, there is higher monodispersity.
Obtain after being copolymerized benzoxazine-resin based carbon balls, the electrode of double layer capacitor is prepared into it, it follows that Copolymerization benzoxazine-resin based carbon balls provided by the invention may be used as the electrode material of double layer capacitor.The present invention is to obtaining The charcoal ball electrode arrived carries out cyclic voltammetric sign, and charcoal ball electrode prepared by the present invention has high rate capability；The present invention is to obtaining The charcoal ball electrode arrived carries out constant current charge-discharge sign, and charcoal ball electrode has high capacitor performance and good rate response, The energy density and power density curve being calculated by constant current charge-discharge data, it is higher as a result to show that charcoal ball electrode has Energy density and power density；The present invention carries out cycle performance sign to obtained charcoal ball electrode, and it is steady to illustrate that charcoal ball electrode has Fixed performance.
Embodiment 36
Embodiment 16 is obtained being copolymerized benzoxazine-resin high score bulbec and calcined 4 hours in tube furnace at 600 DEG C, Obtain being copolymerized benzoxazine-resin based carbon balls.
Copolymerization benzoxazine-resin based carbon balls that the present invention obtains embodiment 36 are scanned electron-microscope scanning analysis, knot Fruit shows copolymerization benzoxazine-resin based carbon balls uniform particle sizes prepared by the present invention, there is higher monodispersity.
Obtain after being copolymerized benzoxazine-resin based carbon balls, the electrode of double layer capacitor is prepared into it, it follows that Copolymerization benzoxazine-resin based carbon balls provided by the invention may be used as the electrode material of double layer capacitor.The present invention is to obtaining The charcoal ball electrode arrived carries out cyclic voltammetric sign, and charcoal ball electrode prepared by the present invention has high rate capability；The present invention is to obtaining The charcoal ball electrode arrived carries out constant current charge-discharge sign, and charcoal ball electrode has high capacitor performance and good rate response, The energy density and power density curve being calculated by constant current charge-discharge data, it is higher as a result to show that charcoal ball electrode has Energy density and power density；The present invention carries out cycle performance sign to obtained charcoal ball electrode, and it is steady to illustrate that charcoal ball electrode has Fixed performance.
Embodiment 37
Embodiment 17 is obtained being copolymerized benzoxazine-resin high score bulbec and calcined 4 hours in tube furnace at 650 DEG C, Obtain being copolymerized benzoxazine-resin based carbon balls.
Copolymerization benzoxazine-resin based carbon balls that the present invention obtains embodiment 37 are scanned electron-microscope scanning analysis, knot Fruit shows copolymerization benzoxazine-resin based carbon balls uniform particle sizes prepared by the present invention, there is higher monodispersity.
Obtain after being copolymerized benzoxazine-resin based carbon balls, the electrode of double layer capacitor is prepared into it, it follows that Copolymerization benzoxazine-resin based carbon balls provided by the invention may be used as the electrode material of double layer capacitor.The present invention is to obtaining The charcoal ball electrode arrived carries out cyclic voltammetric sign, and charcoal ball electrode prepared by the present invention has high rate capability；The present invention is to obtaining The charcoal ball electrode arrived carries out constant current charge-discharge sign, and charcoal ball electrode has high capacitor performance and good rate response, The energy density and power density curve being calculated by constant current charge-discharge data, it is higher as a result to show that charcoal ball electrode has Energy density and power density；The present invention carries out cycle performance sign to obtained charcoal ball electrode, and it is steady to illustrate that charcoal ball electrode has Fixed performance.
Embodiment 38
Embodiment 18 is obtained being copolymerized benzoxazine-resin high score bulbec and calcined 4 hours in tube furnace at 850 DEG C, Obtain being copolymerized benzoxazine-resin based carbon balls.
Copolymerization benzoxazine-resin based carbon balls that the present invention obtains embodiment 38 are scanned electron-microscope scanning analysis, knot Fruit shows copolymerization benzoxazine-resin based carbon balls uniform particle sizes prepared by the present invention, there is higher monodispersity.
Obtain after being copolymerized benzoxazine-resin based carbon balls, the electrode of double layer capacitor is prepared into it, it follows that Copolymerization benzoxazine-resin based carbon balls provided by the invention may be used as the electrode material of double layer capacitor.The present invention is to obtaining The charcoal ball electrode arrived carries out cyclic voltammetric sign, and charcoal ball electrode prepared by the present invention has high rate capability；The present invention is to obtaining The charcoal ball electrode arrived carries out constant current charge-discharge sign, and charcoal ball electrode has high capacitor performance and good rate response, The energy density and power density curve being calculated by constant current charge-discharge data, it is higher as a result to show that charcoal ball electrode has Energy density and power density；The present invention carries out cycle performance sign to obtained charcoal ball electrode, and it is steady to illustrate that charcoal ball electrode has Fixed performance.
As seen from the above embodiment, the present invention provide it is a kind of be copolymerized benzoxazine-resin high score bulbec preparation method and M-aminophenol and formaldehyde are polymerize by the preparation method of charcoal ball, the present invention under the conditions of existing for ammoniacal liquor and/or ethylenediamine Reaction, obtain being copolymerized benzoxazine-resin high score bulbec.Formaldehyde, m-aminophenol and ammoniacal liquor and/or second two as catalyst Amine forms micella in a solvent, and in micella, polymerisation occurs for ammoniacal liquor and/or ethylenediamine catalysis m-aminophenol and formaldehyde, So as to obtain being copolymerized benzoxazine-resin high score bulbec；During the course of the reaction, ammoniacal liquor and/or ethylenediamine can be distributed in micella Surface, produce positive charge, the effect of Coulomb repulsion inhibits the bonding between micella, so as to get copolymerization benzoxazine-tree Fat macromolecule ball has very high monodispersity, and the size of resin balls can be adjusted on a large scale, be advantageous to its application.The present invention Charcoal ball is obtained after obtained copolymerization benzoxazine-resin high score bulbec is calcined, therefore charcoal ball provided by the invention also has There is very high monodispersity.

Claims (4)

1. a kind of self-catalysis preparation method for being copolymerized benzoxazine-resin high score bulbec, it is characterised in that comprise the following steps：
M-aminophenol and formaldehyde are dissolved in a solvent, obtain being copolymerized benzoxazine-resin high score bulbec after polymerisation；
The solvent is the mixed solution of water and methanol；
Described water and the volume ratio of methanol are 1：1；
Described m-aminophenol and the mol ratio of formaldehyde are 1：(1.5~5)；
The concentration of described m-aminophenol is 5mmol/L~320mmol/L；
The concentration of described formaldehyde is 7.5mmol/L~1600mmol/L；
The temperature of described dissolving is 10 DEG C~70 DEG C.
2. a kind of self-catalysis preparation method for being copolymerized benzoxazine-resin high score bulbec according to claim 1, its feature It is, the temperature of described polymerisation is 50 DEG C~200 DEG C, and the time of polymerisation is 0.1 hour~50 hours.
3. a kind of self-catalysis preparation method for being copolymerized benzoxazine-resin based carbon balls, it is characterised in that comprise the following steps：
Copolymerization benzoxazine-resin high score bulbec that preparation method described in claim 1-2 any one obtains is forged Burn, obtain being copolymerized benzoxazine-resin based carbon balls.
4. a kind of self-catalysis preparation method for being copolymerized benzoxazine-resin based carbon balls according to claim 3, its feature exist In the temperature of described calcining is 500 DEG C~1300 DEG C, and the time of calcining is 2 hours~12 hours.
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