CN102643513B

CN102643513B - Preparation method of meta-aminophenol-formaldehyde resin spheres and preparation method of carbon spheres

Info

Publication number: CN102643513B
Application number: CN201210148245XA
Authority: CN
Inventors: 徐国宝; 赵建明
Original assignee: Changchun Institute of Applied Chemistry of CAS
Current assignee: Changzhou Institute Of Energy Storage Materials & Devices
Priority date: 2012-05-14
Filing date: 2012-05-14
Publication date: 2013-11-27
Anticipated expiration: 2032-05-14
Also published as: CN102643513A

Abstract

The invention provides a preparation method of meta-aminophenol-formaldehyde resin spheres and a preparation method of carbon spheres. Meta-aminophenol and formaldehyde are subjected to polymerization reaction in the presence of ammonia water and/or ethylene diamine. In the polymerization reaction process, the formaldehyde, the meta-aminophenol and the ammonia water and/or ethylene diamine as the catalyst form a micelle in the solvent; in the micelle, the meta-aminophenol and the formaldehyde are subjected to polymerization reaction under the catalytic action of the ammonia water and/or ethylene diamine to obtain the meta-aminophenolformaldehyde resin spheres; and meanwhile, part of the ammonia water and/or ethylene diamine are/is distributed on the surface of the micelle to form positive charges, and the electrostatic repulsion action inhibits the bonding of the micelle. Thus, the obtained meta-aminophenol-formaldehyde resin spheres have high monodispersity, and the dimensions of the resin spheres can be adjusted within a wide range. The meta-aminophenol-formaldehyde resin spheres are calcined to obtain the corresponding carbon spheres, and the carbon spheres also have high monodispersity, thereby being beneficial to the application of the carbon spheres.

Description

A kind of preparation method of m-aminophenyl resinox ball and the preparation method of carbon ball

Technical field

The present invention relates to technical field of polymer, relate in particular to a kind of preparation method of m-aminophenyl resinox ball and the preparation method of carbon ball.

Background technology

Single dispersoid ball, because shape is single, size is controlled, has widespread use at aspects such as synthesizing of reference materials for particle size analysis, photonic crystal, Ordered Macroporous Materials, macroporous catalyst and proton membrane matrix material.For example, the transmission of medicine, medical diagnosis, alternately catalyzer, complex construction and nano-device.For the preparation of single dispersoid ball, prior art discloses high-temperature cracking method and template, but these two kinds of methods to the having relatively high expectations of equipment, the aftertreatment inconvenience, therefore be not suitable for extensive synthetic carbon ball.In order to simplify the synthesis step of single dispersoid ball, prior art, by the method that micella synthesizes, synthesizes some high score bulbecs, as polystyrene, methyl methacrylate and hydroxyl acrylic methyl esters colloidal spheres, but, because their thermodynamics is stable not, can not carbonization become corresponding carbon ball.

Because resol has higher thermodynamic stability, in order to obtain thermodynamically stable single dispersoid ball, prior art is devoted to the research of phenolic resin balls and corresponding carbon ball thereof.Recently, bibliographical information is arranged a kind of benzoxazine synthesis method prepare the method (J.Am.Chem.Soc.2011 of phenolic resin balls and corresponding carbon ball, 133,15304-15307.), obtained resin balls and corresponding carbon ball by regulating synthesis temperature, it is less that but this method obtains the size interval of resin balls and carbon ball, the controllability of particle diameter is less, and the productive rate of the product obtained is less, and, in the process of preparation, use tensio-active agent, made synthesis step and aftertreatment more loaded down with trivial details.

In order to simplify the preparation technology of phenolic resin balls and carbon ball, improve the performance of phenolic resin balls and carbon ball, prior art discloses a kind of

Method (the Angew.Chem. of the synthetic resorcinol-formaldehyde resin ball of method and corresponding carbon ball, Int.Ed.2011,50,5947-5951.), yet the surface of the resorcinol-formaldehyde resin ball that this method obtains and corresponding carbon ball is more coarse, monodispersity is lower, is unfavorable for the application of resin balls and carbon ball.

Summary of the invention

The object of the present invention is to provide a kind of preparation method of m-aminophenyl resinox ball and the preparation method of carbon ball, m-aminophenyl resinox ball prepared by method provided by the invention and carbon ball have the monodispersity of height,, be conducive to the application of resin balls and carbon ball.

The invention provides a kind of preparation method of m-aminophenyl resinox ball, comprise the following steps:

Catalyzer, Metha Amino Phenon and formaldehyde are dissolved in solvent, after polyreaction, obtain m-aminophenyl resinox ball;

Described catalyzer is ammoniacal liquor and/or quadrol;

Described solvent is the mixing solutions of the aqueous solution, alcoholic solution or water and alcohol compound.

Preferably, described catalyzer is ammoniacal liquor.

Preferably, described alcohol compound is one or more in methyl alcohol, ethanol, Virahol and ethylene glycol.

Preferably, described alcohol compound is ethanol.

Preferably, the temperature of described dissolving is 0 ℃ ~ 90 ℃.

Preferably, the temperature of described polyreaction is 50 ℃ ~ 200 ℃.

Preferably, the time of described polyreaction is 4 hours ~ 50 hours.

The invention provides a kind of preparation method of carbon ball, comprise the following steps:

The m-aminophenyl resinox ball that the described preparation method of technique scheme obtains is calcined, obtained the carbon ball.

Preferably, the temperature of described calcining is 300 ℃ ~ 800 ℃.

Preferably, the time of described calcining is 2 hours ~ 12 hours.

The invention provides a kind of preparation method of m-aminophenyl resinox ball and the preparation method of carbon ball.The present invention is dissolved catalyzer, Metha Amino Phenon and formaldehyde in solvent, after polyreaction, obtain m-aminophenyl resinox ball; Described catalyzer is ammoniacal liquor and/or quadrol, and described solvent is the mixing solutions of the aqueous solution, alcoholic solution or water and alcohol compound.The present invention using ammoniacal liquor and/or quadrol as catalyzer for the polyreaction of Metha Amino Phenon and formaldehyde, formaldehyde, Metha Amino Phenon and in solvent, form micella as ammoniacal liquor and/or the quadrol of catalyzer, in micella, ammoniacal liquor and/or quadrol catalysis Metha Amino Phenon and formaldehyde polymerization reaction take place, thus m-aminophenyl resinox ball obtained; In reaction process, ammoniacal liquor and/or quadrol not only can the catalysis Metha Amino Phenons and the polyreaction of formaldehyde, can also be distributed in the surface of micella, form positive charge, electrostatic repulsion makes the surface of micella with identical electric charge, mutually repels thereby make between micella, suppressed the bonding between micella, the m-aminophenyl resinox ball obtained has higher monodispersity, and the size of resin balls can be regulated on a large scale, is conducive to its application.And method provided by the invention prepares m-aminophenyl resinox ball higher productive rate is arranged.The m-aminophenyl resinox ball that the present invention will obtain obtains the carbon ball after calcining, and therefore carbon ball provided by the invention also has higher monodispersity.Experimental result shows, the monodispersity of Metha Amino Phenon-resin balls provided by the invention mostly is 0.81% ~ 5%, its particle dia is adjustable between 80nm ~ 2527nm, and method provided by the invention prepares the productive rate of m-aminophenyl resinox ball up to 50% ~ 96%.

The accompanying drawing explanation

Fig. 1 is the scanning electron microscope (SEM) photograph of the m-aminophenyl resinox ball of the embodiment of the present invention 1 preparation;

Fig. 2 is the particle diameter statistical graph of the m-aminophenyl resinox ball that obtains of the embodiment of the present invention 1;

Fig. 3 is the scanning electron microscope (SEM) photograph of the carbon ball of the embodiment of the present invention 1 preparation;

Fig. 4 is the scanning electron microscope (SEM) photograph of the carbon ball that supports platinum that obtains of the embodiment of the present invention 1;

Fig. 5 is the carbon ball XRD figure spectrum that supports platinum that the embodiment of the present invention 1 obtains;

Fig. 6 is the hydrogen adsorption desorption curve of the carbon ball that supports platinum that obtains of the embodiment of the present invention 1;

Fig. 7 is the linear time base sweep curve of oxygen reduction on the platinum the embodiment of the present invention 1 obtains/carbon ball modified electrode and carbon ball modified electrode;

Fig. 8 is the cyclic voltammetry curve of methanol oxidation on the platinum the embodiment of the present invention 1 obtains/carbon ball modified electrode and carbon ball modified electrode.

Embodiment

Described catalyzer is ammoniacal liquor and/or quadrol;

At first the present invention dissolves catalyzer, Metha Amino Phenon and formaldehyde in solvent, obtain mixing solutions, and described catalyzer is ammoniacal liquor and/or quadrol, is preferably ammoniacal liquor.The order that the present invention is dissolved in solvent described catalyzer, Metha Amino Phenon and formaldehyde does not have special restriction, adopts the technical scheme for preparing resol well known to those skilled in the art to get final product.The present invention preferably first joins Metha Amino Phenon in solvent, then adds wherein catalyzer, finally adds wherein formaldehyde again, obtains mixing solutions.After described formaldehyde added, Metha Amino Phenon, formaldehyde and catalyzer formed micella in solvent, and in described micella, described catalyst formaldehyde and Metha Amino Phenon carry out polyreaction, obtain m-aminophenyl resinox ball.In order to make raw material fully dissolve and mix, the present invention in Metha Amino Phenon is joined to solvent after, preferably it is carried out to the first stirring and dissolving; After adding catalyzer, the solution that the present invention preferably will obtain carries out second and stirs; After adding formaldehyde wherein, obtain mixing solutions, the present invention preferably carries out the 3rd stirring to the mixing solutions obtained.

In the present invention, described solvent is the mixing solutions of the aqueous solution, alcoholic solution or water and alcohol compound, be preferably the mixing solutions of water and alcohol compound, described alcohol compound is preferably one or more in methyl alcohol, ethanol, Virahol and ethylene glycol, ethanol more preferably, the present invention does not have special restriction to the ratio of water and alcohol compound in the mixing solutions of described water and alcohol compound, can make Metha Amino Phenon, formaldehyde and catalyst dissolution and produce micella to get final product, the present invention does not have special restriction to the ratio of described Metha Amino Phenon and formaldehyde, adopts the ratio of phenolic compound and formaldehyde in phenolic aldehyde polymerization process well known to those skilled in the art to get final product, consumption and the concentration also not restriction of the present invention to described catalyzer, described catalyst member is wrapped in the surface of the micella of formation, form positive charge, electrostatic repulsion has suppressed the reunion of micella, the monodispersity of the m-aminophenyl resinox ball obtained so improved, the present invention does not have special restriction to described ammoniacal liquor and quadrol, adopt the commercial goods of ammoniacal liquor and quadrol to get final product, in the present invention, the volumetric molar concentration of described catalyzer is preferably 0.1mmol/L ~ 800mmol/L, 4.77mmol/L ~ 47.7mmol/L more preferably, in order to bring into play more fully the effect of catalyzer, in the present invention, the volume of described formaldehyde and the mass ratio of described Metha Amino Phenon are preferably (10 ~ 900) μ L:(2 ~ 800) mg, (42 ~ 252) μ L:(30 ~ 180 more preferably) mg.The described first temperature stirred is preferably 0 ℃ ~ 90 ℃, more preferably 10 ℃ ~ 80 ℃, most preferably is 20 ℃ ~ 50 ℃; The present invention does not have special restriction to the first time of stirring, and described Metha Amino Phenon is dissolved and get final product, and in the present invention, the time of described the first stirring is preferably 5 minutes ~ and 15 minutes; The described second purpose stirred is that described catalyzer is mixed with described Metha Amino Phenon, the time of described the second stirring is preferably 5 minutes ~ and 30 minutes, more preferably 10 minutes ~ 25 minutes; The described the 3rd time of stirring was preferably 0.5 hour ~ and 24 hours, more preferably 1 hour ~ 15 hours, most preferably be 4 hours ~ 10 hours; Described the second stirring and the described the 3rd is stirred preferably and is carried out at the described first temperature stirred.

After obtaining the mixing solutions of Metha Amino Phenon, catalyzer and formaldehyde, in described mixing solutions, under the effect of described catalyzer, described Metha Amino Phenon and described formaldehyde polymerization reaction take place, obtain m-aminophenyl resinox ball.The present invention does not have special restriction to the condition of described Metha Amino Phenon and formaldehyde reaction, adopts the technical scheme of the preparation of resol well known to those skilled in the art to get final product.In the present invention, the temperature of described polyreaction is preferably 50 ℃ ~ 200 ℃, and more preferably 100 ℃ ~ 150 ℃, when temperature of reaction during lower than 55 ℃, the present invention preferably carries out described mixing solutions hydro-thermal reaction under hydrothermal condition, obtain m-aminophenyl resinox ball.The present invention also can directly stir described mixing solutions, can obtain m-aminophenyl resinox ball, without carrying out water-heat process.The present invention does not have special restriction to the method for described stirring, adopts the technical scheme of stirring well known to those skilled in the art to get final product.In the present invention, the time of described polyreaction is preferably 4 hours ~ and 50 hours, more preferably 8 hours ~ 40 hours, more preferably 10 hours ~ 30 hours.

In the process of described polyreaction, described formaldehyde, Metha Amino Phenon and catalyzer form micella in solvent, in described micella, as the polyreaction of ammoniacal liquor and/or quadrol catalysis Metha Amino Phenon and the formaldehyde of catalyzer, thereby obtain m-aminophenyl resinox ball; In reaction process, the surface that can also be distributed in micella as ammoniacal liquor and/or the quadrol of catalyzer, make micellar surface with same electric charge, thereby make between micella, there is repulsive interaction, suppressed the bonding between micella, the m-aminophenyl resinox ball obtained has higher monodispersity, and its size has good controllability, is conducive to its application.

After described polyreaction completed, the reaction solution that the present invention preferably will obtain carried out aftertreatment, obtained m-aminophenyl resinox ball, and detailed process is as follows:

The reaction solution that the present invention will obtain carries out solid-liquid separation, and the solid that then will obtain cleans, and the solid after the cleaning obtained is carried out to drying, obtains m-aminophenyl resinox ball.The present invention does not have special restriction to the method for described solid-liquid separation, adopt the technical scheme of solid-liquid separation well known to those skilled in the art to get final product, in the present invention, described solid-liquid separation is preferably centrifugal, the present invention does not have special restriction to described centrifugal parameter setting, adopts centrifugal technical scheme well known to those skilled in the art to get final product.In the present invention, described centrifugal speed is 6000rpm ~ 10000rpm, 7000rpm ~ 9000rpm more preferably, and the described centrifugal time is preferably 1 minute ~ and 20 minutes, more preferably 5 minutes ~ 15 minutes.The present invention does not have special restriction to the method for described cleaning, adopts the technical scheme of cleaning well known to those skilled in the art to get final product.In the present invention, described cleaning is preferably water and cleans, and the number of times of described cleaning is preferably 2 times ~ 5 times.The present invention does not have special restriction to the method for described drying, adopts the technical scheme of drying well known to those skilled in the art to get final product.In the present invention, the temperature of described drying is preferably 60 ℃ ~ 100 ℃, and more preferably 70 ℃ ~ 90 ℃, the time of described drying is preferably 5 hours ~ and 24 hours, more preferably 10 hours ~ 15 hours.

After obtaining m-aminophenyl resinox ball, the present invention carries out the scanning electron microscope scanning analysis to described m-aminophenyl resinox ball, result shows, m-aminophenyl resinox ball provided by the invention has higher monodispersity, and the size of resin balls can be regulated on a large scale.

The invention provides a kind of preparation method of m-aminophenyl resinox ball, by ammoniacal liquor and/or the quadrol polyreaction for Metha Amino Phenon and formaldehyde, formaldehyde, Metha Amino Phenon and in solvent, form micella as ammoniacal liquor and/or the quadrol of catalyzer, in micella, ammoniacal liquor and/or quadrol catalysis Metha Amino Phenon and formaldehyde polymerization reaction take place, thus m-aminophenyl resinox ball obtained; In reaction process, partial ammonia water and/or quadrol can also be distributed in the surface of micella, make micellar surface with identical electric charge, electrostatic repulsion has suppressed the bonding between micella, make the m-aminophenyl obtained resinox ball that higher monodispersity be arranged,, the size of resin balls can be regulated on a large scale, is conducive to its application.

After obtaining m-aminophenyl resinox ball, the present invention calcines described m-aminophenyl resinox ball, and described m-aminophenyl resinox ball obtains charing, thereby obtains the carbon ball.The present invention does not have special restriction to the method for described calcining, adopts the technical scheme of calcining well known to those skilled in the art to get final product.The m-aminophenyl resinox ball that the present invention preferably will obtain is placed in tube furnace, and it is calcined, and obtains the carbon ball, and in the present invention, the temperature of described calcining is preferably 300 ℃ ~ 800 ℃, more preferably 350 ℃ ~ 700 ℃, most preferably is 400 ℃ ~ 600 ℃; The time of described calcining is preferably 2 hours ~ and 12 hours, more preferably 4 hours ~ 8 hours.

After obtaining the carbon ball, the carbon ball that the present invention will obtain carries out the scanning electron microscope scanning analysis, and result shows, carbon ball provided by the invention has higher monodispersity, and the size of the carbon ball obtained can be regulated in the larger context.

The m-aminophenyl resinox ball that the present invention obtains the described preparation method of technique scheme carries out obtaining the carbon ball after charing, so carbon ball prepared by the present invention also has higher monodispersity, and the particle diameter of ball can be regulated interval large, is conducive to its application.

The carbon ball that the present invention obtains can be as the carrier of catalyzer, and detailed process is as follows:

The present invention is carried on platinum on described carbon ball, obtains supporting the carbon ball of platinum.The present invention does not have special restriction to the carrying method of described platinum on the carbon ball, adopts the compound technical scheme of support of the catalyst well known to those skilled in the art and catalyzer to get final product.After obtaining supporting the carbon ball of platinum, the present invention carries out scanning electron microscope scanning analysis and X-ray diffraction analysis by the described carbon ball that supports platinum, and result shows, platinum loads on the surface of carbon ball, obtains the matrix material of carbon and platinum.

The present invention tests the catalytic performance of the carbon ball that supports platinum that obtains, and detailed process is as follows:

The present invention carries out the experiment of hydrogen adsorption desorption by the described carbon ball that supports platinum, and result shows, after carbon ball Supported Pt Nanoparticles provided by the invention, to have larger active area; The described material of the carbon ball of platinum as modified electrode that support usingd in the present invention, obtains carbon ball/platinum modified electrode, using described carbon ball/platinum modified electrode as working electrode, uses it for the catalysis to oxygen reduction, obtains the linear time base sweep curve of oxygen reduction; And, by the catalyzed oxidation of described carbon ball/platinum modified electrode for methyl alcohol, obtain the cyclic voltammetry curve of methyl alcohol.Result shows, the carbon ball that the present invention will obtain is for the carrier of supported catalyst, and the matrix material obtained has catalytic activity preferably.

The invention provides a kind of preparation method of m-aminophenyl resinox ball and the preparation method of carbon ball, catalyzer, Metha Amino Phenon, formaldehyde are dissolved in solvent, after polyreaction, obtain m-aminophenyl resinox ball; Described catalyzer is ammoniacal liquor and/or quadrol, and described solvent is the mixing solutions of the aqueous solution, alcoholic solution or water and alcohol compound.The present invention is used for ammoniacal liquor and/or quadrol the polyreaction of Metha Amino Phenon and formaldehyde, formaldehyde, Metha Amino Phenon and in solvent, form micella as ammoniacal liquor and/or the quadrol of catalyzer, in micella, ammoniacal liquor and/or quadrol catalysis Metha Amino Phenon and formaldehyde polymerization reaction take place, thus m-aminophenyl resinox ball obtained; Simultaneously, partial ammonia water and/or quadrol can also be distributed in the surface of micella, surface at micella produces positive charge, electrostatic repulsion has suppressed the bonding between micella, the m-aminophenyl resinox ball obtained has higher monodispersity, the size of resin balls can be regulated on a large scale, is conducive to its application.The m-aminophenyl resinox ball that the present invention will obtain obtains the carbon ball after calcining, so carbon ball prepared by the present invention also has higher monodispersity.And method provided by the invention prepares m-aminophenyl resinox ball higher productive rate is arranged.Carbon ball provided by the invention can be used as support of the catalyst, has higher catalytic activity.Experimental result shows, the monodispersity overwhelming majority of Metha Amino Phenon-resin balls provided by the invention is 0.81% ~ 5%, and its particle dia is adjustable between 80nm ~ 2527nm, and the productive rate of method provided by the invention can be up to 50% ~ 96%.

In order to further illustrate the present invention, below in conjunction with embodiment, m-aminophenyl resinox ball provided by the invention, carbon ball and preparation method thereof are described in detail, but they can not be interpreted as to the restriction to protection domain of the present invention.

Embodiment 1

The 32.7mg Metha Amino Phenon is joined in the mixing solutions of 12mL water and 4.8mL methyl alcohol, 30 ℃ of lower stirring and dissolving after 10 minutes, adding wherein 0.6 μ L mass concentration is 28% ammoniacal liquor, the mixing solutions that then will obtain stirs after 20 minutes and adds wherein 46 μ L formaldehyde, stir after 4 hours, the mixing solutions obtained is placed in to the 20mL reactor, stirred 24 hours under 100 ℃.By the reaction product that obtains under the 8000rpm rotating speed centrifugal 5 minutes, by obtain centrifugal after solid washing twice, under 80 ℃ dry 12 hours, obtain m-aminophenyl resinox ball.

The quality of the m-aminophenyl resinox ball that weighing of the present invention obtains is 47.7mg, and calculating productive rate is 94%.The present invention carries out the scanning electron microscope scanning analysis to the m-aminophenyl resinox ball obtained, result as shown in Figure 1, Fig. 1 is the scanning electron microscope (SEM) photograph of the m-aminophenyl resinox ball of the embodiment of the present invention 1 preparation, as seen from Figure 1, the phenolic resin balls for preparing of the present invention has higher monodispersity.The scanning electron microscope (SEM) photograph that the present invention will obtain carries out the particle diameter statistics, result as shown in Figure 2, Fig. 2 is the particle diameter statistical graph of the m-aminophenyl resinox ball that obtains of the embodiment of the present invention 1, as seen from Figure 2, the size distribution of m-aminophenyl resinox ball prepared by the present invention is narrower, and monodispersity is better.The particle diameter of m-aminophenyl resinox ball prepared by the present embodiment is 510nm, and monodispersity is 4.7%, and result is as shown in table 1, the detected result of m-aminophenyl resinox ball prepared for the embodiment of the present invention and comparative example by table 1.

After obtaining m-aminophenyl resinox ball, the present invention calcines them 4 hours in tube furnace under 550 ℃, obtain the carbon ball.

The carbon ball that the present invention will obtain carries out the scanning electron microscope scanning analysis, and as shown in Figure 3, Fig. 3 is the scanning electron microscope (SEM) photograph of the carbon ball of the embodiment of the present invention 1 preparation to result, and as seen from Figure 3, carbon spherolite footpath prepared by the present invention is even, has higher monodispersity.

After obtaining the carbon ball, the present invention, at its area load platinum, obtains supporting the carbon ball of platinum, and hence one can see that, and carbon ball provided by the invention can be as the carrier of catalyzer.The carbon ball that supports platinum that the present invention will obtain carries out scanning electron microscope scanning analysis and X-ray diffraction analysis, and as shown in Figure 4 and Figure 5, Fig. 4 is the scanning electron microscope (SEM) photograph of the carbon ball that supports platinum that obtains of the embodiment of the present invention 1 to result; Fig. 5 is the carbon ball XRD figure spectrum that supports platinum that the embodiment of the present invention 1 obtains, and can be found out by Fig. 4 and Fig. 5, and load has platinum on carbon ball provided by the invention.

The present invention carries out the experiment of hydrogen adsorption desorption to the carbon ball that supports platinum obtained, result as shown in Figure 6, Fig. 6 is the hydrogen adsorption desorption curve of the carbon ball that supports platinum that obtains of the embodiment of the present invention 1, and as seen from Figure 6, the carbon ball that supports platinum prepared by the present invention has larger catalysis area; The carbon ball that supports platinum that the present invention will obtain is as the decorative material of electrode, obtain carbon ball/platinum modified electrode, by the carbon ball that obtains/platinum modified electrode for the catalysis to oxygen reduction, result such as Fig. 7, Fig. 7 is the linear time base sweep curve of the oxygen reduction on the platinum that obtains of the embodiment of the present invention 1/carbon ball modified electrode and carbon ball modified electrode, wherein curve a is the linear time base sweep curve of oxygen reduction on platinum/carbon ball modified electrode, and curve b is the linear time base sweep curve of oxygen reduction on carbon ball modified electrode; The electrode that the present invention will obtain is for the catalytic oxidation of methyl alcohol, result as shown in Figure 8, Fig. 8 is the cyclic voltammetry curve of methanol oxidation on the platinum the embodiment of the present invention 1 obtains/carbon ball modified electrode and carbon ball modified electrode, wherein curve a is the cyclic voltammetry curve of methanol oxidation on platinum/carbon ball modified electrode, curve b is the cyclic voltammetry curve of methanol oxidation on carbon ball modified electrode, by Fig. 7 and Fig. 8, can be found out, carbon ball prepared by the present invention has higher catalytic activity after supporting platinum, and the reduction of oxygen and the oxidation of methyl alcohol are had to good electrocatalysis characteristic.

Embodiment 2

The 32.7mg Metha Amino Phenon is joined in the mixing solutions of 12mL water and 4.8mL methyl alcohol, 30 ℃ of lower stirring and dissolving after 10 minutes, adding wherein 12 μ L mass concentrations is 28% ammoniacal liquor, the mixing solutions that then will obtain stirs after 20 minutes and adds wherein 46 μ L formaldehyde, stir after 4 hours, the mixing solutions obtained is placed in to the 20mL reactor, stirred 24 hours under 100 ℃.By the reaction product that obtains under the 8000rpm rotating speed centrifugal 5 minutes, by obtain centrifugal after solid washing twice, under 80 ℃ dry 12 hours, obtain m-aminophenyl resinox ball.

The quality of the m-aminophenyl resinox ball that weighing of the present invention obtains is 46.6mg, and calculating productive rate is 92.0%.The present invention carries out the scanning electron microscope scanning analysis to the m-aminophenyl resinox ball obtained, result shows, phenolic resin balls prepared by the present invention has higher monodispersity, the particle diameter of m-aminophenyl resinox ball prepared by the present embodiment is 503nm, monodispersity is 1.7%, result is as shown in table 1, the detected result of m-aminophenyl resinox ball prepared for the embodiment of the present invention and comparative example by table 1.

After obtaining m-aminophenyl resinox ball, it was calcined 4 hours under 550 ℃ in tube furnace, obtain the carbon ball.

The carbon ball that the present invention will obtain carries out the scanning electron microscope scanning analysis, and result shows, carbon spherolite footpath prepared by the present invention is even, has higher monodispersity.

After obtaining the carbon ball, the present invention, at its area load platinum, obtains supporting the carbon ball of platinum, and hence one can see that, and carbon ball provided by the invention can be as the carrier of catalyzer.The carbon ball that supports platinum that the present invention will obtain carries out scanning electron microscope scanning analysis and X-ray diffraction analysis, and result shows, load has platinum on carbon ball provided by the invention.

The present invention carries out the experiment of hydrogen adsorption desorption to the carbon ball that supports platinum obtained, and result shows, the carbon ball that supports platinum prepared by the present invention has larger catalysis area; The carbon ball that supports platinum that the present invention will obtain is as the decorative material of electrode, obtain carbon ball/platinum modified electrode, by the carbon ball that obtains/platinum modified electrode for the reduction of oxygen and the oxidation of methyl alcohol, result shows, carbon ball prepared by the present invention supports after platinum to have higher catalytic activity the reduction of oxygen and the oxidation of methyl alcohol are had to good electrocatalysis characteristic.。

Embodiment 3

The 32.7mg Metha Amino Phenon is joined in the mixing solutions of 12mL water and 4.8mL methyl alcohol, 30 ℃ of lower stirring and dissolving after 10 minutes, adding wherein 18 μ L mass concentrations is 28% ammoniacal liquor, the mixing solutions that then will obtain stirs after 20 minutes and adds wherein 46 μ L formaldehyde, stir after 4 hours, the mixing solutions obtained is placed in to the 20mL reactor, stirred 24 hours under 100 ℃.By the reaction product that obtains under the 8000rpm rotating speed centrifugal 5 minutes, by obtain centrifugal after solid washing twice, under 80 ℃ dry 12 hours, obtain m-aminophenyl resinox ball.

The quality of the m-aminophenyl resinox ball that weighing of the present invention obtains is 48mg, and calculating productive rate is 94.7%.The present invention carries out the scanning electron microscope scanning analysis to the m-aminophenyl resinox ball obtained, result shows, phenolic resin balls prepared by the present invention has higher monodispersity, the particle diameter of m-aminophenyl resinox ball prepared by the present embodiment is 468nm, monodispersity is 1.8%, result is as shown in table 1, the detected result of m-aminophenyl resinox ball prepared for the embodiment of the present invention and comparative example by table 1.

The present invention carries out the experiment of hydrogen adsorption desorption to the carbon ball that supports platinum obtained, and result shows, the carbon ball that supports platinum prepared by the present invention has larger catalysis area; The carbon ball that supports platinum that the present invention will obtain is as the decorative material of electrode, obtain carbon ball/platinum modified electrode, by the carbon ball that obtains/platinum modified electrode for the reduction of oxygen and the catalytic oxidation of methyl alcohol, result shows, carbon ball prepared by the present invention has higher catalytic activity after supporting platinum, and the reduction of oxygen and the oxidation of methyl alcohol are had to good electrocatalysis characteristic.

Embodiment 4

The 32.7mg Metha Amino Phenon is joined in the mixing solutions of 12mL water and 4.8mL methyl alcohol, 30 ℃ of lower stirring and dissolving after 10 minutes, adding wherein 30 μ L mass concentrations is 28% ammoniacal liquor, the mixing solutions that then will obtain stirs after 20 minutes and adds wherein 46 μ L formaldehyde, stir after 4 hours, the mixing solutions obtained is placed in to the 20mL reactor, stirred 24 hours under 100 ℃.By the reaction product that obtains under the 8000rpm rotating speed centrifugal 5 minutes, by obtain centrifugal after solid washing twice, under 80 ℃ dry 12 hours, obtain m-aminophenyl resinox ball.

The quality of the m-aminophenyl resinox ball that weighing of the present invention obtains is 45mg, and calculating productive rate is 88.8%.The present invention carries out the scanning electron microscope scanning analysis to the m-aminophenyl resinox ball obtained, result shows, phenolic resin balls prepared by the present invention has higher monodispersity, the particle diameter of m-aminophenyl resinox ball prepared by the present embodiment is 454nm, monodispersity is 1.9%, result is as shown in table 1, the detected result of m-aminophenyl resinox ball prepared for the embodiment of the present invention and comparative example by table 1.

The present invention carries out the experiment of hydrogen adsorption desorption to the carbon ball that supports platinum obtained, and result shows, the carbon ball that supports platinum prepared by the present invention has larger catalysis area; The carbon ball that supports platinum that the present invention will obtain is as the decorative material of electrode, obtain carbon ball/platinum modified electrode, by the carbon ball that obtains/platinum modified electrode for the reduction of oxygen and the catalytic oxidation of methyl alcohol, result shows, carbon ball prepared by the present invention supports after platinum to have higher catalytic activity the reduction of oxygen and the oxidation of methyl alcohol are had to good electrocatalysis characteristic.

Embodiment 5

The 32.7mg Metha Amino Phenon is joined in the mixing solutions of 12mL water and 4.8mL methyl alcohol, 30 ℃ of lower stirring and dissolving after 10 minutes, adding wherein 33.4 μ L mass concentrations is 28% ammoniacal liquor, the mixing solutions that then will obtain stirs after 20 minutes and adds wherein 46 μ L formaldehyde, stir after 4 hours, the mixing solutions obtained is placed in to the 20mL reactor, stirred 24 hours under 100 ℃.By the reaction product that obtains under the 8000rpm rotating speed centrifugal 5 minutes, by obtain centrifugal after solid washing twice, under 80 ℃ dry 12 hours, obtain m-aminophenyl resinox ball.

The quality of the m-aminophenyl resinox ball that weighing of the present invention obtains is 43.3mg, and calculating productive rate is 85.4%.The present invention carries out the scanning electron microscope scanning analysis to the m-aminophenyl resinox ball obtained, result shows, phenolic resin balls prepared by the present invention has higher monodispersity, the particle diameter of m-aminophenyl resinox ball prepared by the present embodiment is 426nm, monodispersity is 2.3%, result is as shown in table 1, the detected result of m-aminophenyl resinox ball prepared for the embodiment of the present invention and comparative example by table 1.

Embodiment 6

The 32.7mg Metha Amino Phenon is joined in the mixing solutions of 12mL water and 4.8mL ethanol, 30 ℃ of lower stirring and dissolving after 10 minutes, adding wherein 60 μ L mass concentrations is 28% ammoniacal liquor, the mixing solutions that then will obtain stirs after 20 minutes and adds wherein 46 μ L formaldehyde, stir after 4 hours, the mixing solutions obtained is placed in to the 20mL reactor, stirred 24 hours under 100 ℃.By the reaction product that obtains under the 8000rpm rotating speed centrifugal 5 minutes, by obtain centrifugal after solid washing twice, under 80 ℃ dry 12 hours, obtain m-aminophenyl resinox ball.

The quality of the m-aminophenyl resinox ball that weighing of the present invention obtains is 44.1mg, and calculating productive rate is 87.0%.The present invention carries out the scanning electron microscope scanning analysis to the m-aminophenyl resinox ball obtained, result shows, phenolic resin balls prepared by the present invention has higher monodispersity, the particle diameter of m-aminophenyl resinox ball prepared by the present embodiment is 413nm, monodispersity is 2.4%, result is as shown in table 1, the detected result of m-aminophenyl resinox ball prepared for the embodiment of the present invention and comparative example by table 1.

Embodiment 7

The 32.7mg Metha Amino Phenon is joined in the mixing solutions of 12mL water and 4.8mL ethanol, 30 ℃ of lower stirring and dissolving after 10 minutes, adding wherein 90 μ L mass concentrations is 28% ammoniacal liquor, the mixing solutions that then will obtain stirs after 20 minutes and adds wherein 46 μ L formaldehyde, stir after 4 hours, the mixing solutions obtained is placed in to the 20mL reactor, stirred 24 hours under 100 ℃.By the reaction product that obtains under the 8000rpm rotating speed centrifugal 5 minutes, by obtain centrifugal after solid washing twice, under 80 ℃ dry 12 hours, obtain m-aminophenyl resinox ball.

The quality of the m-aminophenyl resinox ball that weighing of the present invention obtains is 37.2mg, and calculating productive rate is 74.2%.The present invention carries out the scanning electron microscope scanning analysis to the m-aminophenyl resinox ball obtained, result shows, phenolic resin balls prepared by the present invention has higher monodispersity, the particle diameter of m-aminophenyl resinox ball prepared by the present embodiment is 362nm, monodispersity is 2.1%, result is as shown in table 1, the detected result of m-aminophenyl resinox ball prepared for the embodiment of the present invention and comparative example by table 1.

Embodiment 8

The 32.7mg Metha Amino Phenon is joined in the mixing solutions of 12mL water and 4.8mL ethanol, 30 ℃ of lower stirring and dissolving after 10 minutes, adding wherein 180 μ L mass concentrations is 28% ammoniacal liquor, the mixing solutions that then will obtain stirs after 20 minutes and adds wherein 46 μ L formaldehyde, stir after 4 hours, the mixing solutions obtained is placed in to the 20mL reactor, stirred 24 hours under 100 ℃.By the reaction product that obtains under the 8000rpm rotating speed centrifugal 5 minutes, by obtain centrifugal after solid washing twice, under 80 ℃ dry 12 hours, obtain m-aminophenyl resinox ball.

The quality of the m-aminophenyl resinox ball that weighing of the present invention obtains is 30.3mg, and calculating productive rate is 60.4%.The present invention carries out the scanning electron microscope scanning analysis to the m-aminophenyl resinox ball obtained, result shows, phenolic resin balls prepared by the present invention has higher monodispersity, the particle diameter of m-aminophenyl resinox ball prepared by the present embodiment is 331nm, monodispersity is 2.2%, result is as shown in table 1, the detected result of m-aminophenyl resinox ball prepared for the embodiment of the present invention and comparative example by table 1.

The present invention carries out the experiment of hydrogen adsorption desorption to the carbon ball that supports platinum obtained, and result shows, the carbon ball that supports platinum prepared by the present invention has larger catalysis area; The carbon ball that supports platinum that the present invention will obtain is as the decorative material of electrode, obtain carbon ball/platinum modified electrode, by the carbon ball that obtains/platinum modified electrode for the reduction of sample and the catalytic oxidation of methyl alcohol, result shows, carbon ball prepared by the present invention has higher catalytic activity after supporting platinum, and the reduction of oxygen and the oxidation of methyl alcohol are had to good electrocatalysis characteristic.

Embodiment 9

The 32.7mg Metha Amino Phenon is joined in the mixing solutions of 12mL water and 4.8mL ethanol, 30 ℃ of lower stirring and dissolving after 10 minutes, adding wherein 240 μ L mass concentrations is 28% ammoniacal liquor, the mixing solutions that then will obtain stirs after 20 minutes and adds wherein 46 μ L formaldehyde, stir after 4 hours, the mixing solutions obtained is placed in to the 20mL reactor, stirred 24 hours under 100 ℃.By the reaction product that obtains under the 8000rpm rotating speed centrifugal 5 minutes, by obtain centrifugal after solid washing twice, under 80 ℃ dry 12 hours, obtain m-aminophenyl resinox ball.

The quality of the m-aminophenyl resinox ball that weighing of the present invention obtains is 23.3mg, and calculating productive rate is 51.1%.The present invention carries out the scanning electron microscope scanning analysis to the m-aminophenyl resinox ball obtained, result shows, phenolic resin balls prepared by the present invention has higher monodispersity, the particle diameter of m-aminophenyl resinox ball prepared by the present embodiment is 297nm, monodispersity is 2.4%, result is as shown in table 1, the detected result of m-aminophenyl resinox ball prepared for the embodiment of the present invention and comparative example by table 1.

Embodiment 10

The 9mg Metha Amino Phenon is joined in the mixing solutions of 12mL water and 4.8mL ethanol, 30 ℃ of lower stirring and dissolving after 10 minutes, adding wherein 60 μ L mass concentrations is 28% ammoniacal liquor, the mixing solutions that then will obtain stirs after 20 minutes and adds wherein 12.6 μ L formaldehyde, stir after 4 hours, the mixing solutions obtained is placed in to the 20mL reactor, stirred 24 hours under 100 ℃.By the reaction product that obtains under the 8000rpm rotating speed centrifugal 5 minutes, by obtain centrifugal after solid washing twice, under 80 ℃ dry 12 hours, obtain m-aminophenyl resinox ball.

The quality of the m-aminophenyl resinox ball that weighing of the present invention obtains is 10.5mg, and calculating productive rate is 75.0%.The present invention carries out the scanning electron microscope scanning analysis to the m-aminophenyl resinox ball obtained, result shows, phenolic resin balls prepared by the present invention has higher monodispersity, the particle diameter of m-aminophenyl resinox ball prepared by the present embodiment is 80nm, monodispersity is 1.1%, result is as shown in table 1, the detected result of m-aminophenyl resinox ball prepared for the embodiment of the present invention and comparative example by table 1.

Embodiment 11

The 12mg Metha Amino Phenon is joined in the mixing solutions of 12mL water and 4.8mL ethanol, 30 ℃ of lower stirring and dissolving after 10 minutes, adding wherein 60 μ L mass concentrations is 28% ammoniacal liquor, the mixing solutions that then will obtain stirs after 20 minutes and adds wherein 16.8 μ L formaldehyde, stir after 4 hours, the mixing solutions obtained is placed in to the 20mL reactor, stirred 24 hours under 100 ℃.By the reaction product that obtains under the 8000rpm rotating speed centrifugal 5 minutes, by obtain centrifugal after solid washing twice, under 80 ℃ dry 12 hours, obtain m-aminophenyl resinox ball.The quality of the m-aminophenyl resinox ball that weighing of the present invention obtains is 14.5mg, and calculating productive rate is 78.0%.The present invention carries out the scanning electron microscope scanning analysis to the m-aminophenyl resinox ball obtained, result shows, phenolic resin balls prepared by the present invention has higher monodispersity, the particle diameter of m-aminophenyl resinox ball prepared by the present embodiment is 117nm, monodispersity is 0.94%, result is as shown in table 1, the detected result of m-aminophenyl resinox ball prepared for the embodiment of the present invention and comparative example by table 1.

Embodiment 12

The 18mg Metha Amino Phenon is joined in the mixing solutions of 12mL water and 4.8mL ethanol, 30 ℃ of lower stirring and dissolving after 10 minutes, adding wherein 60 μ L mass concentrations is 28% ammoniacal liquor, the mixing solutions that then will obtain stirs after 20 minutes and adds wherein 25.2 μ L formaldehyde, stir after 4 hours, the mixing solutions obtained is placed in to the 20mL reactor, stirred 24 hours under 100 ℃.By the reaction product that obtains under the 8000rpm rotating speed centrifugal 5 minutes, by obtain centrifugal after solid washing twice, under 80 ℃ dry 12 hours, obtain m-aminophenyl resinox ball.The quality of the m-aminophenyl resinox ball that weighing of the present invention obtains is 22.3mg, and calculating productive rate is 80.1%.The present invention carries out the scanning electron microscope scanning analysis to the m-aminophenyl resinox ball obtained, result shows, phenolic resin balls prepared by the present invention has higher monodispersity, the particle diameter of m-aminophenyl resinox ball prepared by the present embodiment is 167nm, monodispersity is 0.81%, result is as shown in table 1, the detected result of m-aminophenyl resinox ball prepared for the embodiment of the present invention and comparative example by table 1.

Embodiment 13

The 30mg Metha Amino Phenon is joined in the mixing solutions of 12mL water and 4.8mL Virahol, 30 ℃ of lower stirring and dissolving after 10 minutes, adding wherein 60 μ L mass concentrations is 28% ammoniacal liquor, the mixing solutions that then will obtain stirs after 20 minutes and adds wherein 42 μ L formaldehyde, stir after 4 hours, the mixing solutions obtained is placed in to the 20mL reactor, stirred 24 hours under 100 ℃.By the reaction product that obtains under the 8000rpm rotating speed centrifugal 5 minutes, by obtain centrifugal after solid washing twice, under 80 ℃ dry 12 hours, obtain m-aminophenyl resinox ball.

The quality of the m-aminophenyl resinox ball that weighing of the present invention obtains is 38.2mg, and calculating productive rate is 82.2%.The present invention carries out the scanning electron microscope scanning analysis to the m-aminophenyl resinox ball obtained, result shows, phenolic resin balls prepared by the present invention has higher monodispersity, the particle diameter of m-aminophenyl resinox ball prepared by the present embodiment is 323nm, monodispersity is 2.8%, result is as shown in table 1, the detected result of m-aminophenyl resinox ball prepared for the embodiment of the present invention and comparative example by table 1.

Embodiment 14

The 42mg Metha Amino Phenon is joined in the mixing solutions of 12mL water and 4.8mL Virahol, 30 ℃ of lower stirring and dissolving after 10 minutes, adding wherein 60 μ L mass concentrations is 28% ammoniacal liquor, the mixing solutions that then will obtain stirs after 20 minutes and adds wherein 58.8 μ L formaldehyde, stir after 4 hours, the mixing solutions obtained is placed in to the 20mL reactor, stirred 24 hours under 100 ℃.By the reaction product that obtains under the 8000rpm rotating speed centrifugal 5 minutes, by obtain centrifugal after solid washing twice, under 80 ℃ dry 12 hours, obtain m-aminophenyl resinox ball.

The quality of the m-aminophenyl resinox ball that weighing of the present invention obtains is 54.9mg, and calculating productive rate is 84.3%.The present invention carries out the scanning electron microscope scanning analysis to the m-aminophenyl resinox ball obtained, result shows, phenolic resin balls prepared by the present invention has higher monodispersity, the particle diameter of m-aminophenyl resinox ball prepared by the present embodiment is 362nm, monodispersity is 2.9%, result is as shown in table 1, the detected result of m-aminophenyl resinox ball prepared for the embodiment of the present invention and comparative example by table 1.

Embodiment 15

The 90mg Metha Amino Phenon is joined in the mixing solutions of 12mL water and 4.8mL Virahol, 30 ℃ of lower stirring and dissolving after 10 minutes, adding wherein 60 μ L mass concentrations is 29% ammoniacal liquor, the mixing solutions that then will obtain stirs after 20 minutes and adds wherein 126 μ L formaldehyde, stir after 4 hours, the mixing solutions obtained is placed in to the 20mL reactor, stirred 24 hours under 100 ℃.By the reaction product that obtains under the 8000rpm rotating speed centrifugal 5 minutes, by obtain centrifugal after solid washing twice, under 80 ℃ dry 12 hours, obtain m-aminophenyl resinox ball.

The quality of the m-aminophenyl resinox ball that weighing of the present invention obtains is 125.4mg, and calculating productive rate is 89.9%.The present invention carries out the scanning electron microscope scanning analysis to the m-aminophenyl resinox ball obtained, result shows, phenolic resin balls prepared by the present invention has higher monodispersity, the particle diameter of m-aminophenyl resinox ball prepared by the present embodiment is 458nm, monodispersity is 2.4%, result is as shown in table 1, the detected result of m-aminophenyl resinox ball prepared for the embodiment of the present invention and comparative example by table 1.

Embodiment 16

The 120mg Metha Amino Phenon is joined in the mixing solutions of 12mL water and 4.8mL Virahol, 30 ℃ of lower stirring and dissolving after 10 minutes, adding wherein 60 μ L mass concentrations is 29% ammoniacal liquor, the mixing solutions that then will obtain stirs after 20 minutes and adds wherein 168 μ L formaldehyde, stir after 4 hours, the mixing solutions obtained is placed in to the 20mL reactor, stirred 24 hours under 100 ℃.By the reaction product that obtains under the 8000rpm rotating speed centrifugal 5 minutes, by obtain centrifugal after solid washing twice, under 80 ℃ dry 12 hours, obtain m-aminophenyl resinox ball.

The quality of the m-aminophenyl resinox ball that weighing of the present invention obtains is 175.2mg, and calculating productive rate is 94.2%.The present invention carries out the scanning electron microscope scanning analysis to the m-aminophenyl resinox ball obtained, result shows, phenolic resin balls prepared by the present invention has higher monodispersity, the particle diameter of m-aminophenyl resinox ball prepared by the present embodiment is 492nm, monodispersity is 1.6%, result is as shown in table 1, the detected result of m-aminophenyl resinox ball prepared for the embodiment of the present invention and comparative example by table 1.

The present invention carries out the experiment of hydrogen adsorption desorption to the carbon ball that supports platinum obtained, and result shows, the carbon ball that supports platinum prepared by the present invention has larger catalysis area; The carbon ball that supports platinum that the present invention will obtain is as the decorative material of electrode, obtain carbon ball/platinum modified electrode, by the carbon ball that obtains/platinum modified electrode for the reduction of oxygen and the catalytic oxidation of methyl alcohol, result shows, carbon ball prepared by the present invention has higher catalytic activity after supporting platinum, to the good electrocatalysis characteristic that has of the reduction of oxygen and methyl alcohol.

Embodiment 17

The 180mg Metha Amino Phenon is joined in the mixing solutions of 12mL water and 4.8mL Virahol, 30 ℃ of lower stirring and dissolving after 10 minutes, adding wherein 60 μ L mass concentrations is 29% ammoniacal liquor, the mixing solutions that then will obtain stirs after 20 minutes and adds wherein 252 μ L formaldehyde, stir after 4 hours, the mixing solutions obtained is placed in to the 20mL reactor, stirred 24 hours under 100 ℃.By the reaction product that obtains under the 8000rpm rotating speed centrifugal 5 minutes, by obtain centrifugal after solid washing twice, under 80 ℃ dry 12 hours, obtain m-aminophenyl resinox ball.

The quality of the m-aminophenyl resinox ball that weighing of the present invention obtains is 264mg, and calculating productive rate is 94.9%.The present invention carries out the scanning electron microscope scanning analysis to the m-aminophenyl resinox ball obtained, result shows, phenolic resin balls prepared by the present invention has higher monodispersity, the particle diameter of m-aminophenyl resinox ball prepared by the present embodiment is 528nm, monodispersity is 2.1%, result is as shown in table 1, the detected result of m-aminophenyl resinox ball prepared for the embodiment of the present invention and comparative example by table 1.

Embodiment 18

The 240mg Metha Amino Phenon is joined in the mixing solutions of 12mL water and 4.8mL Virahol, 30 ℃ of lower stirring and dissolving after 10 minutes, adding wherein 60 μ L mass concentrations is 29% ammoniacal liquor, the mixing solutions that then will obtain stirs after 20 minutes and adds wherein 336 μ L formaldehyde, stir after 4 hours, the mixing solutions obtained is placed in to the 20mL reactor, stirred 24 hours under 100 ℃.By the reaction product that obtains under the 8000rpm rotating speed centrifugal 5 minutes, by obtain centrifugal after solid washing twice, under 80 ℃ dry 12 hours, obtain m-aminophenyl resinox ball.

The quality of the m-aminophenyl resinox ball that weighing of the present invention obtains is 264.8mg, and calculating productive rate is 94.9%.The present invention carries out the scanning electron microscope scanning analysis to the m-aminophenyl resinox ball obtained, result shows, phenolic resin balls prepared by the present invention has higher monodispersity, the particle diameter of m-aminophenyl resinox ball prepared by the present embodiment is 555nm, monodispersity is 1.4%, result is as shown in table 1, the detected result of m-aminophenyl resinox ball prepared for the embodiment of the present invention and comparative example by table 1.

Embodiment 19

The 300mg Metha Amino Phenon is joined in the mixing solutions of 12mL water and 4.8mL ethanol, 30 ℃ of lower stirring and dissolving after 10 minutes, adding wherein 60 μ L mass concentrations is 29% ammoniacal liquor, the mixing solutions that then will obtain stirs after 20 minutes and adds wherein 320 μ L formaldehyde, stir after 4 hours, the mixing solutions obtained is placed in to the 20mL reactor, stirred 24 hours under 100 ℃.By the reaction product that obtains under the 8000rpm rotating speed centrifugal 5 minutes, by obtain centrifugal after solid washing twice, under 80 ℃ dry 12 hours, obtain m-aminophenyl resinox ball.

The quality of the m-aminophenyl resinox ball that weighing of the present invention obtains is 441.8mg, and calculating productive rate is 95.0%.The present invention carries out the scanning electron microscope scanning analysis to the m-aminophenyl resinox ball obtained, result shows, phenolic resin balls prepared by the present invention has higher monodispersity, the particle diameter of m-aminophenyl resinox ball prepared by the present embodiment is 617nm, monodispersity is 1.8%, result is as shown in table 1, the detected result of m-aminophenyl resinox ball prepared for the embodiment of the present invention and comparative example by table 1.

The present invention carries out the experiment of hydrogen adsorption desorption to the carbon ball that supports platinum obtained, and result shows, the carbon ball that supports platinum prepared by the present invention has larger catalysis area; The carbon ball that supports platinum that the present invention will obtain is as the decorative material of electrode, obtain carbon ball/platinum modified electrode, by the carbon ball that obtains/platinum modified electrode for the reduction of oxygen and the catalytic oxidation of methyl alcohol, result shows, carbon ball prepared by the present invention has higher catalytic activity after supporting platinum, and the reduction of oxygen and the catalytic oxidation of methyl alcohol are had to good electrocatalysis characteristic.

Embodiment 20

The 420mg Metha Amino Phenon is joined in the mixing solutions of 12mL water and 4.8mL ethanol, 30 ℃ of lower stirring and dissolving after 10 minutes, adding wherein 60 μ L mass concentrations is 29% ammoniacal liquor, the mixing solutions that then will obtain stirs after 20 minutes and adds wherein 588 μ L. formaldehyde, stir after 4 hours, the mixing solutions obtained is placed in to the 20mL reactor, stirred 24 hours under 100 ℃.By the reaction product that obtains under the 8000rpm rotating speed centrifugal 5 minutes, by obtain centrifugal after solid washing twice, under 80 ℃ dry 12 hours, obtain m-aminophenyl resinox ball.

The quality of the m-aminophenyl resinox ball that weighing of the present invention obtains is 626.9mg, and calculating productive rate is 96.0%.The present invention carries out the scanning electron microscope scanning analysis to the m-aminophenyl resinox ball obtained, result shows, phenolic resin balls prepared by the present invention has higher monodispersity, the particle diameter of m-aminophenyl resinox ball prepared by the present embodiment is 654nm, monodispersity is 3.4%, result is as shown in table 1, the detected result of m-aminophenyl resinox ball prepared for the embodiment of the present invention and comparative example by table 1.

Embodiment 21

The 60mg Metha Amino Phenon is joined in 16.8mL water, 30 ℃ of lower stirring and dissolving after 10 minutes, adding wherein 60 μ L mass concentrations is 30% ammoniacal liquor, the mixing solutions that then will obtain stirs after 20 minutes and adds wherein 84 μ L formaldehyde, stir after 4 hours, the mixing solutions obtained is placed in to the 20mL reactor, stirred 24 hours under 100 ℃.By the reaction product that obtains under the 8000rpm rotating speed centrifugal 5 minutes, by obtain centrifugal after solid washing twice, under 80 ℃ dry 12 hours, obtain m-aminophenyl resinox ball.

The quality of the m-aminophenyl resinox ball that weighing of the present invention obtains is 80.9mg, and calculating productive rate is 87.2%.The present invention carries out the scanning electron microscope scanning analysis to the m-aminophenyl resinox ball obtained, result shows, phenolic resin balls prepared by the present invention has higher monodispersity, the particle diameter of m-aminophenyl resinox ball prepared by the present embodiment is 2527nm, monodispersity is 34.1%, result is as shown in table 1, the detected result of m-aminophenyl resinox ball prepared for the embodiment of the present invention and comparative example by table 1.

Embodiment 22

The 60mg Metha Amino Phenon is joined in the mixing solutions of 14.8mL water and 2mL ethylene glycol, 30 ℃ of lower stirring and dissolving after 10 minutes, adding wherein 60 μ L mass concentrations is 30% ammoniacal liquor, the mixing solutions that then will obtain stirs after 20 minutes and adds wherein 84 μ L formaldehyde, stir after 4 hours, the mixing solutions obtained is placed in to the 20mL reactor, stirred 24 hours under 100 ℃.By the reaction product that obtains under the 8000rpm rotating speed centrifugal 5 minutes, by obtain centrifugal after solid washing twice, under 80 ℃ dry 12 hours, obtain m-aminophenyl resinox ball.

The quality of the m-aminophenyl resinox ball that weighing of the present invention obtains is 84.8mg, and calculating productive rate is 91.2%.The present invention carries out the scanning electron microscope scanning analysis to the m-aminophenyl resinox ball obtained, result shows, phenolic resin balls prepared by the present invention has higher monodispersity, the particle diameter of m-aminophenyl resinox ball prepared by the present embodiment is 1150nm, monodispersity is 10.1%, result is as shown in table 1, the detected result of m-aminophenyl resinox ball prepared for the embodiment of the present invention and comparative example by table 1.

Embodiment 23

The 60mg Metha Amino Phenon is joined in the mixing solutions of 13.8mL water and 3mL ethylene glycol, 30 ℃ of lower stirring and dissolving after 10 minutes, adding wherein 60 μ L mass concentrations is 30% ammoniacal liquor, the mixing solutions that then will obtain stirs after 20 minutes and adds wherein 84 μ L formaldehyde, stir after 4 hours, the mixing solutions obtained is placed in to the 20mL reactor, stirred 24 hours under 100 ℃.By the reaction product that obtains under the 8000rpm rotating speed centrifugal 5 minutes, by obtain centrifugal after solid washing twice, under 80 ℃ dry 12 hours, obtain m-aminophenyl resinox ball.

The quality of the m-aminophenyl resinox ball that weighing of the present invention obtains is 85.9mg, and calculating productive rate is 92.4%.The present invention carries out the scanning electron microscope scanning analysis to the m-aminophenyl resinox ball obtained, result shows, phenolic resin balls prepared by the present invention has higher monodispersity, the particle diameter of m-aminophenyl resinox ball prepared by the present embodiment is 706nm, monodispersity is 7.4%, result is as shown in table 1, the detected result of m-aminophenyl resinox ball prepared for the embodiment of the present invention and comparative example by table 1.

Embodiment 24

The 60mg Metha Amino Phenon is joined in the mixing solutions of 11.8mL water and 5mL ethylene glycol, 30 ℃ of lower stirring and dissolving after 10 minutes, adding wherein 60 μ L mass concentrations is 30% ammoniacal liquor, the mixing solutions that then will obtain stirs after 20 minutes and adds wherein 84 μ L formaldehyde, stir after 4 hours, the mixing solutions obtained is placed in to the 20mL reactor, stirred 24 hours under 100 ℃.By the reaction product that obtains under the 8000rpm rotating speed centrifugal 5 minutes, by obtain centrifugal after solid washing twice, under 80 ℃ dry 12 hours, obtain m-aminophenyl resinox ball.

The quality of the m-aminophenyl resinox ball that weighing of the present invention obtains is 81.2mg, and calculating productive rate is 87.4%.The present invention carries out the scanning electron microscope scanning analysis to the m-aminophenyl resinox ball obtained, result shows, phenolic resin balls prepared by the present invention has higher monodispersity, the particle diameter of m-aminophenyl resinox ball prepared by the present embodiment is 581nm, monodispersity is 3.5%, result is as shown in table 1, the detected result of m-aminophenyl resinox ball prepared for the embodiment of the present invention and comparative example by table 1.

Embodiment 25

The 60mg Metha Amino Phenon is joined in the mixing solutions of 9.6mL water and 7.2mL ethylene glycol, 30 ℃ of lower stirring and dissolving after 10 minutes, add wherein 60 μ L quadrols, the mixing solutions that then will obtain stirs after 20 minutes and adds wherein 84 μ L formaldehyde, stir after 4 hours, the mixing solutions obtained is placed in to the 20mL reactor, stirred 24 hours under 100 ℃.By the reaction product that obtains under the 8000rpm rotating speed centrifugal 5 minutes, by obtain centrifugal after solid washing twice, under 80 ℃ dry 12 hours, obtain m-aminophenyl resinox ball.

The quality of the m-aminophenyl resinox ball that weighing of the present invention obtains is 80.9mg, and calculating productive rate is 86.9%.The present invention carries out the scanning electron microscope scanning analysis to the m-aminophenyl resinox ball obtained, result shows, phenolic resin balls prepared by the present invention has higher monodispersity, the particle diameter of m-aminophenyl resinox ball prepared by the present embodiment is 486nm, monodispersity is 2.5%, result is as shown in table 1, the detected result of m-aminophenyl resinox ball prepared for the embodiment of the present invention and comparative example by table 1.

Embodiment 26

The 60mg Metha Amino Phenon is joined in the mixing solutions of 8.4mL water and 8.4mL ethylene glycol, 30 ℃ of lower stirring and dissolving after 10 minutes, add wherein 60 μ L quadrols, the mixing solutions that then will obtain stirs after 20 minutes and adds wherein 84 μ L formaldehyde, stir after 4 hours, the mixing solutions obtained is placed in to the 20mL reactor, stirred 24 hours under 100 ℃.By the reaction product that obtains under the 8000rpm rotating speed centrifugal 5 minutes, by obtain centrifugal after solid washing twice, under 80 ℃ dry 12 hours, obtain m-aminophenyl resinox ball.

The quality of the m-aminophenyl resinox ball that weighing of the present invention obtains is 79.6mg, and calculating productive rate is 85.6%.The present invention carries out the scanning electron microscope scanning analysis to the m-aminophenyl resinox ball obtained, result shows, phenolic resin balls prepared by the present invention has higher monodispersity, the particle diameter of m-aminophenyl resinox ball prepared by the present embodiment is 463nm, monodispersity is 2.5%, result is as shown in table 1, the detected result of m-aminophenyl resinox ball prepared for the embodiment of the present invention and comparative example by table 1.

Embodiment 27

The 60mg Metha Amino Phenon is joined in the mixing solutions of 16.8mL ethanol, 30 ℃ of lower stirring and dissolving after 10 minutes, add wherein 60 μ L quadrols, the mixing solutions that then will obtain stirs after 20 minutes and adds wherein 84 μ L formaldehyde, stir after 4 hours, the mixing solutions obtained is placed in to the 20mL reactor, stirred 24 hours under 100 ℃.By the reaction product that obtains under the 8000rpm rotating speed centrifugal 5 minutes, by obtain centrifugal after solid washing twice, under 80 ℃ dry 12 hours, obtain m-aminophenyl resinox ball.

The quality of the m-aminophenyl resinox ball that weighing of the present invention obtains is 78.3mg, and calculating productive rate is 84.2%.The present invention carries out the scanning electron microscope scanning analysis to the m-aminophenyl resinox ball obtained, result shows, phenolic resin balls prepared by the present invention has higher monodispersity, the particle diameter of m-aminophenyl resinox ball prepared by the present embodiment is 445nm, monodispersity is 2.1%, result is as shown in table 1, the detected result of m-aminophenyl resinox ball prepared for the embodiment of the present invention and comparative example by table 1.

Embodiment 28

The quality of the m-aminophenyl resinox ball that weighing of the present invention obtains is 79.4mg, and calculating productive rate is 85.3%.The present invention carries out the scanning electron microscope scanning analysis to the m-aminophenyl resinox ball obtained, result shows, phenolic resin balls prepared by the present invention has higher monodispersity, the particle diameter of m-aminophenyl resinox ball prepared by the present embodiment is 285nm, monodispersity is 1.6%, result is as shown in table 1, the detected result of m-aminophenyl resinox ball prepared for the embodiment of the present invention and comparative example by table 1.

Embodiment 29

The 60mg Metha Amino Phenon is joined in the 16.8mL Virahol, 30 ℃ of lower stirring and dissolving after 10 minutes, add wherein 60 μ L quadrols, the mixing solutions that then will obtain stirs after 20 minutes and adds wherein 84 μ L formaldehyde, stir after 4 hours, the mixing solutions obtained is placed in to the 20mL reactor, stirred 24 hours under 100 ℃.By the reaction product that obtains under the 8000rpm rotating speed centrifugal 5 minutes, by obtain centrifugal after solid washing twice, under 80 ℃ dry 12 hours, obtain m-aminophenyl resinox ball.

The quality of the m-aminophenyl resinox ball that weighing of the present invention obtains is 81.6mg, and calculating productive rate is 87.7%.The present invention carries out the scanning electron microscope scanning analysis to the m-aminophenyl resinox ball obtained, result shows, phenolic resin balls prepared by the present invention has higher monodispersity, the particle diameter of m-aminophenyl resinox ball prepared by the present embodiment is 283nm, monodispersity is 1.6%, result is as shown in table 1, the detected result of m-aminophenyl resinox ball prepared for the embodiment of the present invention and comparative example by table 1.

The detected result of m-aminophenyl resinox ball prepared by table 1 embodiment of the present invention and comparative example

Comparative example 1

The 32.7mg Metha Amino Phenon is joined in the mixing solutions of 4.8mL water and 12mL ethanol, 30 ℃ of lower stirring and dissolving, after 10 minutes, add wherein 46 μ L formaldehyde, stir after 4 hours, the mixing solutions obtained is placed in to the 20mL reactor, stirred 24 hours under 100 ℃.By the reaction product that obtains under the 8000rpm rotating speed centrifugal 5 minutes, by obtain centrifugal after solid washing twice, under 80 ℃ dry 12 hours, obtain m-aminophenyl resinox ball.

The m-aminophenyl resinox ball that the present invention will obtain carries out the scanning electron microscope scanning analysis, and result shows, the distribution of sizes of the m-aminophenyl resinox ball that this comparative example obtains is wider, and monodispersity is poor.

As seen from the above embodiment, the invention provides a kind of preparation method of m-aminophenyl resinox ball and the preparation method of carbon ball, the present invention carries out polyreaction by Metha Amino Phenon and formaldehyde under the condition of ammoniacal liquor and/or quadrol existence, obtain m-aminophenyl resinox ball.Formaldehyde, Metha Amino Phenon and in solvent, form micella as ammoniacal liquor and/or the quadrol of catalyzer, in micella, ammoniacal liquor and/or quadrol catalysis Metha Amino Phenon and formaldehyde polymerization reaction take place, thus obtain m-aminophenyl resinox ball; In reaction process, ammoniacal liquor and/or quadrol can be distributed in the surface of micella, produce positive charge, the effect of Coulomb repulsion has suppressed the bonding between micella, make the m-aminophenyl obtained resinox ball that higher monodispersity be arranged, the size of resin balls can be regulated on a large scale, is conducive to its application.The m-aminophenyl resinox ball that the present invention will obtain obtains the carbon ball after calcining, and therefore carbon ball provided by the invention also has higher monodispersity.

The above is only the preferred embodiment of the present invention; it should be pointed out that for those skilled in the art, under the premise without departing from the principles of the invention; can also make some improvements and modifications, these improvements and modifications also should be considered as protection scope of the present invention.

Claims

1. the preparation method of a m-aminophenyl resinox ball comprises the following steps:

Described catalyzer is ammoniacal liquor and/or quadrol;

Described solvent is the mixed solvent of water, alcohol or water and alcohol compound;

The temperature of described polyreaction is 50 ℃～200 ℃;

The time of described polyreaction is 4 hours～50 hours;

The volumetric molar concentration of described catalyzer is 0.1mmol/L～800mmol/L;

The volume of described formaldehyde and the mass ratio of described Metha Amino Phenon are (10～900) μ L:(2～800) mg.

2. preparation method according to claim 1, is characterized in that, described catalyzer is ammoniacal liquor.

3. preparation method according to claim 1, is characterized in that, described alcohol compound is one or more in methyl alcohol, ethanol, Virahol and ethylene glycol.

4. preparation method according to claim 3, is characterized in that, described alcohol compound is ethanol.

5. preparation method according to claim 1, is characterized in that, the temperature of described dissolving is 0 ℃～90 ℃.

6. the preparation method of a carbon ball comprises the following steps:

The m-aminophenyl resinox ball that the described preparation method of claim 1～5 any one obtains is calcined, obtained the carbon ball.

7. method according to claim 6, is characterized in that, the temperature of described calcining is 300 ℃～800 ℃.

8. method according to claim 6, is characterized in that, the time of described calcining is 2 hours～12 hours.