CN101555008A - Method for preparing monodisperse carbon microsphere with controllable configuration - Google Patents
Method for preparing monodisperse carbon microsphere with controllable configuration Download PDFInfo
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- CN101555008A CN101555008A CNA2009100648973A CN200910064897A CN101555008A CN 101555008 A CN101555008 A CN 101555008A CN A2009100648973 A CNA2009100648973 A CN A2009100648973A CN 200910064897 A CN200910064897 A CN 200910064897A CN 101555008 A CN101555008 A CN 101555008A
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Abstract
The invention belongs to the field of novel carbon material preparation and particularly discloses a method for preparing a monodisperse carbon microsphere with controllable configuration. The method comprises the following steps of: firstly carrying out an soap-free emulsion polymerization by using a cinnamene taken as monomer, a water taken as medium, a water-soluble initiator and a cross linking agent so as to synthesize a monodispersion crosslinked polystyrene microsphere; subsequently carrying out a Friedel -Crafts alkylation reaction by arranging the crosslinked polystyrene microsphere into a Chlorinated methanes organic solvent/metal chloride catalyst system; removing the organic solvent and the catalyst after reaction ends; obtaining the crosslinked polystyrene microsphere after drying; and finally obtaining the monodispersion carbon microsphere by carbonizing the crosslinked polystyrene microsphere with the oxygen isolated. The method has simple and feasible process, low cost of experimental equipment and easy realization, can obtain the monodispersion carbon microsphere with regular and uniform ball shape and can realize controlling the final configuration of the carbon microsphere by simply adjusting the experimental parameters.
Description
Technical field
The invention belongs to the new carbon preparation field, particularly a kind of method for preparing the controlled monodisperse carbon microsphere of form.
Background technology
Carbosphere is a kind of of new carbon, and profile is spherical shape or approximate circle is spherical, and size distribution is a kind of new carbon that grows up in recent ten years on nanometer or micron number magnitude.Because its intensity height, thermal resistance is big, and density is little, thermostability and chemical stability excellence, and advantage such as heat-conductivity conducting is functional, and day by day be subject to people's attention, become the focus of research, be applied to growing field.
People have developed the preparation that several different methods realizes carbosphere at present, as chemical vapour deposition (MiaoJ Y, Hwang D W, Narasimhulu K V, et al.Carbon, 2004,42:813; Qian H S, Han F M, Zhang B, et al.Carbon, 2004,42:761), chemical reduction (Liu J W, Shao M W, Tang Q, et al.Carbon, 2003,41:1682), solvent thermal (Wang Q, Li H, Chen L Q, et al.Carbon, 2001,39:2211), pyrolytic decomposition (Xu L Q, Zhang W Q, Yang Q, et al.Carbon, 2005,43:1090), arc-over (Qiu J S, Li Y F, Wang Y P, et al.Carbon, 2003,41:767) etc., by some method in these, people can prepare a large amount of carbospheres easily, comprise hollow carbosphere and solid carbon microballoon.
In aforesaid method, chemical Vapor deposition process is used the most extensively.In this method, reactive material issues biochemical reaction in the gaseous state condition, generates solid matter and is deposited on the solid matrix surface of heating, and then make solid material.It belongs to the gaseous state mass transfer process of former subcategory in essence, can prepare carbosphere quickly and easily, if adopt clean carbon source, is hopeful to prepare purified carbosphere.But, general unpredictable or control carbon spherolite size and the form directly of this method, microspherulite diameter presents the polydispersion feature, and shape mostly is irregular sphere.
Be seen at present the prepared carbosphere of reported method and mostly had in following several shortcoming one or more: spherical irregular (the spherical distortion); The size heterogeneity, size distribution is in hundreds of nanometers even wideer scope; Serious adhesion usually takes place between ball and the ball.In addition, the more important thing is, can only prepare a kind of carbosphere (hollow or solid) of form effectively by existing a certain method, can not prepare solid carbon microballoon or hollow carbosphere to controllability by simple adjusting processing parameter, this also is a focus place in the current carbosphere research topic.
At present, the monodisperse carbon microsphere with a kind of method controllability ground preparation different shape does not have bibliographical information as yet.
Summary of the invention
The object of the present invention is to provide a kind of method for preparing the controlled monodisperse carbon microsphere of form.
The technical solution used in the present invention is as follows:
A kind of method for preparing the controlled monodisperse carbon microsphere of form: at first be that monomer, water are that medium carries out emulsifier-free emulsion polymerization with water soluble starter, linking agent, synthesize monodisperse cross-linked polystyrene microsphere with vinylbenzene; Then this crosslinked polystyrene microsphere is carried out Fu-Ke alkylated reaction in methane chloride organic solvent/metal chloride catalyst system, reaction is removed organic solvent, catalyzer after finishing, and drying obtains the back crosslinked polystyrene microsphere; With back crosslinked polystyrene microsphere starvation charing, promptly obtain carbosphere at last.
Preferably, described water soluble starter is a persulfuric acid salt initiator, and linking agent is Vinylstyrene or Ethylene glycol dimethacrylate.
Further, by mass ratio, each raw material consumption of emulsifier-free emulsion polymerization is a vinylbenzene: water: persulfuric acid salt initiator: linking agent=1: 25～75: 0.03～0.09: 0.2～0.7, each raw material consumption of Fu-Ke alkylated reaction is a crosslinked polystyrene microsphere: methane chloride: metal chloride=1: 50～200: 3～7.
Preferably, persulfuric acid salt initiator is Potassium Persulphate or ammonium persulphate, and methane chloride is tetracol phenixin, chloroform or methylene dichloride, and metal chloride is wherein a kind of or its combination of Aluminum chloride anhydrous, Anhydrous Ferric Chloride, anhydrous stannic chloride.
Further, at first be that monomer, water are that medium and water soluble starter carry out emulsifier-free emulsion polymerization reaction 3～7h in 40～85 ℃ under inert atmosphere with vinylbenzene, add linking agent afterwards again and continue reaction, the time of whole emulsifier-free emulsion polymerization reaction is 22～30h.
Preferably, the adding mode of linking agent is disposable the adding fully or injection adding in batches, and per minute injection 10～20 μ L.
Further, Fu-Ke alkylated reaction temperature is 40～60 ℃, and the time is 2～24h; Carbonization temperature is 600～800 ℃, and the time is 2～4h.
Particularly, emulsifier-free emulsion polymerization is undertaken by following process: at room temperature vinylbenzene and portion water are mixed earlier, the consumption of this portion water is 0.8～0.95 times of water total mass, feed the rare gas element excluding air simultaneously, be warming up to 40～85 ℃ of temperature of reaction afterwards, add the water of initiator and surplus, this is designated as the time of origin of reaction constantly, add linking agent behind reaction 3～7h and continue reaction, the time of whole emulsifier-free emulsion polymerization reaction is 22～30h.
Particularly, Fu-Ke alkylated reaction is undertaken by following process: at room temperature mix earlier methane chloride organic solvent and metal chloride catalyst, the crosslinked polystyrene microsphere that adds the emulsifier-free emulsion polymerization gained behind 10～40min, behind 10～40min, temperature control reacts at 40～60 ℃, this is designated as the time of origin of reaction constantly, finishes behind reaction 2～24h.
Preferably, Fu-Ke alkylated reaction is removed organic solvent, catalyzer with the dilute hydrochloric acid cleaning product of acetone, mass concentration 5～40%, successively in order to avoid influence the purity of carbosphere after finishing, the gained solids gets the back crosslinked polystyrene microsphere with acetone dispersion, drying.
The technology of the present invention effect analysis: Figure 1A, B, C, D and Fig. 2 A, B, C, D are respectively the saturating look Electronic Speculum (TEM) and scanning electron microscope (SEM) photos of embodiment 1,4,8,12 (different alkylated reaction time) gained carbosphere, from Figure 1A, B, C, D and Fig. 2 A, B, C, D, as can be known: the dispersiveness of these carbospheres is all relatively good, the monodispersity of polystyrene microsphere has guaranteed the monodispersity of last gained carbosphere, so the inventive method has overcome the phenomenon that serious adhesion takes place between the carbosphere that often occurs in the traditional method to a certain extent.Simultaneously, it can also be seen that from figure these carbospheres present the spherical shape of rule mostly, size is basic identical, is distributed in the narrower scope of 270～295nm, and this is because of being presoma with the monodisperse polystyrene microsphere, has guaranteed the homogeneity of carbosphere particle diameter.But their internal structure is also inequality, and when the alkylated reaction time was 2h, its corresponding carbon ball had hollow structure, sees Figure 1A; When the alkylated reaction time was 8h, part had hollow structure in its corresponding carbon ball, and part has solid construction, and hollow structure and solid construction are also deposited, and see Figure 1B; When the alkylated reaction time was 16h or 24h, its corresponding carbon ball had solid construction, as Fig. 1 C and D.And then the inventive method has also overcome the limitation that a kind of in the past method can only obtain a kind of carbosphere of form.
Analysis on Mechanism of the present invention: in Fu-Ke alkylation process, organic solvent methane chloride (CCl
4, CCl
3, CHCl
2) and metal chloride catalyst (AlCl
3, FeCl
3, SnCl
4) reaction generates the C positive ion, the C positive ion attack macromolecular chain with the position of the C atom of phenyl ring, the generation that induces reaction.Starting stage, reaction mainly occurs in the surf zone of polystyrene (PS) microballoon.In fact, the organic solvent methane chloride also produces swelling action to microballoon except participating in chemical reaction, that is, the organic solvent molecule can infiltrate microballoon inside gradually, thereby the position of reaction is extended to gradually the interior region of microballoon.Yet this swelling action needs long process, and the surf zone that reaction preferentially is chosen in microballoon all the time takes place, rather than interior region.Like this, if the reaction times is shorter, reaction mainly takes place at the surf zone of microballoon so, only the macromole of surf zone has obtained enough big cross-linking density and molecular weight, so, after the charing step, microballoon is outer to take place that charing is retained and kernel generation thermolysis is removed, thereby forms hollow carbon sphere; If the reaction times is long, the PS microballoon can be by organic solvent swelling fully, reaction can take place at all sites of whole microballoon so, thereby make all macromole all obtain enough big molecular weight, so, after the charing step, charing all takes place in all sites of microballoon, obtains the solid carbon ball; Not hard to imagine, when the reaction times is moderate, will obtain hollow carbon sphere and solid carbon ball simultaneously.
With respect to prior art, simple, the easy row of preparation technology of the present invention, required experimental installation cost is low, obtains easily; Can access spherical rule, carbosphere homogeneous, monodispersity; Can realize control by regulating experiment parameter (alkylated reaction time) simply to the final form of carbosphere.
Description of drawings
Fig. 1: saturating look Electronic Speculum (TEM) photo of the inventive method gained carbosphere, wherein Figure 1A, B, C, D are respectively saturating look Electronic Speculum (TEM) photos of embodiment 1,4,8,12 gained carbospheres;
Fig. 2: scanning electron microscope (SEM) photo of the inventive method gained carbosphere, wherein Fig. 2 A, B, C, D are respectively scanning electron microscope (SEM) photos of embodiment 1,4,8,12 gained carbospheres.
Embodiment:
Below with specific embodiment technical scheme of the present invention is described, but protection scope of the present invention is not limited thereto:
Embodiment 1
With 2.1g St/90g H
2The mixed solution of O adds in the four-hole bottle, opens and stirs (200rpm), behind feeding nitrogen (1～2 bubble p.s.) the excluding air 30min, begins to heat up.When temperature rises to 70 ℃, with 10gH
2The mixed solution of O/0.12g Potassium Persulphate adds in the reaction flask, this is designated as the initial moment of emulsifier-free emulsion polymerization reaction constantly, after 3h is carried out in reaction, injection in batches adds the Vinylstyrene (DVB) that total amount reaches 0.9g, and per minute is injected 15 μ L, whole emulsifier-free emulsion polymerization reaction is carried out stopping behind the 24h, obtains crosslinked polystyrene microsphere.
With 30g CCl
4With the anhydrous AlCl of 1.8g
3The capacity of putting into is the there-necked flask of 100mL, and room temperature is opened and stirred (160rpm); Behind the 20min, in flask, add the 0.30g crosslinked polystyrene microsphere; Behind the 20min, reaction flask is put into 60 ℃ water-bath, this is considered as the time of origin of alkylated reaction constantly, and reaction is carried out finishing behind the 2h, collects product; The washing with acetone of products obtained therefrom usefulness 15ml three times, mass concentration 10% dilute hydrochloric acid with 10ml washs three times then; The gained solid product disperses with small amount of acetone, places 45 ℃ air dry oven, and dried overnight gets solid phase prod.
The back crosslinked polystyrene microsphere of dried and clean is placed tube furnace, under the protection of nitrogen atmosphere, carry out the intelligent temperature control program: be warming up to 700 ℃ equably by room temperature, keep 700 ℃ and reach 2h, be cooled to room temperature naturally, collect product, porphyrize.The TEM picture of present embodiment gained carbosphere pattern is shown in Figure 1A, and the SEM picture is shown in Fig. 2 A.
Embodiment 2～12
The time of alkylated reaction is adjusted to 4h, 6h, 8h, 10h, 12h, 14h, 16h, 18h, 20h, 22h, 24h respectively, and other condition is with embodiment 1.Wherein shown in Figure 1B, C, D, the SEM picture is respectively shown in Fig. 2 B, C, D respectively for the TEM picture of embodiment 4 (8h), embodiment 8 (16h), embodiment 12 (24h) gained carbosphere pattern.
Embodiment 13
With 2.1g St/50g H
2The mixed solution of O adds in the four-hole bottle, opens and stirs (200rpm), behind feeding nitrogen (1～2 bubble p.s.) the excluding air 25min, begins to heat up.When temperature rises to 40 ℃, with 2.5gH
2The mixed solution of O/0.063g ammonium persulphate adds in the reaction flask, this is designated as the initial moment of emulsifier-free emulsion polymerization reaction constantly, after 7h is carried out in reaction, injection in batches adds the DVB that total amount reaches 0.42g, and per minute is injected 10 μ L, whole emulsifier-free emulsion polymerization reaction is carried out stopping behind the 22h, obtains crosslinked polystyrene microsphere.
With 15g CCl
3With the anhydrous FeCl of 0.9g
3The capacity of putting into is the there-necked flask of 100mL, and room temperature is opened and stirred (160rpm); Behind the 10min, in flask, add the 0.30g crosslinked polystyrene microsphere; Behind the 10min, reaction flask is put into 40 ℃ water-bath, this is considered as the time of origin of alkylated reaction constantly, and reaction is carried out finishing behind the 13h, collects product; The washing with acetone of products obtained therefrom usefulness 15ml three times, mass concentration 5% dilute hydrochloric acid with 30ml washs three times then; The gained solid product disperses with small amount of acetone, places 45 ℃ air dry oven, and dried overnight gets solid phase prod.
The back crosslinked polystyrene microsphere of dried and clean is placed tube furnace, under the protection of nitrogen atmosphere, carry out the intelligent temperature control program: be warming up to 600 ℃ equably by room temperature, keep 600 ℃ and reach 4h, be cooled to room temperature naturally, collect product, porphyrize.
Embodiment 14
With 2.1g St/126g H
2The mixed solution of O adds in the four-hole bottle, opens and stirs (200rpm), behind feeding nitrogen (1～2 bubble p.s.) the excluding air 40min, begins to heat up.When temperature rises to 85 ℃, with 31.5g H
2The mixed solution of O/0.189g Potassium Persulphate adds in the reaction flask, this is designated as the initial moment of emulsifier-free emulsion polymerization reaction constantly, after 5h is carried out in reaction, injection in batches adds the Ethylene glycol dimethacrylate that total amount reaches 1.47g, and per minute is injected 20 μ L, whole emulsifier-free emulsion polymerization reaction is carried out stopping behind the 30h, obtains crosslinked polystyrene microsphere.
With 60g CHCl
2With the anhydrous SnCl of 2.1g
4The capacity of putting into is the there-necked flask of 100mL, and room temperature is opened and stirred (160rpm); Behind the 40min, in flask, add the 0.30g crosslinked polystyrene microsphere; Behind the 40min, reaction flask is put into 50 ℃ water-bath, this is considered as the time of origin of alkylated reaction constantly, and reaction is carried out finishing behind the 19h, collects product; The washing with acetone of products obtained therefrom usefulness 30ml three times, mass concentration 40% dilute hydrochloric acid with 50ml washs three times then; The gained solid product disperses with small amount of acetone, places 45 ℃ air dry oven, and dried overnight gets solid phase prod.
The back crosslinked polystyrene microsphere of dried and clean is placed tube furnace, under the protection of nitrogen atmosphere, carry out the intelligent temperature control program: be warming up to 800 ℃ equably by room temperature, keep 800 ℃ and reach 3h, be cooled to room temperature naturally, collect product, porphyrize.
Embodiment 15
The adding mode of DVB is disposablely to pour into fully, and other condition is with embodiment 1.
Embodiment 16～18
Use anhydrous AlCl successively instead
3: anhydrous FeCl
3=60%: 40%, 50%: 50%, 30%: 70% (quality percentage composition) replaces simple anhydrous AlCl
3As the catalyzer of alkylated reaction, other condition is with embodiment 1.
Embodiment 19～21
Use anhydrous FeCl successively instead
3: anhydrous SnCl
4=70%: 30%, 50%: 50%, 20%: 80% (quality percentage composition) replaces simple anhydrous FeCl
3As the catalyzer of alkylated reaction, other condition is with embodiment 13.
Embodiment 22～24
Use anhydrous AlCl successively instead
3: anhydrous SnCl
4=60%: 40%, 50%: 50%, 20%: 80% (quality percentage composition) replaces simple anhydrous SnCl
4As the catalyzer of alkylated reaction, other condition is with embodiment 14.
Embodiment 25～27
Use anhydrous AlCl successively instead
3: anhydrous FeCl
3: anhydrous SnCl
4=50%: 30%: 20%, 33.3%: 33.3%: 33.4%, 10%: 30%: 60% (quality percentage composition) replaced simple anhydrous SnCl
4As the catalyzer of alkylated reaction, other condition is with embodiment 14.
Claims (10)
1. a method for preparing the controlled monodisperse carbon microsphere of form is characterized in that at first being that monomer, water are that medium carries out emulsifier-free emulsion polymerization with water soluble starter, linking agent with vinylbenzene, synthesizes monodisperse cross-linked polystyrene microsphere; Then this crosslinked polystyrene microsphere is carried out Fu-Ke alkylated reaction in methane chloride organic solvent/metal chloride catalyst system, reaction is removed organic solvent, catalyzer after finishing, and drying obtains the back crosslinked polystyrene microsphere; With back crosslinked polystyrene microsphere starvation charing, promptly obtain carbosphere at last.
2. the method for the monodisperse carbon microsphere that preparation form as claimed in claim 1 is controlled is characterized in that: described water soluble starter is a persulfuric acid salt initiator, and linking agent is Vinylstyrene or Ethylene glycol dimethacrylate.
3. the method for the monodisperse carbon microsphere that preparation form as claimed in claim 2 is controlled, it is characterized in that by mass ratio, each raw material consumption of emulsifier-free emulsion polymerization is a vinylbenzene: water: persulfuric acid salt initiator: linking agent=1: 25～75: 0.03～0.09: 0.2～0.7, each raw material consumption of Fu-Ke alkylated reaction is a crosslinked polystyrene microsphere: methane chloride: metal chloride=1: 50～200: 3～7.
4. the method for the monodisperse carbon microsphere that preparation form as claimed in claim 3 is controlled, it is characterized in that: persulfuric acid salt initiator is Potassium Persulphate or ammonium persulphate, methane chloride is tetracol phenixin, chloroform or methylene dichloride, and metal chloride is wherein a kind of or its combination of Aluminum chloride anhydrous, Anhydrous Ferric Chloride, anhydrous stannic chloride.
5. as the method for the controlled monodisperse carbon microsphere of any described preparation form of claim 1～4, it is characterized in that: at first be that monomer, water are that medium and water soluble starter carry out emulsifier-free emulsion polymerization reaction 3～7h in 40～85 ℃ under inert atmosphere with vinylbenzene, add linking agent afterwards again and continue reaction, the time of whole emulsifier-free emulsion polymerization reaction is 22～30h.
6. the method for the monodisperse carbon microsphere that preparation form as claimed in claim 5 is controlled is characterized in that: the adding mode of linking agent is disposable the adding fully or injection adding in batches, and per minute injection 10～20 μ L.
7. the method for the monodisperse carbon microsphere that preparation form as claimed in claim 6 is controlled is characterized in that: Fu-Ke alkylated reaction temperature is 40～60 ℃, and the time is 2～24h; Carbonization temperature is 600～800 ℃, and the time is 2～4h.
8. the method for the monodisperse carbon microsphere that preparation form as claimed in claim 7 is controlled, it is characterized in that emulsifier-free emulsion polymerization is specifically undertaken by following process: at room temperature vinylbenzene and portion water are mixed earlier, the consumption of this portion water is 0.8～0.95 times of water total mass, feed the rare gas element excluding air simultaneously, be warming up to 40～85 ℃ of temperature of reaction afterwards, the water that adds initiator and surplus, this is designated as the time of origin of reaction constantly, add linking agent behind reaction 3～7h and continue reaction, the time of whole emulsifier-free emulsion polymerization reaction is 22～30h.
9. the method for the monodisperse carbon microsphere that preparation form as claimed in claim 8 is controlled, it is characterized in that Fu-Ke alkylated reaction is specifically undertaken by following process: at room temperature mix earlier methane chloride organic solvent and metal chloride catalyst, the crosslinked polystyrene microsphere that adds the emulsifier-free emulsion polymerization gained behind 10～40min, behind 10～40min, temperature control reacts at 40～60 ℃, this is designated as the time of origin of reaction constantly, finishes behind reaction 2～24h.
10. the method for the monodisperse carbon microsphere that preparation form as claimed in claim 9 is controlled, it is characterized in that: after Fu-Ke alkylated reaction finishes, use the dilute hydrochloric acid cleaning product of acetone, mass concentration 5～40% successively, the gained solids gets the back crosslinked polystyrene microsphere with acetone dispersion, drying.
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| CN101830457A (en) * | 2010-05-20 | 2010-09-15 | 湖南大学 | Method for preparing carbon microspheres and application of heteropolyacid in carbon microsphere preparation and graphitization |
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| CN101830457A (en) * | 2010-05-20 | 2010-09-15 | 湖南大学 | Method for preparing carbon microspheres and application of heteropolyacid in carbon microsphere preparation and graphitization |
| CN101857700A (en) * | 2010-06-21 | 2010-10-13 | 郑州大学 | Method for self assembling non-spherical polystyrene grains to form into multihole and ordered structure |
| CN101857700B (en) * | 2010-06-21 | 2011-08-17 | 郑州大学 | Method for self assembling non-spherical polystyrene grains to form into multihole and ordered structure |
| CN104275152A (en) * | 2014-10-29 | 2015-01-14 | 苏州纳微科技有限公司 | Carbonized micro-ball and preparation method thereof |
| CN105174243A (en) * | 2015-06-16 | 2015-12-23 | 郑州大学 | Graphitized multi-level pore carbon sphere preparation method |
| CN106040121A (en) * | 2016-05-25 | 2016-10-26 | 中国科学院大学 | Method for synthesizing skeleton microsphere material |
| CN107640757A (en) * | 2017-09-07 | 2018-01-30 | 中南大学 | A kind of preparation method of compound carbosphere and compound carbosphere and its lithium-ion capacitor being prepared |
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| CN109354007A (en) * | 2018-11-08 | 2019-02-19 | 郑州大学 | A kind of regulatable bivalve layer hollow caged carbosphere of foreign components of structure |
| CN111362252A (en) * | 2020-04-27 | 2020-07-03 | 西北工业大学 | Hypercrosslinked polystyrene based low-porosity carbon material and preparation method and application thereof |
| CN111362252B (en) * | 2020-04-27 | 2023-03-24 | 西北工业大学 | Hypercrosslinked polystyrene based low-porosity carbon material and preparation method and application thereof |
| CN114393763A (en) * | 2021-12-20 | 2022-04-26 | 美盛隆制罐（惠州）有限公司 | Polystyrene microsphere nano-imprinting mother board based on self-assembly and preparation method and application thereof |
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