CN101219785A - Method for manufacturing carbon nano-hollow sphere with polymethyl methacrylate/polyacrylonitrile nucleocapsid polymer as forerunner body - Google Patents
Method for manufacturing carbon nano-hollow sphere with polymethyl methacrylate/polyacrylonitrile nucleocapsid polymer as forerunner body Download PDFInfo
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- CN101219785A CN101219785A CNA2008100329437A CN200810032943A CN101219785A CN 101219785 A CN101219785 A CN 101219785A CN A2008100329437 A CNA2008100329437 A CN A2008100329437A CN 200810032943 A CN200810032943 A CN 200810032943A CN 101219785 A CN101219785 A CN 101219785A
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Abstract
The invention discloses a manufacture method of carbon nanometer hollow spheres from a precursor of core-shell polymer of PMMA/PAN; the invention comprises the following steps of a. soap-free emulsion polymerization of PMMA spheres; b. preparation of the core-shell polymer of PMMA/PAN; c. low-temperature stabilization of PMMA/PAN spheres; and d. high-temperature carbonization of the PMMA/PAN spheres. By adjusting the mixture ratio, the invention can obtain PMMA core particles with different particle sizes and PAN shell layers with different thicknesses; the size and thickness of the shell spheres is uniform and controllable. The invention has simple method, few operation steps and high productive rate, and the obtained products have stable quality, which provides a possibility for low cost and large scale production of the carbon nanometer hollow spheres.
Description
Technical field
The present invention relates to a kind of preparation method of carbon nano-hollow sphere, more particularly relating to a kind of is the method that presoma passes through high temperature carbonization Processing of Preparation carbon nano-hollow sphere with the core-shell polymer.
Background technology
Carbon nano-hollow sphere is a kind of spherical carbon nano material, has unique hollow, charcoal containment structure, has characteristics such as high-specific surface area, low density, high strength and high chemical stability, can be used as the inclusion, support of the catalyst, sorbent material of nano material etc.The method for preparing at present carbon nano-hollow sphere has template, chemical Vapor deposition process, cryochemistry reaction method, core-shell polymer method etc.Wherein the core-shell polymer method is a kind of excellent process of producing carbon nano-hollow sphere, can prepare the adjustable carbon nano-hollow sphere of size and thickness, this method comprises two key steps, be the preparation of core-shell polymer and the pyroprocessing of polymkeric substance, its key is to select two kinds of suitable polymers, and promptly the stratum nucleare polymkeric substance is that to be high temperature become charcoal to retain material for pyrolytic decomposition ease empty matter and shell polymkeric substance.People such as Hisashi Tamai are at (Preparation and characteristics of fine hollow carbon particles.Journal of Colloid and Interface Science1996; 177 (2): be that presoma has prepared carbon nano-hollow sphere with polystyrene/polyacrylonitrile nucleocapsid 325-328.).People such as Jyongsik Jang are at (Fabrication of carbon nanocapsules using PMMA/PDVBcore/shell nanoparticles.Chemistry of Materials2003; 15 (11): be that presoma has prepared carbon nano-hollow sphere with polymethylmethacrylate/polydivinylbenezene 2109-2111).Polymethylmethacrylate (PMMA) is a kind of polymkeric substance that can decompose fully, its representative species as letex polymerization has been carried out research extensively and profoundly, polyacrylonitrile (PAN) has occupied consequence as good carbon precursor material in the production of charcoal fiber, prepare the carbon nanospheres hollow ball with its nucleocapsid structure polymkeric substance as presoma and be not seen in report as yet but above-mentioned two kinds of typical presomas are combined.
Summary of the invention
It is the method that presoma prepares carbon nano-hollow sphere that technical problem to be solved by this invention provides a kind of core-shell polymer with polymethylmethacrylate/polyacrylonitrile, and this method technology is simple, the productive rate height, and cost is low, is suitable for scale operation.
The technical solution used in the present invention: a kind of is the method that presoma prepares carbon nano-hollow sphere with polymethylmethacrylate/polyacrylonitrile nucleocapsid polymer, comprises the steps:
A. the emulsifier-free emulsion polymerization of polymethylmethacrylate ball
Methyl methacrylate, deionized water are mixed, methyl methacrylate monomer concentration is 20～100g/L, vigorous stirring is removed air under nitrogen protection, be warming up to 60～80 ℃ of adding initiators then and carry out letex polymerization, reaction 4～8h obtains white polymethylmethacrylate emulsion, and size is at 100～300nm, wherein said initiator is selected from Potassium Persulphate or ammonium persulphate, and initiator concentration is 0.10～0.4g/L;
B. the preparation of polymethylmethacrylate/polyacrylonitrile nucleocapsid polymer
The polymethylmethacrylate emulsion that step a obtains is mixed with the deionized water of 0.5～1 times of volume, vigorous stirring is removed air under nitrogen protection, be warming up to 60～80 ℃ then, in concentration is under the initiator initiation of 0.10～0.4g/L, add 0.5～2 times of acrylonitrile monemer of seed emulsion add-on with absorption method or hungry volumetry, go out the polyacrylonitrile shell at polymethylmethacrylate nuclear outside surface emulsifier-free emulsion polymerization, shell thickness is between 10～50nm, to obtain polymethylmethacrylate/polyacrylonitrile particles white powder after this emulsion lyophilize, wherein said initiator is selected from Potassium Persulphate or ammonium persulphate;
C. the cryostatic stabilizationization of polymethylmethacrylate/polyacrylonitrile ball
Polymethylmethacrylate/polyacrylonitrile particles uniform spreading that step b is obtained is on stainless (steel) wire, put into air dry oven air blast and temperature programming, between 180～350 ℃, carry out preoxidation stabilization treatment 1～10h, obtain the polymethylmethacrylate/polyacrylonitrile ball after brown or the black stabilization;
D. the high temperature carbonization of polymethylmethacrylate/polyacrylonitrile ball
Polymethylmethacrylate/polyacrylonitrile ball temperature programming to 700 under protection of inert gas after the stabilization that step c is obtained～1500 ℃ is handled 0.5～5h and is carried out charing and handle, and obtains the hollow carbon nanospheres of black at last.
The temperature programming that polymethylmethacrylate among the step c/polyacrylonitrile ball cryostatic stabilization process is taked is to be warming up to 100 ℃ with 2～5 ℃/min heat-up rate earlier, insulation 1～2h, be warming up to 180～350 ℃ with 0.5～2 ℃/min heat-up rate again, insulation 1～10h.
Temperature programming under the high temperature carbonization protection of inert gas of polymethylmethacrylate in the steps d/polyacrylonitrile ball is to be warming up to 300～500 ℃ with 2～5 ℃/min heat-up rate earlier; insulation 1～3h; be warming up to 700～1500 ℃ with 3～5 ℃/min heat-up rate again, insulation 0.5～5h.
The present invention possesses following advantage:
1, can obtain the polymethylmethacrylate nuclear particle of different-grain diameter and the polyacrylonitrile shell of different thickness, the size of shell ball and thickness homogeneous, controlled by regulating proportioning.
2, the inventive method is simple, and operation steps is few, the productive rate height, and the products obtained therefrom steady quality is for low-cost, scale operation carbon nano-hollow sphere provide possibility.
Description of drawings
Figure 1A is poly methyl methacrylate polymer ball SEM figure;
Figure 1B is polymethylmethacrylate/polyacrylonitrile polymer ball SEM figure;
Fig. 2 A is carbon nano-hollow sphere TEM figure;
Fig. 2 B is carbon nano-hollow sphere TEM figure.
Embodiment
Below by drawings and Examples the present invention is described in further detail: a kind of is the method that presoma prepares carbon nano-hollow sphere with polymethylmethacrylate/polyacrylonitrile nucleocapsid polymer, comprises the steps:
A. the emulsifier-free emulsion polymerization of polymethylmethacrylate ball
Methyl methacrylate, deionized water are mixed, methyl methacrylate monomer concentration is 20～100g/L, vigorous stirring is removed air under nitrogen protection, be warming up to 60～80 ℃ of adding initiators then and carry out letex polymerization, reaction 4～8h obtains white polymethylmethacrylate emulsion, and size is at 100～300nm, wherein said initiator is selected from Potassium Persulphate or ammonium persulphate, and initiator concentration is 0.10～0.4g/L;
B. the preparation of polymethylmethacrylate/polyacrylonitrile nucleocapsid polymer
The polymethylmethacrylate emulsion that step a obtains is mixed with the deionized water of 0.5～1 times of volume, vigorous stirring is removed air under nitrogen protection, be warming up to 60～80 ℃ then, in concentration is under the initiator initiation of 0.10～0.4g/L, add 0.5～2 times of acrylonitrile monemer of seed emulsion add-on with absorption method or hungry volumetry, go out the polyacrylonitrile shell at polymethylmethacrylate nuclear outside surface emulsifier-free emulsion polymerization, shell thickness is between 10～50nm, to obtain polymethylmethacrylate/polyacrylonitrile particles white powder after this emulsion lyophilize, wherein said initiator is selected from peroxide initiators such as Potassium Persulphate or ammonium persulphate;
C. the cryostatic stabilizationization of polymethylmethacrylate/polyacrylonitrile ball
Polymethylmethacrylate/polyacrylonitrile particles uniform spreading that step b is obtained is on stainless (steel) wire, put into air dry oven air blast and temperature programming, between 180～350 ℃, carry out preoxidation stabilization treatment 1～10h, obtain the polymethylmethacrylate/polyacrylonitrile ball after brown or the black stabilization;
D. the high temperature carbonization of polymethylmethacrylate/polyacrylonitrile ball
Polymethylmethacrylate/polyacrylonitrile ball temperature programming to 700 under protection of inert gas after the stabilization that step c is obtained～1500 ℃ is handled 0.5～5h and is carried out charing and handle, and obtains the hollow carbon nanospheres of black at last.
Embodiment 1
With methyl methacrylate (MMA) monomer 9g, deionized water 300ml uniform mixing, feed high pure nitrogen under the vigorous stirring to remove air, after half an hour temperature is risen to 75 ℃, add Potassium Persulphate 30mg reaction 5h, obtain the median size size for the polymethylmethacrylate of 200nm (PMMA) ball emulsion, shown in Figure 1A.Getting 150ml PMMA emulsion mixes with the 100ml deionized water, feed high pure nitrogen under the vigorous stirring to remove air, after half an hour temperature is risen to 75 ℃, add the 25mg Potassium Persulphate, carry out the shell polymerization with the hungry vinyl cyanide (AN) that drips 6g of the mode of 3g/h, drip back insulation 0.5h, the PMMA/PAN core-shell polymer ball that obtains the about 260nm of size is shown in Figure 1B.Obtain PMMA/PAN nucleocapsid ion ball white powder after the lyophilize, with this powder uniform spreading on stainless (steel) wire, put into air dry oven air blast and temperature programming, mode with 2 ℃/min is warming up to 100 ℃ of insulation 1h, be warming up to 220 ℃ of insulation 2h in the mode of 0.5 ℃/min, be warming up to 250 ℃ of insulation 5h in the mode of 1 ℃/min.Nucleocapsid ion ball after the resulting stabilization is placed porcelain crucible; high pure nitrogen protection temperature programming charing down; specific procedure is: the mode with 1 ℃/min is warming up to 350 ℃ of insulation 1h; mode with 1 ℃/min is warming up to 500 ℃; mode with 3 ℃/min is warming up to 1000 ℃ of insulation 1h again; obtaining size is the black PMMA/PAN core-shell polymer base carbon nano-hollow sphere of the homogeneous of 100～150nm, the about 15nm of shell thickness, shown in Fig. 2 A, Fig. 2 B.
Embodiment 2
With MMA monomer 10g, deionized water 100ml uniform mixing, feed high pure nitrogen under the vigorous stirring to remove air, after half an hour temperature is risen to 80 ℃, add ammonium persulphate 10mg reaction 4h, obtain the median size size and be the PMMA ball emulsion of 300nm.Getting the 80mlPMMA emulsion mixes with the AN of 80ml deionized water and 4g, feed high pure nitrogen under the vigorous stirring to remove air, adsorb and after 1.5 hours temperature is risen to 80 ℃, add the 80mg ammonium persulphate, reacted 5 hours, obtain the PMMA/PAN core-shell polymer ball of the about 350nm of size, obtain PMMA/PAN nucleocapsid ion ball white powder after the lyophilize, with this powder uniform spreading on stainless (steel) wire, put into air dry oven air blast and temperature programming, be warming up to 100 ℃ of insulation 1h in the mode of 5 ℃/min, be warming up to 180 ℃ of insulation 10h in the mode of 2 ℃/min.Core-shell particles ball after the resulting stabilization is placed the diamond spar crucible; temperature programming charing under the argon shield; specific procedure is: the mode with 2 ℃/min is warming up to 1000 ℃; mode with 3 ℃/min is warming up to 1500 ℃ of insulation 0.5h again, and obtaining size is the black PMMA/PAN core-shell polymer base carbon nano-hollow sphere of 200～250nm, the about 10nm of shell thickness.
Embodiment 3
With the concentration uniform mixing of MMA monomer 3g, deionized water 150ml, feed high pure nitrogen under the vigorous stirring to remove air, after half an hour temperature is risen to 60 ℃, add Potassium Persulphate 60mg reaction 8h, obtain the median size size and be the PMMA ball emulsion of 100nm.Getting the 100mlPMMA emulsion mixes with the 50ml deionized water, feed high pure nitrogen under the vigorous stirring to remove air, after half an hour temperature is risen to 60 ℃, add the 60mg Potassium Persulphate, the AN of 1.5g is carried out the shell polymerization with the hungry adding of 2 hours time, reacted 5 hours, obtain the PMMA/PAN core-shell polymer ball of the about 150nm of size, obtain PMMA/PAN nucleocapsid ion ball white powder after the lyophilize, with this powder uniform spreading on stainless (steel) wire, put into air dry oven air blast and temperature programming, be warming up to 100 ℃ of insulation 2h, be warming up to 350 ℃ of insulation 1h in the mode of 1 ℃/min in the mode of 3 ℃/min.Nucleocapsid ion ball after the resulting stabilization is placed porcelain crucible; high pure nitrogen protection temperature programming charing down; specific procedure is: the mode with 5 ℃/min is warming up to 350 ℃ of insulation 1h; mode with 5 ℃/min is warming up to 700 ℃; insulation 5h, obtaining size is the black PMMA/PAN core-shell polymer base carbon nano-hollow sphere of 100～120nm, the about 30nm of shell thickness.
Above said content only is the basic explanation of the present invention under conceiving, and according to any equivalent transformation that technical scheme of the present invention is done, all should belong to protection scope of the present invention.
Claims (3)
1. one kind is the method that presoma prepares carbon nano-hollow sphere with polymethylmethacrylate/polyacrylonitrile nucleocapsid polymer, comprises the steps:
A. the emulsifier-free emulsion polymerization of polymethylmethacrylate ball
Methyl methacrylate, deionized water are mixed, methyl methacrylate monomer concentration is 20～100g/L, vigorous stirring is removed air under nitrogen protection, be warming up to 60～80 ℃ of adding initiators then and carry out letex polymerization, reaction 4～8h obtains white polymethylmethacrylate emulsion, and size is at 100～300nm, wherein said initiator is selected from Potassium Persulphate or ammonium persulphate, and initiator concentration is 0.10～0.4g/L;
B. the preparation of polymethylmethacrylate/polyacrylonitrile nucleocapsid polymer
The polymethylmethacrylate emulsion that step a obtains is mixed with the deionized water of 0.5～1 times of volume, vigorous stirring is removed air under nitrogen protection, be warming up to 60～80 ℃ then, in concentration is under the initiator initiation of 0.10～0.4g/L, add 0.5～2 times of acrylonitrile monemer of seed emulsion add-on with absorption method or hungry volumetry, go out the polyacrylonitrile shell at polymethylmethacrylate nuclear outside surface emulsifier-free emulsion polymerization, shell thickness is between 10～50nm, to obtain polymethylmethacrylate/polyacrylonitrile particles white powder after this emulsion lyophilize, wherein said initiator is selected from Potassium Persulphate or ammonium persulphate;
C. the cryostatic stabilizationization of polymethylmethacrylate/polyacrylonitrile ball
Polymethylmethacrylate/polyacrylonitrile particles uniform spreading that step b is obtained is on stainless (steel) wire, put into air dry oven air blast and temperature programming, between 180～350 ℃, carry out preoxidation stabilization treatment 1～10h, obtain the polymethylmethacrylate/polyacrylonitrile ball after brown or the black stabilization;
D. the high temperature carbonization of polymethylmethacrylate/polyacrylonitrile ball
Polymethylmethacrylate/polyacrylonitrile ball temperature programming to 700 under protection of inert gas after the stabilization that step c is obtained～1500 ℃ is handled 0.5～5h and is carried out charing and handle, and obtains the hollow carbon nanospheres of black at last.
According to claim 1 described a kind of be the method that presoma prepares carbon nano-hollow sphere with polymethylmethacrylate/polyacrylonitrile nucleocapsid polymer, it is characterized in that: the temperature programming that polymethylmethacrylate among the step c/polyacrylonitrile ball cryostatic stabilization process is taked is to be warming up to 100 ℃ with 2～5 ℃/min heat-up rate earlier, insulation 1～2h, be warming up to 180～350 ℃ with 0.5～2 ℃/min heat-up rate again, insulation 1～10h.
According to claim 1 described a kind of be the method that presoma prepares carbon nano-hollow sphere with polymethylmethacrylate/polyacrylonitrile nucleocapsid polymer; it is characterized in that: the temperature programming under the high temperature carbonization protection of inert gas of polymethylmethacrylate in the steps d/polyacrylonitrile ball is to be warming up to 300～500 ℃ with 2～5 ℃/min heat-up rate earlier; insulation 1～3h; be warming up to 700～1500 ℃ with 3～5 ℃/min heat-up rate again, insulation 0.5～5h.
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| CN101638452B (en) * | 2009-08-10 | 2012-05-16 | 佛山市顺德区巴德富实业有限公司 | High-solid content pure acrylate elastic emulsion |
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| CN110482521A (en) * | 2019-07-24 | 2019-11-22 | 厦门大学 | A kind of preparation method of hollow carbon balls |
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| CN101638452B (en) * | 2009-08-10 | 2012-05-16 | 佛山市顺德区巴德富实业有限公司 | High-solid content pure acrylate elastic emulsion |
| CN101798077A (en) * | 2010-04-08 | 2010-08-11 | 哈尔滨工业大学 | Preparation method of hollow carbon sphere with resorcinol and formaldehyde as raw materials |
| CN102502582A (en) * | 2011-10-31 | 2012-06-20 | 上海理工大学 | Preparation method of three dimensional ordered macroporous charcoal material |
| CN108039288A (en) * | 2017-11-22 | 2018-05-15 | 西安交通大学 | A kind of preparation method of C-base composte material for ultracapacitor |
| CN108039288B (en) * | 2017-11-22 | 2019-09-24 | 西安交通大学 | A kind of preparation method of the C-base composte material for supercapacitor |
| CN108305789A (en) * | 2017-12-29 | 2018-07-20 | 西安交通大学 | A kind of preparation method of polyacrylonitrile/molybdenum disulfide composite material for ultracapacitor |
| CN108305789B (en) * | 2017-12-29 | 2020-04-07 | 西安交通大学 | Preparation method of polyacrylonitrile/molybdenum disulfide composite material for supercapacitor |
| CN112585084A (en) * | 2018-07-20 | 2021-03-30 | 小利兰·斯坦福大学托管委员会 | Novel polyacrylonitrile system for preparing multifunctional carbon pattern material and other superstructure |
| CN112585084B (en) * | 2018-07-20 | 2023-12-22 | 小利兰·斯坦福大学托管委员会 | Novel polyacrylonitrile system for preparing multifunctional carbon flower type object and other super structures |
| CN110482521A (en) * | 2019-07-24 | 2019-11-22 | 厦门大学 | A kind of preparation method of hollow carbon balls |
| CN110482521B (en) * | 2019-07-24 | 2021-04-06 | 厦门大学 | Preparation method of hollow carbon spheres |
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