CN107829169A - A kind of preparation method of high-ratio surface hollow tubular carbon nano-fiber - Google Patents
A kind of preparation method of high-ratio surface hollow tubular carbon nano-fiber Download PDFInfo
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- CN107829169A CN107829169A CN201711055360.1A CN201711055360A CN107829169A CN 107829169 A CN107829169 A CN 107829169A CN 201711055360 A CN201711055360 A CN 201711055360A CN 107829169 A CN107829169 A CN 107829169A
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- D01F9/00—Artificial filaments or the like of other substances; Manufacture thereof; Apparatus specially adapted for the manufacture of carbon filaments
- D01F9/08—Artificial filaments or the like of other substances; Manufacture thereof; Apparatus specially adapted for the manufacture of carbon filaments of inorganic material
- D01F9/12—Carbon filaments; Apparatus specially adapted for the manufacture thereof
- D01F9/14—Carbon filaments; Apparatus specially adapted for the manufacture thereof by decomposition of organic filaments
- D01F9/20—Carbon filaments; Apparatus specially adapted for the manufacture thereof by decomposition of organic filaments from polyaddition, polycondensation or polymerisation products
- D01F9/24—Carbon filaments; Apparatus specially adapted for the manufacture thereof by decomposition of organic filaments from polyaddition, polycondensation or polymerisation products from macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
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Abstract
The present invention relates to a kind of preparation method of high-ratio surface hollow tubular carbon nano-fiber, using the super cross-linked polymeric in double oil-based systems, the tubular nanometer fiber with hollow structure has been prepared in one step, the fiber can obtain high-ratio surface hollow tubular carbon nano-fiber by carbonization, this method reaction condition is gentle, and operability, industrialization property are strong.Prepared high-ratio surface hollow tubular carbon nano-fiber diameter can be adjustable in the range of 100 300nm, and specific surface area can reach 500m2/ more than g, pipe thickness is in 30 130nm range-controllables.Obtained hollow tubular carbon nano-fiber has broad application prospects in adsorbing separation and load, the energy and catalytic field.
Description
Technical field
The invention belongs to carbon fibre material field, is related to a kind of preparation side of high-ratio surface hollow tubular carbon nano-fiber
Method.
Background technology
Nanofiber can be divided into organic polymer fiber, inorganic fibre as the important member in material family by composition
Dimension and composite fibre, wherein with organic polymer fiber and carbon fiber due to wide application and preparation method it is various and by pass
, and there is therebetween very big correlation in note, organic polymer fiber can be the presoma of carbon fiber, by vacuum/lazy
Property atmosphere under high-temperature calcination i.e. can be achieved conversion.At present, the preparation method of polymer fiber is a lot, including Thermal inactive
Method, self-assembly method, hot candied method, template, electrochemical process and vapour deposition process etc., the above method can prepare different major diameters
Than the polymeric fibre material of, different material composition and different-shape.It is real by sequence of chemical or physical reactions in solution
The preparation of existing polymer fiber has larger advantage, including reaction is easily-controllable, mild condition, device require the features such as low.It is existing
By the self assembly of high molecular polymer in the liquid phase prepare fiber (CN2014104939216, CN201410493922.0) and
Hollow tubular material (Sylvain Vauthey et al.PNAS.2002,99 (8):5355) research, but it is fresh rare to application
This kind of material is carbonized again prepares the report of carbon fiber.Meanwhile there is not yet hollow tubular polymerization is prepared using a step liquid phase polymerization
Carbonization prepares the pertinent literature of carbonization nanotube and open report after fibres.
The content of the invention
Technical problems to be solved
In order to avoid the shortcomings of the prior art, the present invention proposes a kind of high-ratio surface hollow tubular carbon nano-fiber
Preparation method, using the super cross-linked polymeric in double oil-based systems, it is fine that the tubular nanometer with hollow structure has been prepared in a step
Dimension, the fiber can obtain high-ratio surface hollow tubular carbon nano-fiber by carbonization, and this method reaction condition is gentle, operable
Property, industrialization property are strong.
Technical scheme
A kind of preparation method of high-ratio surface hollow tubular carbon nano-fiber, it is characterised in that step is as follows：
Step 1：By monomer dissolving in a solvent, solution A is obtained；Wherein monomer mass fraction is 5-10%；The monomer
It is 1,4- to cyclite, the bromobenzyls of 1,3,5- tri-, 3,5- bis- (bromomethyl) toluene, 1,3- bis- (bromomethyl) benzene, (the bromine first of 1,2- bis-
Base) benzene or 1,3- bis- (bromomethyl) toluene；
Step 2：Solution A is added in the there-necked flask for filling silicone oil, after opening 10~30min of stirring, added thereto
Dissolved with the solvent of catalyst；Wherein the volume ratio of solution A and silicone oil is 1: 5~10；The mass ratio of catalyst and monomer be 1: 3~
5；The mass fraction of the catalyst is 4~6%；
Step 3：6~12h is reacted at being 75~85 DEG C in temperature by system, after being cooled to room temperature, is filtered, solvent cleans directly
It is water white transparency to filtrate, obtains red brown solid；
Step 4：Obtained red brown solid is loaded into gauze bag, surname extraction is carried out to it using absolute ethyl alcohol, is extracted
It is vacuum dried to produce hollow tubular polymer nanofiber after 24h；
Step 5：Obtained hollow tubular polymer nanofiber is calcined into 3-8h for 500-700 DEG C under vacuum, with
Stove is cooled to room temperature, produces high-ratio surface hollow tubular carbon nano-fiber.
The solvent is 1,2- dichloroethanes, chloroform, hexamethylene or normal heptane.
The silicone oil is methyl-silicone oil, ethyl silicon oil, Methyl Hydrogen Polysiloxane Fluid, methyl phenyl silicone oil or ethyl containing hydrogen silicone oil.
The catalyst is anhydrous ferric trichloride or aluminum trichloride (anhydrous).
(25 DEG C, cps) of the silicon oil viscosity is less than 1500.
Beneficial effect
The preparation method of a kind of high-ratio surface hollow tubular carbon nano-fiber proposed by the present invention, using in double oil-based systems
Super cross-linked polymeric, the tubular nanometer fiber with hollow structure has been prepared in a step, and the fiber can obtain by carbonization
High-ratio surface hollow tubular carbon nano-fiber, this method reaction condition is gentle, and operability, industrialization property are strong.Prepared
High-ratio surface hollow tubular carbon nano-fiber diameter can be adjustable in the range of 100-300nm, and specific surface area can reach
500m2/ more than g, pipe thickness is in 30-130nm range-controllables.Obtained hollow tubular carbon nano-fiber is in adsorbing separation and bears
Carry, the energy and catalytic field have broad application prospects.
Brief description of the drawings
Fig. 1 is the preparation technology flow chart of high-ratio surface hollow tubular carbon nano-fiber
Fig. 2 is SEM the and TEM photos of high-ratio surface hollow tubular carbon nano-fiber
Fig. 3 is the pore size distribution curve of high-ratio surface hollow tubular carbon nano-fiber
Fig. 4 is the BET curves of high-ratio surface hollow tubular carbon nano-fiber
Embodiment
In conjunction with embodiment, accompanying drawing, the invention will be further described：
Embodiment 1：The preparation of high-ratio surface hollow tubular carbon nano-fiber
2g Isosorbide-5-Nitraes-to cyclite are weighed, are dissolved in 40g 1, in 2- dichloroethanes, obtain solution A；By solution A plus
Enter into the there-necked flask for filling methyl-silicone oil, open stirring.Wherein the volume ratio of solution A and methyl-silicone oil is 1：5；Stirring
After 10min, 1, the 2- dichloroethanes dissolved with anhydrous ferric trichloride is added thereto.Wherein anhydrous ferric trichloride quality is 0.5g,
1,2- dichloroethanes quality is 6.25g；System temperature is set as 75 DEG C, sustained response 12h is incubated, after being cooled to room temperature, takes out
Filter, solvent cleaning until filtrate be water white transparency, obtain red brown solid；Obtained red brown solid is loaded into gauze bag, adopted
Surname extraction is carried out to it with absolute ethyl alcohol, it is vacuum dried to produce hollow tubular polymer nanofiber after extracting 24h.Will
Obtained hollow tubular polymer nanofiber calcines 8h for 500 DEG C under vacuum, cools to room temperature with the furnace, produces Gao Bibiao
Face hollow tubular carbon nano-fiber.
Embodiment 2：The preparation of high-ratio surface hollow tubular carbon nano-fiber
The bromobenzyls of 3g 1,3,5- tri- are weighed, is dissolved in 50g chloroforms, obtains solution A；Solution A is added to and fills second
In the there-necked flask of base silicone oil, stirring is opened.Wherein the volume ratio of solution A and ethyl silicon oil is 1：6；After stirring 15min, thereto
Add the chloroform dissolved with aluminum trichloride (anhydrous).Wherein aluminum trichloride (anhydrous) quality is 1g, and chloroform quality is 20g；By system temperature
Be set as 80 DEG C, be incubated sustained response 8h, after being cooled to room temperature, filter, solvent cleaning until filtrate is water white transparency, obtain red
Brown solid；Obtained red brown solid is loaded into gauze bag, surname extraction is carried out to it using absolute ethyl alcohol, after extracting 24h,
It is vacuum dried to produce hollow tubular polymer nanofiber.By obtained hollow tubular polymer nanofiber in vacuum condition
Lower 550 DEG C of calcinings 6h, cools to room temperature with the furnace, produces high-ratio surface hollow tubular carbon nano-fiber.
Embodiment 3：The preparation of high-ratio surface hollow tubular carbon nano-fiber
4g 3 is weighed, 5- bis- (bromomethyl) toluene, is dissolved in 66.67g hexamethylenes, obtains solution A；By solution A
It is added in the there-necked flask for filling Methyl Hydrogen Polysiloxane Fluid, opens stirring.Wherein the volume ratio of solution A and Methyl Hydrogen Polysiloxane Fluid is 1：
10；After stirring 10min, the hexamethylene dissolved with anhydrous ferric trichloride is added thereto.Wherein anhydrous ferric trichloride quality is 0.8g,
Hexamethylene quality is 13.33g；System temperature is set as 85 DEG C, is incubated sustained response 6h, after being cooled to room temperature, is filtered, solvent
Cleaning is water white transparency up to filtrate, obtains red brown solid；Obtained red brown solid is loaded into gauze bag, using anhydrous second
Alcohol carries out surname extraction to it, vacuum dried to produce hollow tubular polymer nanofiber after extracting 24h.In obtaining
Blank pipe shaped polymer nanofiber calcines 5h for 600 DEG C under vacuum, cools to room temperature with the furnace, produces high-ratio surface hollow tube
Shape carbon nano-fiber.
Embodiment 4：The preparation of high-ratio surface hollow tubular carbon nano-fiber
3g 1 is weighed, 3- bis- (bromomethyl) benzene, is dissolved in 42.88g normal heptanes, obtains solution A；By solution A plus
Enter into the there-necked flask for filling methyl phenyl silicone oil, open stirring.Wherein the volume ratio of solution A and methyl phenyl silicone oil is 1：9；
After stirring 20min, the normal heptane dissolved with aluminum trichloride (anhydrous) is added thereto.Wherein aluminum trichloride (anhydrous) quality is 0.6g, just
Heptane quality is 10g；System temperature is set as 75 DEG C, is incubated sustained response 12h, after being cooled to room temperature, is filtered, solvent cleaning
Until filtrate is water white transparency, red brown solid is obtained；Obtained red brown solid is loaded into gauze bag, using absolute ethyl alcohol pair
It carries out surname extraction, vacuum dried to produce hollow tubular polymer nanofiber after extracting 24h.The hollow tube that will be obtained
Shaped polymer nanofiber calcines 4h for 650 DEG C under vacuum, cools to room temperature with the furnace, produces high-ratio surface hollow tubular carbon
Nanofiber.
Embodiment 5：The preparation of high-ratio surface hollow tubular carbon nano-fiber
Weigh 2g 1,2- bis- (bromomethyl) benzene is dissolved in 25g 1, in 2- dichloroethanes, obtains solution A；By solution
A is added in the there-necked flask for filling ethyl containing hydrogen silicone oil, opens stirring.Wherein solution A and the volume ratio of ethyl containing hydrogen silicone oil be
1：7；After stirring 25min, 1, the 2- dichloroethanes dissolved with anhydrous ferric trichloride is added thereto.Wherein anhydrous ferric trichloride quality
For 0.66g, 1,2- dichloroethanes quality is 16.67g；System temperature is set as 80 DEG C, sustained response 10h is incubated, is cooled to
After room temperature, filter, solvent cleaning until filtrate be water white transparency, obtain red brown solid；Obtained red brown solid is loaded
Gauze bag, surname extraction is carried out to it using absolute ethyl alcohol, it is vacuum dried to produce hollow tubular polymer nano after extracting 24h
Rice fiber.Obtained hollow tubular polymer nanofiber is calcined into 3h for 700 DEG C under vacuum, cools to room temperature with the furnace,
Produce high-ratio surface hollow tubular carbon nano-fiber.
Embodiment 6：The preparation of high-ratio surface hollow tubular carbon nano-fiber
1g 1 is weighed, 3- bis- (bromomethyl) toluene, is dissolved in 20g chloroforms, obtains solution A；Solution A is added to
Fill in the there-necked flask of methyl-silicone oil, open stirring.Wherein the volume ratio of solution A and methyl-silicone oil is 1：5；After stirring 10min,
The chloroform dissolved with aluminum trichloride (anhydrous) is added thereto.Wherein aluminum trichloride (anhydrous) quality is 0.25g, and chloroform quality is 5g；Will
System temperature is set as 85 DEG C, is incubated sustained response 6h, after being cooled to room temperature, filters, solvent cleans until filtrate is colourless
It is bright, obtain red brown solid；Obtained red brown solid is loaded into gauze bag, surname extraction is carried out to it using absolute ethyl alcohol,
It is vacuum dried to produce hollow tubular polymer nanofiber after extracting 24h.The hollow tubular polymer nanofiber that will be obtained
500 DEG C of calcining 8h under vacuum, cool to room temperature with the furnace, produce high-ratio surface hollow tubular carbon nano-fiber.
Embodiment 7：The preparation of high-ratio surface hollow tubular carbon nano-fiber
The bromobenzyls of 3g 1,3,5- tri- are weighed, is dissolved in 30g hexamethylenes, obtains solution A；Solution A is added to and filled
In the there-necked flask of ethyl containing hydrogen silicone oil, stirring is opened.The volume ratio of wherein solution A and ethyl containing hydrogen silicone oil is 1：8；Stirring
After 30min, the hexamethylene dissolved with anhydrous ferric trichloride is added thereto.Wherein anhydrous ferric trichloride quality is 1g, hexamethylene matter
Measure as 20g；System temperature is set as 80 DEG C, is incubated sustained response 8h, after being cooled to room temperature, is filtered, solvent cleans until filter
Liquid is water white transparency, obtains red brown solid；Obtained red brown solid is loaded into gauze bag, it carried out using absolute ethyl alcohol
Surname extraction, it is vacuum dried to produce hollow tubular polymer nanofiber after extracting 24h.Obtained hollow tubular is polymerize
Thing nanofiber calcines 5h for 550 DEG C under vacuum, cools to room temperature with the furnace, produces high-ratio surface hollow tubular carbon Nanowire
Dimension.
Claims (4)
1. a kind of preparation method of high-ratio surface hollow tubular carbon nano-fiber, it is characterised in that step is as follows：
Step 1：By monomer dissolving in a solvent, solution A is obtained；Wherein monomer mass fraction is 5-10%；The monomer is 1,
4- is to cyclite, the bromobenzyls of 1,3,5- tri-, 3,5- bis- (bromomethyl) toluene, 1,3- bis- (bromomethyl) benzene, 1,2- bis- (bromomethyl) benzene
Or 1,3- bis- (bromomethyl) toluene；
Step 2：Solution A is added in the there-necked flask for filling silicone oil, open stirring 10~30min after, add thereto dissolved with
The solvent of catalyst；Wherein the volume ratio of solution A and silicone oil is 1: 5~10；The mass ratio of catalyst and monomer is 1: 3~5；Institute
The mass fraction for stating catalyst is 4~6%；
Step 3：6~12h is reacted at being 75~85 DEG C in temperature by system, after being cooled to room temperature, is filtered, solvent cleans until filter
Liquid is water white transparency, obtains red brown solid；
Step 4：Obtained red brown solid is loaded into gauze bag, surname extraction is carried out to it using absolute ethyl alcohol, extracts 24h
Afterwards, it is vacuum dried to produce hollow tubular polymer nanofiber；
Step 5：Obtained hollow tubular polymer nanofiber is calcined into 3-8h for 500-700 DEG C under vacuum, it is cold with stove
But to room temperature, high-ratio surface hollow tubular carbon nano-fiber is produced.
2. the preparation method of high-ratio surface hollow tubular carbon nano-fiber according to claim 1, it is characterised in that：It is described molten
Agent is 1,2- dichloroethanes, chloroform, hexamethylene or normal heptane.
3. the preparation method of high-ratio surface hollow tubular carbon nano-fiber according to claim 1, it is characterised in that：The silicon
Oil is methyl-silicone oil, ethyl silicon oil, Methyl Hydrogen Polysiloxane Fluid, methyl phenyl silicone oil or ethyl containing hydrogen silicone oil.
4. the preparation method of high-ratio surface hollow tubular carbon nano-fiber according to claim 1, it is characterised in that：It is described to urge
Agent is anhydrous ferric trichloride or aluminum trichloride (anhydrous).
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108823881A (en) * | 2018-06-29 | 2018-11-16 | 宁波辉励铭诚汽车零部件有限公司 | A kind of device for car carpeting fluffing |
| CN113529205A (en) * | 2021-08-03 | 2021-10-22 | 西北工业大学 | Super-crosslinked porous polymer fiber and preparation method thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101824118A (en) * | 2010-05-26 | 2010-09-08 | 华中科技大学 | Porous polymer nanoparticles and preparation method thereof |
| CN105399981A (en) * | 2015-11-17 | 2016-03-16 | 西北工业大学 | Preparation method of resin balls with microcellular structure and ultrahigh specific surface area |
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2017
- 2017-10-31 CN CN201711055360.1A patent/CN107829169A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101824118A (en) * | 2010-05-26 | 2010-09-08 | 华中科技大学 | Porous polymer nanoparticles and preparation method thereof |
| CN105399981A (en) * | 2015-11-17 | 2016-03-16 | 西北工业大学 | Preparation method of resin balls with microcellular structure and ultrahigh specific surface area |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108823881A (en) * | 2018-06-29 | 2018-11-16 | 宁波辉励铭诚汽车零部件有限公司 | A kind of device for car carpeting fluffing |
| CN113529205A (en) * | 2021-08-03 | 2021-10-22 | 西北工业大学 | Super-crosslinked porous polymer fiber and preparation method thereof |
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Application publication date: 20180323 |