CN103103629B - Fullerene-polymer composite nanofiber and preparation method thereof - Google Patents
Fullerene-polymer composite nanofiber and preparation method thereof Download PDFInfo
- Publication number
- CN103103629B CN103103629B CN201310058421.5A CN201310058421A CN103103629B CN 103103629 B CN103103629 B CN 103103629B CN 201310058421 A CN201310058421 A CN 201310058421A CN 103103629 B CN103103629 B CN 103103629B
- Authority
- CN
- China
- Prior art keywords
- fullerene
- preparation
- composite nanofiber
- polymer composite
- spinning solution
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Abstract
The invention discloses a fullerene-polymer composite nanofiber and a preparation method thereof. The preparation method comprises the following steps: conducting ball milling mixing on 2-20 wt% of fullerene and 80-98 wt% of a polymer material; dissolving the uniformly mixed mixture in a solvent, and thoroughly stirring to obtain a spinning solution; and preparing the uniformly stirred spinning solution into the fullerene-polymer composite nanofiber by an electrospinning method. The method provided by the invention solves the problem of incompatibility of fullerene and polymer material in solvent; meanwhile, the invention can greatly improve addition amount of the fullerene; and under high addition amount of fullerenes, the prepared composite nanofiber shows no phenomenon of fullerene particle aggregation.
Description
Technical field
The present invention relates to nano-fiber material field, particularly relate to a kind of Fullerene-polymer composite nanofiber and preparation method thereof.
Background technology
At present, C
60, C
70deng fullerene-based material with the extremely people's attention of the structures and characteristics of its uniqueness, become the important selection in the fields such as current physics, chemistry, material and life science.The molecular structure of the closed shell football shaped of fullerene high degree of symmetry determines it and has unique process based prediction model, the various chemical modification objects of fullerene have the performance of various uniqueness, and such as fullerene polymer derivative is as the using value good in photoelectricity, biologically active, catalysis, lubricant etc. of functional material.
Nanofiber is a kind of nano material of accurate one-dimentional structure, has the high length-diameter ratio similar with CNT, except having the features such as excellent in mechanical performance, specific area be large, also has the advantages such as easy machine-shaping, microstructure be controlled.
But, fullerene and Polymer materialspreparation is not also had to obtain the simple and effective method of blended fiber at present, expect the blended fiber of several different material, need first prepare fullerene polymer mixed solution, but due to the deliquescent restriction of fullerene, therefore be difficult to when preparing fullerene polymer mixed solution find suitable solvent that two kinds of material Homogeneous phase mixing are dissolved completely, cause existing fullerene cannot obtain mixing nanofiber with Polymer materialspreparation, fullerene and macromolecular material cannot realize effective compound at aspect of performance.
Therefore, prior art has yet to be improved and developed.
Summary of the invention
In view of above-mentioned the deficiencies in the prior art, the object of the present invention is to provide a kind of Fullerene-polymer composite nanofiber and preparation method thereof, be intended to solve existing fullerene and macromolecule is incompatible, cannot prepare the problem of blended fiber.
Technical scheme of the present invention is as follows:
A preparation method for Fullerene-polymer composite nanofiber, wherein, comprises step:
S1, by mass percentage, 2% ~ 20% fullerene and 80% ~ 98% macromolecular material are carried out ball milling and mixes;
S2, the mixture mixed to be dissolved in solvent, and fully to stir and make spinning solution;
S3, by electrospinning process, the spinning solution stirred is made fullerene-high molecular composite nano fiber.
The preparation method of described Fullerene-polymer composite nanofiber, wherein, in described step S1, the mass percentage of described fullerene is 3% ~ 10%.
The preparation method of described Fullerene-polymer composite nanofiber, wherein, described macromolecular material is one or more in polyacrylonitrile, polymethyl methacrylate, PVK, polyvinylpyrrolidone, chitin, carboxymethyl cellulose or shitosan.
The preparation method of described Fullerene-polymer composite nanofiber, wherein, described fullerene is C
60, C
70or C
60with C
70mixture.
The preparation method of described Fullerene-polymer composite nanofiber, wherein, in described step S1, adopt ball mill to carry out ball milling to fullerene and macromolecular material and mix, described ball mill is low temperature intermittent ball mill.
The preparation method of described Fullerene-polymer composite nanofiber, wherein, described solvent is DMF.
A kind of Fullerene-polymer composite nanofiber, wherein, adopts preparation method as claimed in claim 1 to prepare.
Beneficial effect: Fullerene-polymer composite nanofiber provided by the invention and preparation method thereof solves fullerene and macromolecular material inconsistent problem in a solvent, the present invention simultaneously can also improve the addition of fullerene greatly, and when higher fullerene addition, there is not the phenomenon that fullerenic particles is assembled in obtained composite nano fiber.
Accompanying drawing explanation
Fig. 1 is the morphology characterization figure of the Fullerene-polymer composite nanofiber that embodiment 1 prepares.
Fig. 2 is the morphology characterization figure of the Fullerene-polymer composite nanofiber that embodiment 2 prepares.
Fig. 3 is the morphology characterization figure of the Fullerene-polymer composite nanofiber that embodiment 3 prepares.
Fig. 4 to Fig. 5 is the electron microscope scanning figure of the spinning solution different amplification that embodiment 4 prepares.
Fig. 6 is the afm scan figure of the spinning solution that embodiment 4 prepares.
Detailed description of the invention
The invention provides a kind of Fullerene-polymer composite nanofiber and preparation method thereof, for making object of the present invention, technical scheme and effect clearly, clearly, the present invention is described in more detail below.Should be appreciated that specific embodiment described herein only in order to explain the present invention, be not intended to limit the present invention.
The preparation method of Fullerene-polymer composite nanofiber provided by the invention, it comprises step:
S1, by mass percentage, 2% ~ 20% fullerene and 80% ~ 98% macromolecular material are carried out ball milling and mixes;
S2, the mixture mixed to be dissolved in solvent, and fully to stir and make spinning solution;
S3, by electrospinning process, the spinning solution stirred is made fullerene-high molecular composite nano fiber.
In step sl, the present invention makes fullerene be dispersed among the powder of macromolecular material by ball milling hybrid mode, after mixture is dissolved into solvent, macromolecular material has good hydrotropy effect for fullerene, macromolecular material can form micella in a solvent simultaneously, has good burden effect for fullerene, and these two kinds of effects can ensure in the final composite nano fiber formed, fullerene is dispersed, and can not assemble.So, method provided by the invention solves fullerene and macromolecular material inconsistent problem in a solvent, the present invention simultaneously can also improve the addition of fullerene greatly, and when higher fullerene addition, there is not the phenomenon that fullerenic particles is assembled in obtained composite nano fiber.
Further, in step sl, the mass percentage of described fullerene is preferably 3% ~ 10%, can ensure the fullerene containing high level in last obtained composite nano fiber like this, fullerene can be made again to there will not be the situation of particle aggregation.
Further, described macromolecular material is preferably one or more in polyacrylonitrile, polymethyl methacrylate, PVK, polyvinylpyrrolidone, chitin, carboxymethyl cellulose or shitosan.These macromolecular materials have better solubilization-aid effect for fullerene, from the quality stability that improve composite nano fiber.
Further, described fullerene is C
60, C
70or C
60with C
70mixture, C
60, C
70best with the com-patibilising effect of macromolecular material.
In step sl, the present invention preferably adopts ball mill to carry out ball milling to fullerene and macromolecular material to mix, described ball mill is low temperature intermittent ball mill, as its name suggests, low temperature intermittent ball mill adopts exactly and carries out ball milling in step mode to fullerene and macromolecular material under cryogenic and mix, such temperature when the two can be made to carry out ball milling is unlikely to too high, avoids the molecular structure destroying fullerene, macromolecular material.Temperature-controllable during ball mill ball milling is built in 15 ~ 20 DEG C, and ball mill start and stop once: operate after 1 ~ 20 minute, stop 20 ~ 40 minutes, according to this ball milling method, ball milling mixing is carried out to mixture, good ball milling effect can be ensured, again can control temperature unlikely too high.
Further, in step s 2, described solvent is DMF(N, dinethylformamide), DMF is a kind of solvent of function admirable, and it is all good solvent to multiple macromolecular material, can be used for synthesizing the composite nano fiber in the present invention.
In step s3, the present invention adopts electrospinning process that spinning solution is prepared into composite nano fiber, realize particular by an electrostatic spinning apparatus, described electrostatic spinning apparatus comprises high voltage source, measuring pump, shower nozzle, receiver, (structure about electrostatic spinning apparatus can with reference to content of the prior art for container, the present invention repeats no more), spinning solution is moved in the container of electrostatic spinning apparatus, this container is provided with a taphole, described taphole place is provided with a metal needle, the aperture of described metal needle can be set to 0.1 ~ 1.6mm, the receiving range of receiver and metal needle is set to 10 ~ 20cm, and switch on power, the output voltage of high voltage source is adjusted to suitable voltage, spinning solution in container flows out from taphole and carries out electrostatic spinning, and the flow velocity of spinning solution is controlled by measuring pump, preferred control is 0.1 ~ 5ml/h, after treating spinning solution spinning all in container like this, collect the nonwoven fabric on receiver, obtained nonwoven fabric is size has tens to form to the long fiber of hundreds of nanometer.
The general principle of electrostatic spinning is by by high-pressure electrostatic on spinning solution band, and the drop of charged spinning solution is accelerated on the taylor cone summit of capillary under the effect of electric field, forms electrified jet, finally deposits on the receiver.
Based on the preparation method of above-mentioned Fullerene-polymer composite nanofiber, the present invention also provides a kind of Fullerene-polymer composite nanofiber, and it adopts above-mentioned preparation method to prepare.
Below by specific embodiment, the present invention will be described in more detail.
Embodiment one
1.5g polyacrylonitrile and 100mgC
60move to after mixing in ball grinder, ball grinder is contained in ball mill.Arrange ball milling speed 500 turns/h, ball milling temperature is set to 20 degree, and start and stop once comprise: often turn 10 minutes, stops 20 minutes, carries out obtained mixture after 12 start and stop continuously like this, is dissolved into by mixture in DMF, is made into the spinning solution that mass fraction is 10%.In the container of device for spinning, inject spinning solution, arranging voltage is 20kv, and accepting distance is 15cm.After spinning terminates, collect nonwoven fabric, carry out morphology characterization.
As can be seen from Fig. 1, although the composite nano fiber thickness obtained uneven, there is not the large-scale clustering phenomena of fullerenic particles in obtained composite nano fiber thickness.
Embodiment two
1.5g polymethyl methacrylate and 100mgC
60move to after mixing in ball grinder, ball grinder is contained in ball mill.Arrange ball milling speed 600 turns/h, ball milling temperature is 20 degree, and start and stop once comprise: often turn 15 minutes, stops 30 minutes, carries out obtained mixture after 12 start and stop continuously like this, is dissolved into by mixture in DMF, is made into the spinning solution that mass fraction is 12%.In the container of device for spinning, inject spinning solution, arranging voltage is 15kv, and accepting distance is 10cm.After spinning terminates, collect nonwoven fabric, carry out morphology characterization.
Fullerene and polymethyl methacrylate define uniform composite nano fiber as can be seen from Figure 2, and do not occur the phenomenon that fullerene is assembled on a large scale.
Embodiment three: 1.5g PVK and 100mgC
60move to after mixing in ball grinder, ball grinder is contained in ball mill.Arrange ball milling speed 600 turns/h, ball milling temperature is 20 degree, and start and stop once comprise: often turn 15 minutes, stops 30 minutes, carries out obtained mixture after 12 start and stop continuously like this, is dissolved into by mixture in DMF, is made into the spinning solution that mass fraction is 12%.In the container of device for spinning, inject spinning solution, arranging voltage is 15kv, and accepting distance is 10cm.After spinning terminates, collect nonwoven fabric, carry out morphology characterization.
As can be seen from Figure 3, fullerene and PVK define uniform composite nano fiber, do not occur the phenomenon that fullerene is assembled on a large scale simultaneously.
Embodiment four
In order to the existence of fullerene in spinning solution and macromolecular material is described, the present invention is by TEM(electron microscope) and AFM(AFM) carry out morphology characterization.For polyacrylonitrile, specific as follows: to mix fullerene and polyacrylonitrile powder completely in ball mill and be dissolved in DMF, make spinning solution after fully stirring, filter out a small amount of insoluble matter, lower floor's solution carries out AFM and TEM and characterizes.
As can be seen from Fig. 4 to Fig. 6, fullerenic particles is surrounded by polyacrylonitrile, and dispersed, and fullerene cluster size is about 10nm.In ball milling mixed process, fullerene has just been dispersed among polyacrylonitrile powder, there is good hydrotropy effect for fullerene in polyacrylonitrile after being dissolved into by mixed-powder in DMF, simultaneously polyacrylonitrile forms micella in DMF also can have good burden effect to fullerene, and two kinds of effects ensure that the dispersed of in the final nanofiber formed fullerene and do not find the clustering phenomena of fullerene.
In sum, preparation method provided by the invention, make use of hydrotropy effect and the burden effect of macromolecular material, fullerene can be dispersed in spinning solution, finally obtained composite nano fiber had both improve the addition of fullerene, can ensure that again fullerenic particles there will not be clustering phenomena, the composite nano fiber obtained has had that good mechanical performance, specific area are large concurrently, the process based prediction model of the various uniquenesses of the controlled and fullerene of easily machine-shaping, microstructure.
Should be understood that, application of the present invention is not limited to above-mentioned citing, for those of ordinary skills, can be improved according to the above description or convert, and all these improve and convert the protection domain that all should belong to claims of the present invention.
Claims (2)
1. a preparation method for Fullerene-polymer composite nanofiber, is characterized in that, comprises step:
S1, by mass percentage, 2% ~ 20% fullerene and 80% ~ 98% macromolecular material are carried out ball milling mix, adopt ball mill to carry out ball milling to fullerene and macromolecular material to mix, described ball mill is low temperature intermittent ball mill, and temperature during ball mill ball milling controls at 15 ~ 20 DEG C;
S2, to be dissolved in solvent by the mixture mixed, and fully to stir and make spinning solution, described solvent is DMF;
S3, by electrospinning process, the spinning solution stirred is made fullerene-high molecular composite nano fiber;
Described macromolecular material is one or more in polyacrylonitrile, polymethyl methacrylate, PVK, polyvinylpyrrolidone, chitin, carboxymethyl cellulose or shitosan;
Described fullerene is C
60, C
70or C
60with C
70mixture.
2. the preparation method of Fullerene-polymer composite nanofiber according to claim 1, it is characterized in that, in described step S1, the mass percentage of described fullerene is 3% ~ 10%.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310058421.5A CN103103629B (en) | 2013-02-25 | 2013-02-25 | Fullerene-polymer composite nanofiber and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310058421.5A CN103103629B (en) | 2013-02-25 | 2013-02-25 | Fullerene-polymer composite nanofiber and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN103103629A CN103103629A (en) | 2013-05-15 |
| CN103103629B true CN103103629B (en) | 2015-03-25 |
Family
ID=48311810
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201310058421.5A Active CN103103629B (en) | 2013-02-25 | 2013-02-25 | Fullerene-polymer composite nanofiber and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN103103629B (en) |
Families Citing this family (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105926053A (en) * | 2016-06-08 | 2016-09-07 | 海南大学 | Electrostatic spinning method of chitosan |
| CN108904302B (en) * | 2018-08-02 | 2021-01-29 | 北京福纳康生物技术有限公司 | Water-soluble fullerene external composition |
| CN110306256B (en) * | 2019-07-16 | 2021-10-01 | 高金鹿 | Preparation method of high-temperature-resistant para-aramid fiber |
| CN110496694B (en) * | 2019-08-30 | 2021-07-09 | 大连工业大学 | Waste wool fiber powder and preparation method and application thereof |
| CN110669511B (en) * | 2019-10-18 | 2022-07-26 | 安徽大学 | Fullerene crystal near-infrared light-emitting film and preparation method thereof |
| CN110904522A (en) * | 2019-12-12 | 2020-03-24 | 上海奥领纺织新材料有限公司 | Fullerene skin-friendly composite fiber and preparation method thereof |
| CN111172664B (en) * | 2019-12-27 | 2021-06-25 | 常熟市欣鑫经纬编有限公司 | Rabbit hair wool fiber-like fabric |
| CN113122959B (en) * | 2021-04-09 | 2021-12-10 | 天津工业大学 | Bulletproof composite fiber material and preparation method thereof |
| CN114622347A (en) * | 2022-02-28 | 2022-06-14 | 五邑大学 | Fiber membrane and preparation method and application thereof |
| CN115772725A (en) * | 2022-11-03 | 2023-03-10 | 苏州经贸职业技术学院 | Preparation of functional fullerene fiber blended silk fabric |
| CN115582104B (en) * | 2022-11-28 | 2023-03-14 | 佛山(华南)新材料研究院 | Dioxin separation membrane and preparation method thereof |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5350794A (en) * | 1993-07-22 | 1994-09-27 | E. I. Du Pont De Nemours And Company | Aliphatic polyamide compositions and fibers |
| US5591312A (en) * | 1992-10-09 | 1997-01-07 | William Marsh Rice University | Process for making fullerene fibers |
| CN1664182A (en) * | 2005-03-25 | 2005-09-07 | 东南大学 | Device and method for preparing combined continuous electro-spinning nano fibrous membrane |
| CN1844513A (en) * | 2006-03-22 | 2006-10-11 | 浙江大学 | Preparation of acrylon nano fiber membrane carrier materials and use thereof |
| CN1955213A (en) * | 2006-10-17 | 2007-05-02 | 北京服装学院 | Polymer nanofibre film mixed with fullerene and its preparation method |
-
2013
- 2013-02-25 CN CN201310058421.5A patent/CN103103629B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5591312A (en) * | 1992-10-09 | 1997-01-07 | William Marsh Rice University | Process for making fullerene fibers |
| US5350794A (en) * | 1993-07-22 | 1994-09-27 | E. I. Du Pont De Nemours And Company | Aliphatic polyamide compositions and fibers |
| CN1664182A (en) * | 2005-03-25 | 2005-09-07 | 东南大学 | Device and method for preparing combined continuous electro-spinning nano fibrous membrane |
| CN1844513A (en) * | 2006-03-22 | 2006-10-11 | 浙江大学 | Preparation of acrylon nano fiber membrane carrier materials and use thereof |
| CN1955213A (en) * | 2006-10-17 | 2007-05-02 | 北京服装学院 | Polymer nanofibre film mixed with fullerene and its preparation method |
Non-Patent Citations (2)
| Title |
|---|
| 电纺C60/PMMA微纳米纤维的结构与性能研究;贾清秀等;《合成纤维》;20081031(第10期);第15页1.2 * |
| 静电纺丝工艺参数对PMMA/富勒烯纤维形貌的影响;贾清秀等;《合成纤维》;20090630(第6期);第25页1.2 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN103103629A (en) | 2013-05-15 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103103629B (en) | Fullerene-polymer composite nanofiber and preparation method thereof | |
| KR101777975B1 (en) | Nanofiber-Nanowire Composite and The Manufacturing Method of The Same | |
| CN101721389B (en) | Method for preparing in-situ therapeutic substance-loaded microcapsules | |
| CN107119346B (en) | A kind of preparation method of carbon nano tube/graphene composite fibre | |
| Yu et al. | Liposomes self-assembled from electrosprayed composite microparticles | |
| CN107475798A (en) | A kind of nano-fiber material for the extraction of uranium from seawater and preparation method thereof | |
| Ewaldz et al. | Material selection in electrospinning microparticles | |
| CN102517020B (en) | Superparamagnetic fluorescent multifunctional mesoporous nanometer spherical material and preparation method thereof | |
| CN105951210A (en) | Beaded ultrafine fiber material with bead morphology and preparation method thereof | |
| CN103865104B (en) | A kind of preparation method of core shell nanoparticles | |
| CN108847492A (en) | A kind of N doping metals cobalt carbon nano-fiber composite material and its preparation method and application | |
| CN102389395A (en) | Preparation of n-HA/PLGA electrostatic spinning composite nanofiber medicament loading system | |
| Chen et al. | Synthesis and characterization of PVP/LiCoO2 nanofibers by electrospinning route | |
| CN106521646B (en) | A kind of preparation method of poly lactide-glycolide acid electrostatic spinning solution | |
| Li et al. | Fabrication and applications of multi-fluidic electrospinning multi-structure hollow and core–shell nanofibers | |
| CN102560733B (en) | Preparation of double-medicine-carrying system based on PLGA (poly(lactide-co-glycolide))-LAP (Laponite) composite nano fiber | |
| CN111472093A (en) | Nano-hydroxyapatite/polylactic acid composite fiber membrane and preparation method thereof | |
| CN105776180B (en) | A kind of preparation method of nanometer porous carbosphere | |
| Qian et al. | Triple-component drug-loaded nanocomposites prepared using a modified coaxial electrospinning | |
| Xu et al. | Electrospun nanoporous materials: reality, potential and challenges | |
| CN106581777A (en) | Polycaprolactone-graphene oxide composite porous scaffold material preparation method | |
| KR20130117744A (en) | Process for preparing highly dispersed and concentrated carbon nanotube aqueous solution | |
| CN106435805B (en) | A kind of preparation method of polystyrene electrostatic spinning solution | |
| CN103061043A (en) | Method for manufacturing polysuccinimide nano-fiber mat by electrostatic spinning | |
| CN102697727A (en) | Method for preparing self-assembly ketoprofen liposome by electrostatic spinning technology |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CP03 | Change of name, title or address | ||
| CP03 | Change of name, title or address |
Address after: No. 1001, Longgang Avenue, Longgang District, Shenzhen, Guangdong 518000 Patentee after: Shenzhen Lihe Technology Innovation Co.,Ltd. Patentee after: PEKING University SHENZHEN GRADUATE SCHOOL Address before: No. 49, Wuhe South Road, Buji Bantian, Shenzhen, Guangdong 518112 Patentee before: SHENZHEN BEAUTY STAR Co.,Ltd. Patentee before: PEKING University SHENZHEN GRADUATE SCHOOL |
|
| TR01 | Transfer of patent right | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20210629 Address after: No. 1001, Longgang Avenue, Pingxi community, Pingdi street, Longgang District, Shenzhen, Guangdong 518000 Patentee after: Shenzhen TONGCHAN Lixing Technology Group Co.,Ltd. Patentee after: PEKING University SHENZHEN GRADUATE SCHOOL Address before: No. 1001, Longgang Avenue, Longgang District, Shenzhen, Guangdong 518000 Patentee before: Shenzhen Lihe Technology Innovation Co.,Ltd. Patentee before: PEKING University SHENZHEN GRADUATE SCHOOL |