CN1803858A - Dispersion and directional arraying method of carbon nanotube based magnetic material in polymer - Google Patents
Dispersion and directional arraying method of carbon nanotube based magnetic material in polymer Download PDFInfo
- Publication number
- CN1803858A CN1803858A CN 200510112180 CN200510112180A CN1803858A CN 1803858 A CN1803858 A CN 1803858A CN 200510112180 CN200510112180 CN 200510112180 CN 200510112180 A CN200510112180 A CN 200510112180A CN 1803858 A CN1803858 A CN 1803858A
- Authority
- CN
- China
- Prior art keywords
- reactor
- magnetic material
- carbon nanotube
- ray
- lamp box
- 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.)
- Granted
Links
Landscapes
- Polymerisation Methods In General (AREA)
- Graft Or Block Polymers (AREA)
Abstract
The disclosed method to disperse and arrange directionally the nano carbon tube magnetic material in polymer for the first time comprises: at room temperature, mixing the deionized water and monomer with rotation speed as 150-1400r/min; adding the magnetic material to supersonic disperse for one hour; putting the reactor into UV or radiation lamp box, forcing magnetic field on two sides of reactor, leading inert gas to discharge oxygen, and adding light initiator; filtering the product to clean with deionized water and dry for 36-48h at 50-100Deg. The obtained composite material has much better properties.
Description
Technical field
The present invention relates to a kind of preparation method of polymer carbon nano tube magnetic composite, particularly relate to the dispersion of a kind of carbon nanotube based magnetic material in polymkeric substance and the method that aligns thereof.
Background technology
Carbon nanotube (CNTs) from early 1990s by Japanese scholar Iijima on the Nature 354 (1991) 56 report since, cause the very big attention of scientific circles and industrial community immediately, be the focus of international scientific research in recent years.Carbon nanotube is divided into multi-walled carbon nano-tubes (MWNTs) and Single Walled Carbon Nanotube (SWNTs), and the graphite flake layer structure of being made up of six-ring is curled and the concentric drums that forms constitutes.Different with diameter and spirality, carbon nanotube can present metal or characteristic of semiconductor.Carbon nanotube has excellent mechanical property, and the strength ratio steel is high 100 times, and relative density has only 1/6 of steel.Carbon nanotube has excellent microwave absorbing characteristic in addition, can be used for electromagnetic shielding or absorbing material etc.The polymer/carbon nano-tube matrix material has become the focus of World Science research from A.jayan etc. since Science265 (1994) 1212 reported first.The compound mutual supplement with each other's advantages or the reinforcement that can realize group element material of carbon nanotube and polymkeric substance, matrix material shows excellent more physics and chemical property, as better conductivity, mechanical property, optical property, absorption property and microwave absorbing property etc., has more wide application prospect.
Preparation method about the polymer carbon nano tube matrix material mainly contains the physical blending method, situ aggregation method and improved situ aggregation method etc. at present.I.Musa etc. report on Syn.Met 102 (1999) 1250, utilize the method for solution blending, promptly, will gather (3-octyl group thiophene) and be dissolved in the chloroform by ultrasonic means, the multi-walled carbon nano-tubes blend of crossing with ultra-sonic dispersion in hexene again makes the matrix material of poly-(3-octyl group thiophene)/CNTs.J.Zhaoxin etc. have described on Phys Lett 337 (2001) 43 by the synthetic PMMA/CNTs matrix material of melt blended method.
Situ aggregation method is a kind of another important method for preparing the polymer/carbon nano-tube matrix material.This method is general carries out surface treatment to carbon nanotube earlier, carbon nanotube is dispersed in the reaction monomers, adds initiator, utilize the functional group on CNTs surface to participate in polymerization, or utilize initiator to open the π key of CNTs, make it participate in polymerization and reach excellent compatibility with organic phase.Wan Meixiang etc. report on J Appl Polym Sci 74 (1999) 2605, by carry out home position polymerization reaction on carbon nanotube, prepared carbon nano-tube/poly pyrroles (PPy) matrix material, and its electricity, magnetic, thermal property are studied.Tang etc. have described on Macromolecules 32 (1999) 2569 and have utilized home position polymerization reaction to prepare MWNT/ polyphenylacetylene matrix material, have light limiting effect preferably.Jia Zhijies etc. adopt and improve in-situ compositing, have prepared PA6/CNTs, PMMA/CNTs matrix material at J.Tsinghua University (Natural Sciences) 40 (2000) 14, " developing material and application " 13 (1998) 22 reports respectively.The so-called in-situ compositing that improves promptly allows pure monomer polymerization add carbon nanotube after for some time more earlier and continues reaction.The control of time should guarantee that carbon nanotube is uniformly dispersed in polymkeric substance, make carbon nanotube postpone to add again as far as possible, makes polymer molecule grow up as far as possible.
The physical blending method is difficult to obtain the CNTs of favorable dispersity, and situ aggregation method can improve the dispersiveness of CNTs in polymeric matrix preferably, but CNTs does not realize directed in order dispersion in polymeric matrix.Realize that CNTs homodisperse in polymkeric substance makes its report that reaches oriented and ordered arrangement that discussion is not arranged so far as yet simultaneously.
Summary of the invention
Technical problem to be solved by this invention provides the method that a kind of carbon nanotube based magnetic material disperses and aligns in polymkeric substance, to remedy the deficiencies in the prior art or defective, satisfy the needs of producing with some field development.
In order to solve the problems of the technologies described above, the technical solution adopted in the present invention is: the method that a kind of carbon nanotube based magnetic material disperses and aligns in polymkeric substance comprises the steps:
Under the room temperature, earlier with volume ratio be: 2.5～8: 1 deionized water and reaction monomers mix under 150～400 rev/mins rotating speed, added the carbon nano tube magnetic material ultra-sonic dispersion then 1 hour, the addition of carbon nano tube magnetic material is 0.1～15%wt of monomer weight; Then reactor is put into ultraviolet lamp box or radiation lamp box; apply the magnetic field that an intensity is 200～400Oe on the reactor both sides; and in reactor, feed protection of inert gas; after oxygen in the question response device is drained, add the light trigger initiated polymerization, reacted 10～18 hours; leach product; and use deionized water rinsing, and dried 36～48 hours down at 50～100 ℃, obtain the polymer/carbon nano-tube magnetic composite that even carbon nanotube is disperseed and aligned.
As optimized technical scheme: described monomer is a polar monomer, comprises a kind of or its mixture in methyl methacrylate, vinylbenzene, the vinyl cyanide; The ray that described ultraviolet lamp box or radiation lamp box use is energetic ray, comprises a kind of in ultraviolet ray, alpha-ray, β ray, gamma-rays and the X ray; Described magnetic field comprises a kind of in parallel plate electric field, the coaxial coil; Method adjustment such as the distance of described magneticstrength by regulating voltage, magnetic field and reactor, putting position; Described inert atmosphere is a kind of or its mixture in nitrogen, argon gas or the neon; The flow of described rare gas element is 0.5～2 liter/minute; Ambient temperature refers to 10～40 ℃; Described light trigger is a kind of in bitter almond oil camphor methyl esters or the st-yrax.
Ultimate principle of the present invention is such: at first be coated on carbon nano tube surface with magnetic substance, give carbon nanotube certain magnetic, carry out in-situ polymerization in the carbon nano tube magnetic material adding reaction monomers with gained then, by applying foreign field, carbon nanotube based magnetic material is disperseed and orientations in polymkeric substance simultaneously on the reactor both sides.Wherein, carbon nanotube based magnetic material prepares with Chinese patent (application number is 200510024127.8,200510110183.3) disclosed method.
The invention has the beneficial effects as follows: adopt simple method to realize carbon nano tube magnetic material dispersion and compound preferably in polymkeric substance first, and realized carbon nano tube magnetic material aligning in order in polymeric matrix simultaneously, therefore can bring into play the performance of carbon nano tube magnetic material more fully, the polymer/carbon nano-tube matrix material of gained has excellent more mechanical property, electrical property, magnetic property etc.
Embodiment
Below in conjunction with specific embodiment the present invention is further elaborated.
Embodiment 1
Monomer is a vinyl cyanide, and the volume ratio of monomer and deionized water is 1: 3.Under the room temperature; earlier deionized water and reaction monomers are mixed under 250 rev/mins rotating speed; the carbon nanotube based magnetic material ultra-sonic dispersion 1 hour that adds monomer weight 1%wt then; add light trigger bitter almond oil camphor methyl esters; then reactor is put into the ultraviolet lamp box; applying an intensity on the reactor both sides is 200Oe parallel plate magnetic field; regulating voltage is 220V; the magnetic field distance is 40cm; and in reactor, feed nitrogen protection; after treating the oxygen in the reactor drained, open the light source initiated polymerization, reacted 15 hours; leach product; and with deionized water rinsing repeatedly, further dried 40 hours down at 80 ℃, obtain polyacrylonitrile/carbon nanotube magnetic composite material.
Measure according to GB, carbon nano tube magnetic material is good dispersion in polyacrylonitrile, and carbon nano tube magnetic material orientation degree in polyacrylonitrile is 85%.
Embodiment 2
Monomer is a vinyl cyanide, and the volume ratio of monomer and deionized water is 1: 2.5.Under the room temperature; earlier deionized water and reaction monomers are mixed under 400 rev/mins rotating speed; the carbon nanotube based magnetic material ultra-sonic dispersion 1 hour that adds monomer weight 1%wt then; add light trigger bitter almond oil camphor methyl esters; applying an intensity on the reactor both sides is 400Oe parallel plate magnetic field; regulating voltage is 220V; the magnetic field distance is 60cm; in reactor, feed nitrogen protection, then reactor is put into ultraviolet lamp box initiated polymerization, reacted 10 hours; leach product; and with deionized water rinsing repeatedly, further dried 48 hours down at 50 ℃, obtain polyacrylonitrile/carbon nanotube magnetic composite material.
Measure according to GB, carbon nano tube magnetic material is good dispersion in polyacrylonitrile, and carbon nano tube magnetic material orientation degree in polyacrylonitrile is 80%.
Embodiment 3
Monomer is a vinylbenzene, and the volume ratio of monomer and deionized water is 1: 8.Under the room temperature; earlier deionized water and reaction monomers are mixed under 150 rev/mins rotating speed; the carbon nanotube based magnetic material ultra-sonic dispersion 1 hour that adds monomer weight 15%wt then; add the light trigger st-yrax; applying an intensity on the reactor both sides is 300Oe parallel plate magnetic field; regulating voltage is 220V; the magnetic field distance is 60cm; in reactor, feed argon shield, then reactor is put into gamma-rays lamp box initiated polymerization, reacted 15～18 hours; leach product; and with deionized water rinsing repeatedly, further dried 36 hours down at 100 ℃, obtain polystyrene/carbon nanotube magnetic composite material.
Measure according to GB, carbon nano tube magnetic material is good dispersion in polystyrene, and carbon nano tube magnetic material orientation degree in polystyrene is 78%.
Embodiment 4
Monomer is a methyl methacrylate, and the volume ratio of monomer and deionized water is 1: 4.Under the room temperature; earlier deionized water and reaction monomers are mixed under 300 rev/mins rotating speed; the carbon nanotube based magnetic material ultra-sonic dispersion 1 hour that adds monomer weight 1%wt then; add the light trigger st-yrax; applying an intensity on the reactor both sides is 250Oe parallel plate magnetic field; regulating voltage is 220V; the magnetic field distance is 30～50cm; in reactor, feed the neon protection, then reactor is put into gamma-rays lamp box initiated polymerization, reacted 15 hours; leach product; and with deionized water rinsing repeatedly, further, obtain polymethylmethacrylate/carbon nanotube magnetic composite material 80～100 times oven dry 40 hours.
Measure according to GB, carbon nano tube magnetic material is good dispersion in polymethylmethacrylate, and carbon nano tube magnetic material orientation degree in polymethylmethacrylate is 75%.
Claims (7)
1. the carbon nanotube based magnetic material method of disperseing and aligning in polymkeric substance is characterized in that, comprises the steps:
Under the room temperature, earlier with volume ratio be: 2.5～8: 1 deionized water and reaction monomers mix under 150～400 rev/mins rotating speed, added the carbon nano tube magnetic material ultra-sonic dispersion then 1 hour, the addition of carbon nano tube magnetic material is 0.1～15%wt of monomer weight; Then reactor is put into ultraviolet lamp box or radiation lamp box; apply the magnetic field that an intensity is 200～400Oe on the reactor both sides; and in reactor, feed protection of inert gas; after oxygen in the question response device is drained, add the light trigger initiated polymerization, reacted 10～18 hours; leach product; and use deionized water rinsing, and dried 36～48 hours down at 50～100 ℃, obtain the polymer/carbon nano-tube magnetic composite that even carbon nanotube is disperseed and aligned.
2. method according to claim 1 is characterized in that described monomer is a polar monomer, comprises a kind of or its mixture in methyl methacrylate, vinylbenzene, the vinyl cyanide.
3. method according to claim 1 is characterized in that, the ray that described ultraviolet lamp box or radiation lamp box use is energetic ray, comprises a kind of in ultraviolet ray, alpha-ray, β ray, gamma-rays and the X ray.
4. method according to claim 1 is characterized in that, described magnetic field comprises a kind of in parallel plate electric field, the coaxial coil.
5. method according to claim 1 is characterized in that, method adjustment such as the distance of described magneticstrength by regulating voltage, magnetic field and reactor, putting position.
6. method according to claim 1 is characterized in that, described inert atmosphere is a kind of or its mixture in nitrogen, argon gas or the neon; Thereafter flow is 0.5～2 liter/minute.
7. method according to claim 1 is characterized in that, described light trigger is a kind of in bitter almond oil camphor methyl esters or the st-yrax.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2005101121803A CN100427511C (en) | 2005-12-29 | 2005-12-29 | Dispersion and directional arraying method of carbon nanotube based magnetic material in polymer |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2005101121803A CN100427511C (en) | 2005-12-29 | 2005-12-29 | Dispersion and directional arraying method of carbon nanotube based magnetic material in polymer |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1803858A true CN1803858A (en) | 2006-07-19 |
| CN100427511C CN100427511C (en) | 2008-10-22 |
Family
ID=36866025
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB2005101121803A Expired - Fee Related CN100427511C (en) | 2005-12-29 | 2005-12-29 | Dispersion and directional arraying method of carbon nanotube based magnetic material in polymer |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN100427511C (en) |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102516562A (en) * | 2011-09-28 | 2012-06-27 | 东华大学 | Method for preparing gel by using magnetic hybrid microspheres as cross-link points |
| CN102617758A (en) * | 2012-03-30 | 2012-08-01 | 北京化工大学 | Method for preparing orientated macromolecules in electric field by using ultraviolet polymerization |
| US9312046B2 (en) | 2014-02-12 | 2016-04-12 | South Dakota Board Of Regents | Composite materials with magnetically aligned carbon nanoparticles having enhanced electrical properties and methods of preparation |
| US9666861B2 (en) | 2014-04-25 | 2017-05-30 | South Dakota Board Of Regents | High capacity electrodes |
| US9892835B2 (en) | 2010-09-16 | 2018-02-13 | South Dakota Board Of Regents | Composite materials with magnetically aligned carbon nanoparticles and methods of preparation |
| JPWO2021125341A1 (en) * | 2019-12-20 | 2021-06-24 | ||
| US11824189B2 (en) | 2018-01-09 | 2023-11-21 | South Dakota Board Of Regents | Layered high capacity electrodes |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1164618C (en) * | 2002-03-14 | 2004-09-01 | 四川大学 | Preparation method of polymer/carbon nano pipe composite material and its in situ mass polymerization |
| CN1241979C (en) * | 2004-10-11 | 2006-02-15 | 东华大学 | Composite material fiber based on carbon nano-tube and its preparation method |
-
2005
- 2005-12-29 CN CNB2005101121803A patent/CN100427511C/en not_active Expired - Fee Related
Cited By (15)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US9892835B2 (en) | 2010-09-16 | 2018-02-13 | South Dakota Board Of Regents | Composite materials with magnetically aligned carbon nanoparticles and methods of preparation |
| CN102516562A (en) * | 2011-09-28 | 2012-06-27 | 东华大学 | Method for preparing gel by using magnetic hybrid microspheres as cross-link points |
| CN102617758A (en) * | 2012-03-30 | 2012-08-01 | 北京化工大学 | Method for preparing orientated macromolecules in electric field by using ultraviolet polymerization |
| CN102617758B (en) * | 2012-03-30 | 2013-05-29 | 北京化工大学 | Method for preparing orientated macromolecules in electric field by using ultraviolet polymerization |
| US9312046B2 (en) | 2014-02-12 | 2016-04-12 | South Dakota Board Of Regents | Composite materials with magnetically aligned carbon nanoparticles having enhanced electrical properties and methods of preparation |
| US10950847B2 (en) | 2014-04-25 | 2021-03-16 | South Dakota Board Of Regents | High capacity electrodes |
| US9666861B2 (en) | 2014-04-25 | 2017-05-30 | South Dakota Board Of Regents | High capacity electrodes |
| US11626584B2 (en) | 2014-04-25 | 2023-04-11 | South Dakota Board Of Regents | High capacity electrodes |
| US11824189B2 (en) | 2018-01-09 | 2023-11-21 | South Dakota Board Of Regents | Layered high capacity electrodes |
| JPWO2021125341A1 (en) * | 2019-12-20 | 2021-06-24 | ||
| WO2021125341A1 (en) * | 2019-12-20 | 2021-06-24 | 昭和電工株式会社 | Production method for polymer composition |
| CN114867755A (en) * | 2019-12-20 | 2022-08-05 | 昭和电工株式会社 | Method for producing polymer composition |
| JP7175406B2 (en) | 2019-12-20 | 2022-11-18 | 昭和電工株式会社 | Method for producing polymer composition |
| EP4079772A4 (en) * | 2019-12-20 | 2023-12-27 | Resonac Corporation | Production method for polymer composition |
| CN114867755B (en) * | 2019-12-20 | 2024-02-06 | 株式会社力森诺科 | Method for producing polymer composition |
Also Published As
| Publication number | Publication date |
|---|---|
| CN100427511C (en) | 2008-10-22 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN100427511C (en) | Dispersion and directional arraying method of carbon nanotube based magnetic material in polymer | |
| Zhou et al. | Selective Cu (II) ion removal from wastewater via surface charged self-assembled polystyrene-Schiff base nanocomposites | |
| Zhang et al. | Recent advances in microwave initiated synthesis of nanocarbon materials | |
| CN103160049B (en) | Preparation method for nano-silver/carbon nano-tube (CNT)/polyvinyl alcohol (PVA) composite electroconductive film | |
| CN103173041B (en) | Method for making core-shell polyhedral oligomeric silsesquioxane (POSS) coated multi-walled carbon nanotube (MWNT) | |
| CN108503804B (en) | Method for modifying polyester master batch by graphene material, graphene material modified polyester master batch obtained by method and application | |
| CN1410454A (en) | Preparation method of polymer/carbon nano pipe composite material and its in situ mass polymerization | |
| Qiang et al. | Recyclable 3D konjac glucomannan/graphene oxide aerogel loaded with ZIF-67 for comprehensive adsorption of methylene blue and methyl orange | |
| CN100358943C (en) | Process for preparing carbon nano pipe/polyhenylethylene nano conducting composite | |
| Zhao et al. | Luminescent polymethacrylate composite nanofibers containing a benzoic acid rare earth complex: morphology and luminescence properties | |
| CN104387507B (en) | A kind of method for manufacturing diolefine polymerization catalyst using CNT/anhydrous magnesium chloride as carrier and its preparation method and application | |
| Nisar et al. | Synthesis of polyethylene/nickel–carbon stimuli-responsive material under magnetic field at room temperature: effect of the filler on the properties | |
| Zhang et al. | Preparation and characterization of KGM/CdS nanocomposite film with low infrared emissivity | |
| Wei et al. | Microplasma electrochemistry (MIPEC) strategy for accelerating the synthesis of metal organic frameworks at room temperature | |
| Li et al. | A novel route for preparation of hollow carbon nanospheres without introducing template | |
| Zeng et al. | Cationic polyelectrolyte-assisted synthesis of silica nanochains for enhancing mechanical properties of sodium alginate composite films | |
| Guo et al. | Investigation into the role of poly (vinylpyrrolidone) in the growth of high aspect ratio silver nanowires | |
| Chilukusha et al. | Swift heavy ion irradiation of polyaniline-graphene nanocomposite films: Structural and optical properties | |
| Ali et al. | Facile microwave synthesis of multi‐walled carbon nanotubes for modification of elastomer used as heaters | |
| CN109456586B (en) | Melt blending method modified carbon nano particle/polycarbonate nano composite film and preparation method thereof | |
| Li et al. | High volume fraction and uniform dispersion of carbon nanotubes in aluminium powders | |
| CN1216085C (en) | Method for preparing nano montmorillonite-phenylethylene in-situ intercalation polymer | |
| CN116376058A (en) | Aramid nanofiber conductive hydrogel and preparation method and application thereof | |
| CN101700880A (en) | Carbon nano tube surface modification method | |
| Gao et al. | Synthesis of a novel mesoporous inorganic–organic hybrid and its application in epoxy resins |
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 | ||
| C53 | Correction of patent for invention or patent application | ||
| CB03 | Change of inventor or designer information |
Inventor after: Zhu Meifang Inventor after: Qiu Dahong Inventor after: Zhou Zhe Inventor after: Wu Zhaomian Inventor after: Zhang Kai Inventor after: Cao Huiqun Inventor after: Yang Weizhong Inventor before: Zhu Meifang Inventor before: Wu Zhaomian Inventor before: Zhang Kai Inventor before: Cao Huiqun |
|
| COR | Change of bibliographic data |
Free format text: CORRECT: INVENTOR; FROM: ZHU MEIFANG WU ZHAOMIAN ZHANG KAI CAO HUIQUN TO: ZHU MEIFANG QIU DAHONG ZHOU ZHE WU ZHAOMIAN ZHANG KAI CAO HUIQUN YANG WEIZHONG |
|
| C17 | Cessation of patent right | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20081022 Termination date: 20101229 |