CN100503692C - Method for preparing poly 1,5-naphthalene diamine nano pipe - Google Patents
Method for preparing poly 1,5-naphthalene diamine nano pipe Download PDFInfo
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- CN100503692C CN100503692C CNB2007100375318A CN200710037531A CN100503692C CN 100503692 C CN100503692 C CN 100503692C CN B2007100375318 A CNB2007100375318 A CN B2007100375318A CN 200710037531 A CN200710037531 A CN 200710037531A CN 100503692 C CN100503692 C CN 100503692C
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Abstract
The present invention discloses a method of preparing 1,5-naphthalene diamine nanotube. The preparation method of poly 1,5- naphthalene diamine nanotube, said in the present invention, has the following processes: 1,5-naphthalene diamine monomer is dissolved in propylene glycol ester carbonate, and is blended with acidic aqueous solution to form the oil/water micro-interface; oxidant solution is added then, and is rested to make the complete reaction. Using the method of chemical oxidative polymerization in the present invention can acquire poly 1,5- naphthalene diamine nanotube, of which the diameter is about 100-200 nm, the length is about 1-2 mu m, and the wall thickness is 20 nm around. And only the large particle above the diameter( mu m) of poly naphthalene can be acquired by using the conventional single-phase chemical oxidative polymerization. The present invention which acquires nanotubes by only using oil/water interface to control the growth of polymers, thus needs neither template nor additive, is partly different from mostly conventional methods of preparing conductive polymer nanotube, and can use general methods to take washing and purification in post-processing.
Description
Technical field
The present invention relates to gather 1, the synthetic method field of 5-naphthylene diamine nanotube.
Background technology
The organic conductive polymkeric substance develops into very active research field owing to its unique character and application prospects.Along with developing rapidly of nano science and nanotechnology, the research of nano structural conductive polymkeric substance also more and more is subjected to the great attention of scientists.In an orderly manner, reasonably be assembled into two-dirnentional structure with conductive polymer nanometerization or with one dimension Nano structure, to help studying the influence of size and dimension, and have broad application prospects aspect the utility model quantum device making their optical property, magnetic property etc.Since twentieth century was found the conductivity of polyaniline the eighties, many potential were used also extensive studies, as: lightweight battery electrode, electromagnetic shielding equipment, corrosion prevention film and transmitter.The nanometer blank pipe especially has bigger potentiality in fields such as electronics, optics, catalysis, energy storage and biologies owing to different contacts area is arranged and some novel performances, therefore, has attracted numerous scholars' research interest.
At present, the preparation method about the conductive polymer nanometer pipe mainly contains hard template method, soft template method, microemulsion method, doping method, copolymerization method etc.For example, the polypyrrole nanotube can pass through reverse microemulsion process (Jang J, Yoon H.ChemicalCommunications, 2003,720-721.) or chemical vapor deposition polymerization method (Jang J on porous anodic alumina template, 0h H J.Chemical Communications, 2004,882-883.) make.The polyaniline nano pipe can be by outer adulterating method (Pinto N J, Carrion P L, Ayala A M, et al.Synthetic Metals, 2005,148:271-274) or auto-doping method (Yunze Long, Lijuan Zhang, Yongjun Ma, et al.Rapid Commun.2003,24,938-942) or add method (Zhixiang Wei, Meixiang Wan.Journal of Applied Polymer Science, 2003 of a small amount of napthylamine sulfonic acid and aniline copolymerization, 87,1297-1301) make.Yet above-mentioned template or emulsion method prepare the nano structural conductive polymkeric substance can produce the aftertreatment difficult problem, and may cause the destruction of nanostructure in removing the process of template.Therefore, seek a kind of simple and easy and method effective compositing conducting polymer nanocomposite structure remains a kind of challenging work.
Polydiaminonaphthalene is a kind of in the aromatic amine conductive polymers.Because the singularity of its structure, make polydiaminonaphthalene demonstrate than polyaniline and the more novel multifunctionality of polypyrrole, though its polymerization mechanism and performance also do not have the report determined, have at aspects such as electrocatalysis, electric colour developing, transmitter and electrode modified materials and obviously be different from the present research characteristics of electrically conductive polyaniline and polypyrrole etc. widely.The present inventor is to the literature review (Huang Meirong of fragrant naphthylene diamine, Li upstart, the Li sages and men of virtue. polydiaminonaphthalene synthetic and to the highly effective reaction absorption of heavy metal ion. chemical progress, 2005,17 (2): 299-309) show, most of research work all are the chemical structures of exploring the electrochemically oxidative polymerization resulting polymers by electrochemical method, and the morphological structure of polymkeric substance is not also related to.As Jackowska etc. with electrochemical synthesis poly-1, the 5-naphthylene diamine (Jackowska K, BukowskaJ, Jamkowski M.J.Electroanal Chem, 1995,388:101-108); Oyama etc. utilize electrochemical method to 2,3-naphthylene diamine polymkeric substance and 1,8-naphthylene diamine polymer architecture done some exploratory developments (Oyama N, Sato M, OhsakaT.Synthtic.Metals, 1989,29:E501-E506).Chemical oxidising polymerisation also only is confined to synthesizing micron-grade polydiaminonaphthalene powder in the single-phase polymerisation medium.And do not see the report that utilizes chemical oxidation to prepare the polydiaminonaphthalene nanotube.
Summary of the invention
Purpose of the present invention just provides a kind of economical and effective, easy suitable preparation gathers 1, the method for 5-naphthylene diamine nanotube.
The present invention adopts chemical oxidative polymerization, does not add any template and emulsifying agent and stablizer, and monomer that is dissolved in the organic solvent and the oxygenant that is dissolved in the sour water are reacted at oil/water micro-interface, and preparation gathers 1,5-naphthylene diamine nanotube.
The concrete technical scheme that the present invention takes is:
Poly-1, the preparation method of 5-naphthylene diamine nanotube, this method steps is as follows: with 1,5-naphthylene diamine monomer is dissolved in the propylene glycol carbonate, after carrying out blend and form oil/water micro-interface with acidic aqueous solution, adds oxidizing agent solution, static, it is reacted completely, obtain being dispersed in poly-1 in the water, 5-naphthylene diamine nanotube after the processing.
Gather 1, the nominal polyreaction formula of 5-naphthylene diamine nanotube is as follows:
Contrast with monomeric lavender, this polymkeric substance is a brown powder, has the external appearance characteristic of aromatic series conductive polymers, is indicating the generation of polymkeric substance.
Through X-ray diffraction analysis, gather 1,5-naphthylene diamine polymkeric substance is a undefined structure.Analyze through UV-vis, gather 1, have big pi-conjugated key, the generation that is indicating polymkeric substance in the 5-naphthylene diamine polymkeric substance.
Among the present invention, preparation gathers 1, and during 5-naphthylene diamine nanotube, it is protonated that strong acid environment makes that monomer is easier to.Acidic aqueous solution of the present invention is the aqueous solution of inorganic acid preferably, example hydrochloric acid, the vitriol oil etc.The concentration that these two kinds of acid are used in reaction is all greater than 1mol/L.
Oxygenant of the present invention most preferably is ammonium persulphate.The consumption of oxygenant all has a significant impact polymerization yield rate and polymer nanocomposite structure and morphology, and in the present invention, oxygenant and monomeric mol ratio are preferably 0.5:1～3:1, most preferably 0.75:1～1.5:1.
Organic phase propylene glycol carbonate of the present invention, its consumption all has a significant impact polymerization yield rate and polymer nanocomposite structure and morphology, in the present invention, the volume ratio of propylene glycol carbonate and acidic aqueous solution is preferably 1:10～1:2, and best volume ratio is 1:4.
Polymeric reaction temperature is to polymerization rate or to the formation of micro-interface considerable influence to be arranged all, and it is poly-1 that the temperature of reaction that is higher than room temperature all is unfavorable for, the formation of 5-naphthylene diamine nanotube, and therefore in the present invention, polymeric reaction temperature is preferably 0～5 ℃.
The present invention adopts currently known methods polymerisate to be separated aftertreatments such as purification.This processing comprises removes the monomer of not participating in reaction that remains in the reaction mixture, the oligopolymer that reaction generates, and residual oxygenant.Treatment step is: filtration, organic solvent washing, deionized water wash, precipitation and drying.
Beneficial effect of the present invention: adopt chemical oxidative polymerization method of the present invention can obtain poly-1,5-naphthylene diamine nanotube, caliber is greatly between 100-200nm, pipe range is approximately 1-2 μ m, and tube wall is as thin as about 20nm, and utilize conventional single-phase chemical oxidising polymerisation, can only obtain the above macrobead of polydiaminonaphthalene micron.It is different again that the present invention and major part are used the method for preparing the conductive polymer nanometer pipe always, need not any template or additive, just utilize oil/water termination to come the growth of controlling polymers, obtain nanotube, and aftertreatment can be washed purifying with general method, economical and effective, efficient, convenient.
Description of drawings
Fig. 1 is for gathering 1,5-naphthylene diamine and 1, the monomeric X ray diffracting spectrum of 5-naphthylene diamine.Gather 1, the X ray diffracting spectrum and 1 of 5-naphthylene diamine polymkeric substance, 5-naphthylene diamine monomer are obviously different.Monomer presents multiple sharp-pointed diffraction peak, shows that monomer is a crystalline compound.And polymkeric substance only presents the diffuse peaks of a broadness near 24.3 °, has the diffraction peak feature of amorphous polymer, and that is indicating generation gathers 1, and the 5-naphthylene diamine is a undefined structure.
Fig. 2 is for gathering 1,5-naphthylene diamine and 1, the monomeric infrared spectra of 5-naphthylene diamine.Analyze through FT-IR, gather 1, the infared spectrum and 1 of 5-naphthylene diamine polymkeric substance, 5-naphthylene diamine monomer are obviously different.Monomer presents multiple absorption peak, 3300～3400cm
-1Absorption shows amino existence.And polymkeric substance presents the absorption peak of a broad in this wave-number range, shows in the polymkeric substance except amino, also has imido grpup to have the generation that is indicating polymkeric substance.
Fig. 3 is for gathering 1,5-naphthylene diamine and 1, the ultra-violet absorption spectrum of 5-naphthylene diamine monomer in N-methyl-2-pyrrolidone.Analyze through UV-vis, gather 1, the uv-spectrogram and 1 of 5-naphthylene diamine polymkeric substance, 5-naphthylene diamine monomer are also different.Monomer and polymkeric substance all have absorption to UV-light, and just wavelength is slightly different, by the π-π of naphthalene ring in the molecule
*Transition causes.Different is that polymkeric substance presents the absorption peak of a broad near visible light 530nm, by n-π
*Transition causes that the conjugation absorption corresponding to the polymer macromolecule chain shows to have big pi-conjugated key, the generation that is indicating polymkeric substance in the polymkeric substance.
Fig. 4 gathers 1, the SEM of 5-naphthylene diamine nanotube at propylene glycol carbonate and 2mol/L hydrochloric acid micro-interface synthetic.
Fig. 5 gathers 1, the TEM of 5-naphthylene diamine nanotube at propylene glycol carbonate and 2mol/L hydrochloric acid micro-interface synthetic.
Fig. 6 gathers 1, the SEM of 5-naphthylene diamine nanotube at propylene glycol carbonate and 2mol/L sulfuric acid micro-interface synthetic.
Embodiment
Embodiment 1
Accurately take by weighing 0.158g (1mmol) 1, the 5-naphthylene diamine is dissolved in the propylene glycol carbonate of 5mL, according to oxygenant and monomer mole ratio is 1/1 to take by weighing Ammonium Persulfate 98.5 0.228g (1mmol) and be dissolved in the 5mL2.0mol/L aqueous hydrochloric acid, measures the 15mL2.0mol/L aqueous hydrochloric acid in addition again and pours in the beaker that magnon is housed.After treating three kinds of solution are all reduced to 0-5 ℃, will be dissolved with monomeric carbonate propanediol ester solution and join in the 15mL aqueous hydrochloric acid, stir, add the aqueous hydrochloric acid of 5mL oxygenant again, arrest reaction 24 hours.After reaction finishes, reaction mixture is poured in the beaker with 200mL deionized water termination reaction, centrifugation, with ethanol and deionized water wash 2-3 time, an at room temperature dry week of products therefrom, the brown polymer powder, productive rate about 36.4%.The X ray diffracting spectrum of this polymer powder is seen Fig. 1, as seen resulting polymers is a undefined structure, the infrared spectra of this polymer powder is seen Fig. 2, as seen the existence of amino and imido grpup, the ultra-violet absorption spectrum of the N of this polymkeric substance-methyl-2-pyrrolidone solution is seen Fig. 3, as seen, the existence of big pi-conjugated key.Observe through SEM (Fig. 4) and TEM (Fig. 5), this polymkeric substance pattern is a nanotube, and caliber is about 100-200nm, and pipe range is about 1-2 μ m, and thickness of pipe is about 20nm.
Embodiment 2
Repeat embodiment 1, substitute the 2.0mol/L aqueous hydrochloric acid but use the 2.0mol/L aqueous sulfuric acid instead.Get the brown polymer powder, productive rate about 36.0%.SEM observes and shows that this polymkeric substance pattern is a nanotube, and caliber is about 100-300nm, and pipe range is about 1-2 μ m, the tens of approximately nanometers of thickness of pipe, but also have small amounts of nanoparticles, see Fig. 6.
Embodiment 3
Repeat embodiment 1, but change oxygenant and monomer mole ratio are 1.5/1, get the brown polymer powder, productive rate about 41.7%.SEM observes and shows, this gathers 1, and 5-naphthylene diamine pattern is a nanotube, and caliber is about 100-250nm, and pipe range is about 1-2 μ m, the tens of approximately nanometers of thickness of pipe.
Embodiment 4
Repeat embodiment 1, but change oxygenant and monomer mole ratio are 0.5/1, get the brown polymer powder, productive rate about 27.8%.SEM observes and shows, this gathers 1, and the nanotube that the 5-naphthylene diamine forms is not complete especially.
Embodiment 5
Repeat embodiment 1, but the consumption of change organic phase propylene glycol carbonate is 10mL, gets the brown polymer powder.SEM observes and shows, this gathers 1, and 5-naphthylene diamine pattern is the sub-micro mitron of non-integrity, and caliber is about 500-600nm, and pipe range is about 2-3 μ m, the tens of approximately nanometers of thickness of pipe.
Embodiment 6
Repeat embodiment 1, but the consumption of change organic phase propylene glycol carbonate is 3mL, gets the brown polymer powder.SEM observes and shows, this gathers 1, and 5-naphthylene diamine pattern is sub-micrometer rod and submicron particles coexistence.
Embodiment 7～8
Repeat embodiment 1, the concentration that changes aqueous hydrochloric acid is respectively 0.5mol/L and 1mol/L.Get the brown polymer powder.Through tem observation, resulting polymers is the nano-scale particle about 100nm, and is not nanotube.
Embodiment 9～10
Repeat embodiment 1, the temperature that changes polyreaction is respectively room temperature and 40 ℃.Get the brown polymer powder,, be higher than the polymkeric substance that can't obtain nanostructure under the ambient temperature through tem observation.
Claims (4)
1, poly-1, the preparation method of 5-naphthylene diamine nanotube, this method steps is as follows: with 1,5-naphthylene diamine monomer is dissolved in the propylene glycol carbonate, after carrying out blend and form oil/water micro-interface with acidic aqueous solution, add oxidizing agent solution, static, it is reacted completely, acidic aqueous solution is meant the hydrochloric acid or the vitriolic aqueous solution, and oxygenant is an ammonium persulphate, and oxygenant and monomeric mol ratio are 0.5:1～3:1, the volume ratio of propylene glycol carbonate and acidic aqueous solution is 1:10～1:2, and polymeric reaction temperature is 0～5 ℃.
2, as claimed in claim 1 poly-1, the preparation method of 5-naphthylene diamine nanotube is characterized in that: the concentration of acidic aqueous solution is all greater than 1mol/L.
3, as claimed in claim 1 poly-1, the preparation method of 5-naphthylene diamine nanotube is characterized in that: oxygenant and monomeric mol ratio are 0.75:1～1.5:1.
4, as claimed in claim 1 poly-1, the preparation method of 5-naphthylene diamine nanotube is characterized in that: the volume ratio of propylene glycol carbonate and acidic aqueous solution is 1:4.
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| EP2507288A4 (en) * | 2009-11-30 | 2016-10-19 | Nanoscale Components Inc | Methods for producing textured electrode based energy storage device |
| CN102315424B (en) * | 2010-07-06 | 2014-07-16 | 中国科学院上海硅酸盐研究所 | Composite anode material for lithium sulfur battery, preparation method and application thereof |
| CN109456479A (en) * | 2018-11-08 | 2019-03-12 | 上海萃励电子科技有限公司 | A kind of RuO2Load the synthetic method of poly 1,5-naphthalene diamine nanotube |
| CN112661960B (en) * | 2020-12-01 | 2023-03-07 | 中国科学技术大学 | Poly (1, 8-diaminonaphthalene) nanosheet material, preparation method thereof, electrode material and supercapacitor |
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Non-Patent Citations (6)
| Title |
|---|
| Electrosynthesis of non conventional-polymer nanotubules:anew nanostructured material for analytical applications. A. Curulli, F. Valentini, S. Orlanducci, M.L. Terranova,ClaudiaPaoletti, G. Palleschi.Sensors and Actuators B,Vol.100 No.1-2. 2004 |
| Electrosynthesis of non conventional-polymer nanotubules:anew nanostructured material for analytical applications. A. Curulli, F. Valentini, S. Orlanducci, M.L. Terranova,ClaudiaPaoletti, G. Palleschi.Sensors and Actuators B,Vol.100 No.1-2. 2004 * |
| In situ deposition of poly(1,8-diaminonaphthalene): from thinfilms to nanometer-sized structures. Magdalena Tagowska, Barbara Palys, MaciejMazur, Magdalena Skompska, Krystyna Jackowska.Electrochimica Acta,Vol.50 No.12. 2005 |
| In situ deposition of poly(1,8-diaminonaphthalene): from thinfilms to nanometer-sized structures. Magdalena Tagowska, Barbara Palys, MaciejMazur, Magdalena Skompska, Krystyna Jackowska.Electrochimica Acta,Vol.50 No.12. 2005 * |
| 聚苯胺纳米管的制备及其导电性研究. 邹勇，刘吉平.北京理工大学学报，第25卷第5期. 2005 |
| 聚苯胺纳米管的制备及其导电性研究. 邹勇，刘吉平.北京理工大学学报，第25卷第5期. 2005 * |
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Assignee: Shanghai Gangshen Chemical Co., Ltd. Assignor: Tongji University Contract record no.: 2010310000159 Denomination of invention: Copoly(1,8-diaminonaphthalene) used as golden iron adsorption agent Granted publication date: 20090624 License type: Exclusive License Open date: 20071114 Record date: 20100909 |
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