CN101260187A - Method for preparing nano-stage naphthylamine sulfonate and aniline copolymer - Google Patents
Method for preparing nano-stage naphthylamine sulfonate and aniline copolymer Download PDFInfo
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- CN101260187A CN101260187A CNA2008100365984A CN200810036598A CN101260187A CN 101260187 A CN101260187 A CN 101260187A CN A2008100365984 A CNA2008100365984 A CN A2008100365984A CN 200810036598 A CN200810036598 A CN 200810036598A CN 101260187 A CN101260187 A CN 101260187A
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Abstract
The invention discloses a method for preparing nano sulfonic acid naphthylamine and aniline copolymer. The method is characterized in that: the neutral aqueous solution in sodium sulfonate naphthylamine is added in aniline aqueous solution and fully dissolved; then, oxidizing agent is added; when the reaction is finished, filtration, collection, precipitation, cleaning and drying are carried out to complete the preparation.
Description
Technical field
The present invention relates to a kind of method for preparing nano-stage naphthylamine sulfonate and aniline.
Background technology
Nano polyaniline is as the conjugation conducting polymer composite, specific conductivity controlled range that it is wide and the good doping-reversibility of going to mix has been given unique chemical property, thereby is widely used in fields such as biosensor, antistatic, electromagnetic radiation preventing paint, electrode catalyst active material, heavy metal absorbent.
The method for preparing the polyaniline nano material generally comprises chemical oxidization method and electrochemical process.Utilize chemical oxidization method such as letex polymerization, dispersion polymerization etc., be widely used thereby that the preparation nano polyaniline has is simple, be convenient to advantage such as scale operation.When using letex polymerization synthesized polyaniline nanometer latex particle or nanofiber, need to add a large amount of emulsifying agent such as sodium laurylsulfonate, in the hope of forming " nano-reactor " thus generate the stabilized nano polyaniline.Though the nano polyaniline size of preparation is controlled easily, but owing to add the heavy addition agent, production efficiency is low, the pattern and the purity of the polymkeric substance that cumbersome, the easy destruction of aftertreatment has generated, and a large amount of emulsifying agents of reaction process interpolation cause environmental pollution easily in addition.And utilize electrochemical process to prepare the advantage that the polyaniline nano material has one-step polymerization, and when this method prepares nano polyaniline, can utilize anodised aluminium as template, in nanoporous, carry out in-situ polymerization., electrochemical process limited the possibility of scale operation but being subjected to the restriction of electrode materials.And miscellaneous by adding the method aftertreatment that hard template prepares nano material, must remove hard template, in this process also easily destruction generated the form of polymkeric substance.In addition, according to the traditional preparation process method, the general polymerization reaction requires to carry out in acidic medium, so reaction process has been added a large amount of protonic acids such as 1mol/L hydrochloric acid soln, these acid solutions often do not recycle, and cause the waste to resource.
In recent years, people such as Wang Junsheng are by letex polymerization, adopt the oil soluble benzoyl peroxide to replace water-soluble ammonium persulphate as oxygenant, when hydrochloric acid medium concentration during less than 2mol/L, prepared polyaniline nano fiber in oil/water two-phase system, diameter is about 120nm.Because the nanofiber that forms in organic phase will be deposited in the aqueous solution from the organic solvent that contains oxygenant, this method has effectively solved the oxidant reaction by product and has been difficult to remove problem from the polymerization species.(Wang Zhi waits the people for Wang Junsheng, Wang Jixiao. and with the benzoyl peroxide oxygenant synthesized polyaniline nanofiber [J]. functional materials, 2007,38:2237-2239.).But, when aqueous solution acidity increases as sulphuric acid soln or be difficult to make polyaniline when adopting organic acid as acidic medium, this is to be dissolved in organic phase and to collect less than precipitation because the enhancing of protonated aniline cationic hydrophilic is difficult to cause only generating oligomer or doped polyaniline near the oil soluble oxygenant.Aspect the improvement of template polymerization method, people such as Zhou Jianzhang utilize tensio-active agent antianode aluminum oxide to carry out chemically modified, are the small size polyaniline nano-line of 7nm thereby synthesized diameter.And can regulate and control the diameter of prepared polymer nanotube, line by alkyl chain length on the change modification of surfaces promoting agent.(Zhou Jianzhang, Dong Ping, Cai Chengdong waits the people. and chemically modified anodic oxidation aluminium formwork method is synthesized small size polyaniline nano-line [J]. Acta PhySico-Chimica Sinica, 2004,20 (11): although 1287-1291.) the template technology of preparing updates, optimized the size and the homogeneous degree of prepared polyaniline, but limited by mould material, and its aftertreatment trouble, need or remove template dissolving, thereby restrict the possibility of its large-scale application.
Remove above-mentioned emulsion preparation method and template, recent years, interfacial polymerization prepares the concern that polyaniline nano fiber quite is subjected to the researcher.Interfacial polymerization makes it to be in two phases with oxygenant by the polyaniline nano material that timely separation generated, and has prepared the polyaniline nano material and effectively protected.As people such as Huang, utilize interfacial polymerization, it is the polyaniline nano fiber that 30～120nm does not wait that the agent of change protonic acid doping can prepare diameter.(Huang J X, Richard B K, The intrinsic nanofibrillar morphology of polyaniline[J] .Chem.Commun., 2006,4:367376.) this preparation method has advantages such as synthesis technique is simple, convenient post-treatment, but still need to add a large amount of organic reagents, and polymer yield is not very high.
As seen, the research of the nanometer of polyaniline is still waiting further deeply.Can develop out a kind of economical and effective, have good yield, the method for preparing the polyaniline nano material simple to operate, that universality is strong is very important.
Summary of the invention
The present invention provides a kind of method for preparing nano-stage naphthylamine sulfonate and aniline with good yield according to deficiency of the prior art.
For achieving the above object, the present invention is achieved through the following technical solutions:
Prepare the method for nano-stage naphthylamine sulfonate and aniline, it is characterized in that, the neutral aqueous solution of sodium sulfonate naphthylamines is added in the aniline-water solution, and makes it abundant dissolving, add oxygenant, after reaction finishes, filter collecting precipitation, clean, oven dry gets final product.
Wherein, moles such as stage naphthylamine sulfonate and sodium hydroxide are mixed with the neutral aqueous solution of sodium sulfonate naphthylamines.
Wherein, the mol ratio of described aniline and stage naphthylamine sulfonate is 50: 50～100: 0.5.
Wherein, described comonomer volumetric molar concentration is 0.1～0.5mol/L.
Wherein, described oxygenant is selected from persulphate, is preferably in ammonium persulphate, Sodium Persulfate and the Potassium Persulphate one or more.
Wherein, the monomeric mol ratio of described oxygenant and copolymerization is 0.5～2: 1.
Wherein, behind the adding oxygenant, temperature of reaction keeps 0～20 ℃.
Wherein, behind the adding oxygenant, the reaction times is 24～48h.
Wherein, the adding speed of oxygenant is that every mmole dripped in 0.5～10 minute.
If no special instructions, comonomer is meant two kinds of monomer sums among the present invention.
Among the present invention, AN is an aniline; SNA is meant sulfoacid aniline.
Respectively as Fig. 5, Fig. 6, infrared spectra shown in Figure 7, UV spectrum, X-ray diffraction analysis-by-synthesis, prepared this polymkeric substance has the constitutional features of polymer macromolecule, and the structure of finding prepared polymkeric substance is nonlinearities change with the monomer molar proportioning, confirms that prepared is aniline and stage naphthylamine sulfonate multipolymer.
Through the laser particle analyzer analysis, transmission electron microscope, scanning electron microscope and atomic power Electronic Speculum phenetic analysis confirm to have prepared really nano grade polymer repeatedly.
Beneficial effect of the present invention: method economical and effective of the present invention, have good yield and have general applicability, the productive rate that makes preparation-obtained in this way aniline and stage naphthylamine sulfonate multipolymer is up to more than the 90wt%, the polymkeric substance of preparation can present nanometer rod, nanometer piece and hollow ball shape, because the big naphthalene ring of sulfonic electrostatic interaction and stage naphthylamine sulfonate provides favourable condition for the formation of nano polyaniline, the nanometer of the polyaniline that a spot of stage naphthylamine sulfonate comonomer such as 3mol%～5mol% can realize, and status nascendi polymer nano granules specific conductivity when undoped can reach 10
-2S/cm.
Description of drawings
Fig. 1 is the aniline and the stage naphthylamine sulfonate multipolymer stereoscan photograph of embodiment 2 preparations;
Fig. 2 is the aniline and the stage naphthylamine sulfonate multipolymer transmission electron microscope photo of embodiment 4 preparations;
Fig. 3 is the aniline and the stage naphthylamine sulfonate multipolymer stereoscan photograph of embodiment 6 preparations;
Fig. 4 is the aniline and the stage naphthylamine sulfonate multipolymer stereoscan photograph of embodiment 11 preparations;
Fig. 5 is the polymkeric substance infrared spectrogram of the preparation of the method among the present invention;
Fig. 6 is the polymkeric substance ultraviolet spectrogram of the preparation of the method among the present invention;
Fig. 7 is the polymkeric substance X-ray diffractogram of the preparation of the method among the present invention.
Embodiment
The present invention is further described below in conjunction with embodiment.
7-sulfonic acid-naphthalidine of 0.0893g (0.4mmol) is joined in the 20mL aqueous solution of moles of NaOH (0.4mmol) such as containing, the aniline that adds 0.328mL (3.6mmol) after treating to dissolve fully then, quick magnetic agitation 30min in 20 ℃ water bath with thermostatic control.The 20mL aqueous solution that will be dissolved with 1.3692g (6mmol) ammonium persulphate then slowly splashes in the monomer solution with the 3 seconds/speed of dripping, and 20 minutes times spent dripped off.After oxygenant splashed into several, reaction soln promptly changed burgundy into by incarnadine, changed garnet and intensification gradually subsequently again into, had the grey black particle to generate behind the 15min.The agent of 20min rear oxidation dropwises, and continues to react 48h in 20 ℃ water bath with thermostatic control.After reaction finished, reaction solution was black opaque body system, got the stoste of 1mL and used for particle size analysis to bottle.All the other solution are filtered, and remove impurity such as oxygenant and oligopolymer, transfer to then and in 40 ℃ vacuum drying oven, dry in the watch-glass, obtain the 0.4160g black powder to constant weight with excessive distilled water.According to the ratio of output polymer weight with the monomer input amount, calculating its apparent productive rate is 103.0wt%.Utilize the laser particle analyzer analysis, the median size of the polymkeric substance that obtains is respectively 188nm.
Embodiment 2～6
Following embodiment with different monomers mole proportioning among illustrative explanation the present invention to the influence of polymerization yield rate and polymer sizes.
Repeat embodiment 1, but change the mole proportioning of aniline and 7-sulfonic acid-naphthalidine, making aniline and 7-sulfonic acid-naphthalidine mol ratio is 65: 35,70: 30,95: 5,98: 2,100: 0, and the productive rate that obtains polymkeric substance is respectively 57.9wt%, 60.7%, 104.9wt%, 105.7%, 104.0wt%.Utilize the laser particle analyzer analysis, the median size of the polymkeric substance that obtains is respectively 121nm, 68nm, 151nm, 2.7 μ m, 3.93 μ m.And SEM and TEM characterization result respectively as Fig. 1, Fig. 2, shown in Figure 3, show that the polymkeric substance pattern is respectively nanometer piece, nanometer rod, nanoparticle.The diameter of section of nanometer rod is about 31-63nm.
Embodiment 7～9
Following embodiment with different oxygen digital ratio among illustrative explanation the present invention to the influence of polymerization yield rate and polymer sizes.
Repeat embodiment 1, and the reaction times foreshorten to 24h, when changing the oxygenant add-on, making oxygenant and monomeric ratio is 0.5: 1,1: 1,1.25: 1, the productive rate that obtains polymkeric substance is respectively 16.4wt%, 61.6wt%, 82.7wt%.Utilize the laser particle analyzer analysis, the median size of the polymkeric substance that obtains is respectively 309nm, 162nm, 2.696 μ m.
Following embodiment with comonomer concentration among illustrative explanation the present invention to the influence of polymerization yield rate and polymer sizes.
Repeat embodiment 1, and the reaction times foreshorten to 24h, when comonomer concentration was increased to 0.3mol/L by 0.1mol/L, the productive rate that obtains polymkeric substance was respectively 61.6wt%, 82.7wt%.Utilize the laser particle analyzer analysis, the median size of the polymkeric substance that obtains is respectively 2.179 μ m, 100nm.The TEM characterization result shows that the pattern of polymer nano material is a club shaped structure, as shown in Figure 4.
Embodiment 12～13
Following embodiment is controlled at effect in the polyreaction with polymeric reaction temperature among illustrative explanation the present invention.
Repeat embodiment 1, and the reaction times foreshorten to 24h, the temperature when changing polyreaction makes polymeric reaction temperature be respectively 0 ℃, 5 ℃, the productive rate that obtains polymkeric substance is respectively 95.1wt%, 92.9wt%.Utilize the laser particle analyzer analysis, the median size of the polymkeric substance that obtains is respectively 3.97 μ m, 204nm.
Claims (10)
1. prepare the method for nano-stage naphthylamine sulfonate and aniline, it is characterized in that, the neutral aqueous solution of sodium sulfonate naphthylamines is added in the aniline-water solution, and makes it abundant dissolving, add oxygenant, after reaction finishes, filter collecting precipitation, clean, oven dry gets final product.
2. the method for preparing nano-stage naphthylamine sulfonate and aniline according to claim 1 is characterized in that, moles such as stage naphthylamine sulfonate and sodium hydroxide is mixed with the neutral aqueous solution of sodium sulfonate naphthylamines.
3. the method for preparing nano-stage naphthylamine sulfonate and aniline according to claim 1 is characterized in that, the mol ratio of described aniline and stage naphthylamine sulfonate is 50: 50～100: 0.5.
4. the method for preparing nano-stage naphthylamine sulfonate and aniline according to claim 1 is characterized in that, described comonomer volumetric molar concentration is 0.1～0.5mol/L.
5. the method for preparing nano-stage naphthylamine sulfonate and aniline according to claim 1 is characterized in that described oxygenant is selected from persulphate.
6. the method for preparing nano-stage naphthylamine sulfonate and aniline according to claim 5 is characterized in that described persulphate is selected from one or more in ammonium persulphate, Potassium Persulphate and the Sodium Persulfate.
7. the method for preparing nano-stage naphthylamine sulfonate and aniline according to claim 1 is characterized in that, the monomeric mol ratio of described oxygenant and copolymerization is 0.5～2: 1.
8. the method for preparing nano-stage naphthylamine sulfonate and aniline according to claim 1 is characterized in that, behind the adding oxygenant, temperature of reaction keeps 0～20 ℃.
9. according to claim 1 or the 4 described methods that prepare nano-stage naphthylamine sulfonate and aniline, it is characterized in that the adding speed of oxygenant is that every mmole dripped in 0.5～10 minute.
10. the method for preparing nano-stage naphthylamine sulfonate and aniline according to claim 1 is characterized in that, behind the adding oxygenant, the reaction times is 24～48h.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102153747A (en) * | 2011-02-17 | 2011-08-17 | 中国科学院长春应用化学研究所 | Method for preparing hollow polyaniline microspheres |
| CN103772702A (en) * | 2012-10-18 | 2014-05-07 | 上海纳米技术及应用国家工程研究中心有限公司 | Poly 1-naphthylamine nano hollow structure and its preparation method |
| CN109517168A (en) * | 2018-11-08 | 2019-03-26 | 上海萃励电子科技有限公司 | A kind of synthetic method of poly- naphthalidine -7- sulfonic acid nanotube |
-
2008
- 2008-04-24 CN CN2008100365984A patent/CN101260187B/en not_active Expired - Fee Related
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102153747A (en) * | 2011-02-17 | 2011-08-17 | 中国科学院长春应用化学研究所 | Method for preparing hollow polyaniline microspheres |
| CN102153747B (en) * | 2011-02-17 | 2012-10-31 | 中国科学院长春应用化学研究所 | Method for preparing hollow polyaniline microspheres |
| CN103772702A (en) * | 2012-10-18 | 2014-05-07 | 上海纳米技术及应用国家工程研究中心有限公司 | Poly 1-naphthylamine nano hollow structure and its preparation method |
| CN103772702B (en) * | 2012-10-18 | 2016-02-17 | 上海纳米技术及应用国家工程研究中心有限公司 | A kind of poly-naphthalidine nano hollow structure and preparation method thereof |
| CN109517168A (en) * | 2018-11-08 | 2019-03-26 | 上海萃励电子科技有限公司 | A kind of synthetic method of poly- naphthalidine -7- sulfonic acid nanotube |
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