CN103848987B - High crystalline polyaniline and preparation method thereof - Google Patents
High crystalline polyaniline and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a kind of high crystalline polyaniline and preparation method thereof, described polyaniline is in the Radix Rumicis district of XRD i.e. > 10 ° time spike occurs.Described polyaniline is prepared by following steps: be dissolved in inorganic salt solution by aniline, is placed in the electric field of 10 100V standing, inorganic salt one in sodium chloride, magnesium sulfate or aluminum chloride；Compound enzyme and glucose join initiated polymerization in above-mentioned solution, and control solution ph is 45, and compound enzyme is horseradish peroxidase and glucoseoxidase；Water, ethanol and washing with acetone, vacuum drying are used in reaction after terminating, finally grind and obtain powdery product.The polyaniline obtained has excellent electrochemical properties, in the field such as ultracapacitor, electrochemical sensor, there is good using value, compared to tradition polyaniline, product electrochemical stability and the ability of storing charge and release electric charge that thus method obtains all are greatly improved.
Description
Technical field
The present invention relates to a kind of at high crystalline polyaniline and preparation method thereof, belong to field of chemical preparation.
Background technology
At present conducting polymer is widely used to industrial and agricultural production field, wherein electrically conductive polyaniline (English abbreviation:
Pani) enjoy due to features such as environmental stability is good, synthesis simple, cheap and easy to get, the Bronsted acid doping property of raw material
Pay close attention to.The polyaniline that correlational study and the focus of application concentrate on nanostructured recently is to have ratio based on this material
The advantages such as surface area is big, the evolving path is short, good dispersion, at sensor, anticorrosive paint, composite, electromagnetism
The aspects such as shielding, ultracapacitor and secondary cell are with a wide range of applications.The special conduction that must it is worthy of note
Its chemical property is played vital effect by the crystallinity of polymer, even plays decisive to some performance
Effect, such as in conducting polymer, the mobility of carrier improves with the crystallinity of conducting polymer and accelerates, then
The height of person's performance has been largely fixed the efficiency of related electronic devices and the stability of duty thereof.
Present at present polyaniline synthesis, subject matter has: 1) whole polymerization process lack to monomer, intermediate and
The orientation of end product, limits the crystalline raising of final products；2) initiation method of polyreaction uses once
Property pulse sample loading alternative cause polymerization initial stage product structure to be difficult to regulate and control, reduce product structural order；3) adopt
Easily produce polymerization rate by traditional chemistry initiation method too fast, but be a molecularly oriented and need certain response
Time, the too fast meeting of rate of polymerization causes polyreaction intermediate to be difficult to effectively being orientated.
The synthesis of polyaniline is mainly carried out in aqueous phase system, and corresponding deriving method is also the most based on this.People recently
Having been found that in an experiment and be placed in external physical field by this polymerization reaction system, the structure of products therefrom, character are complete
Corresponding product in the presence of being entirely different from without outfield.Reaction system is mainly played following effect by extraneous physical field: 1)
Being orientated the dominant species in reaction system, the physical field reported has: ultrasonic field, magnetic field, gravitational field,
Microwave field etc. (refer to: Wang Yifan, Zhang Gang etc. synthesize the technical study [J] of electrically conductive polyaniline under ultrasonic field. Shenyang
Polytechnics's journal, 200827 (2): 69-72.；Lintao C,Shibing Y,Shaomin Z.Effects
of the magnetic field on the Polyaniline film studied by in situ conductivity
measurements and X-ray diffraction[J].J.Elecrtoanal.Chem.,1997,421:
45-48.；Xin-wei L,Wei W,Jian-feng C,et al.Preparation of polyaniline
nanofibers by high gravity chemical oxidative polymerization[J].Ind.Eng.
Chem.Res,2011,50:5589–5595.；Marija R,Gizdavic N,Dragomir R,et al.A
rapid and facile synthesis of nanofibrillar polyaniline using microwave
radiation[J].Macromol Rapid Commun,2010,31:657–661.；Ma Li, Chen Chao, Huang Ke
Dragon, Lu Wei, Chen Fengqiang. the magnetic field impact [J] on polyaniline structure, doping behavior and heat stability. " functional material
2007,9:1434-1436)；2) response path is affected to realize the control of product structure (is referred to: Zhenqi
C,Gang L,Zhicheng Z.Effects of electric fields in polymerization on
enthalpy of PMAA anhydridization[J].Thermochimica Acta,2004,411:95–100)。
Although existing lot of documents proves that synthesized polyaniline can improve the properity of polymer in outfield, opens up
Open up its application prospect, but the work of synthesis high crystalline polyaniline is not the most carried out under the electric field.More than compared to
For outfield, electric field is easier to obtain in actual production with practice, the controllability of electric field intensity and the standard of regulation
Really property is the most all easier to manipulation；And the existence of electric field is combined further by well-designed related experiment thinking
Be conducive to synthesis high crystalline electrically conductive polyaniline.
The present invention uses following thinking in synthesis: 1) the most in the electric field by aniline monomer aqueous solution
The long-term regularity standing raising monomer arrangement, it is achieved before reaction, the effective of polymerization system is controlled；2) by compound
Means associated with enzyme solve a difficult problem for initiator slow release, it is possible to realize the fully controllable of trigger rate, be conducive to simultaneously
Product orientation in the electric field in reaction.The conjunction of high crystalline polyaniline is finally realized by these means of integrated application
Become, improve use value and the application of polymer.
Summary of the invention
In order to overcome existing polyaniline material crystallinity poor, electrochemical stability difference causes the repeatability of related device
And the defect that service life is low, the invention provides a kind of high crystalline polyaniline and synthetic method thereof.
The technical solution realizing the object of the invention is: a kind of high crystalline polyaniline, described polyaniline exists
The Radix Rumicis district of XRD is i.e. > 10 ° time spike occurs.
Above-mentioned high crystalline polyaniline is prepared by following steps:
The first step, aniline is dissolved in inorganic salt solution, is placed in the electric field of 10-100V standing, nothing
Machine salt one in sodium chloride, magnesium sulfate or aluminum chloride；
Second step, compound enzyme and glucose are joined initiated polymerization in above-mentioned solution, control pH value of solution
Value is at 4-5, and compound enzyme is horseradish peroxidase and glucoseoxidase；
Water, ethanol and washing with acetone, vacuum drying are used in 3rd step, reaction after terminating, finally grind and obtain powder
Shape product.
Aniline molar concentration described in the first step is 0.086M, and described sodium chloride concentration is 0.2-0.6M, preferably
0.4M；Described magnesium sulfate concentration is 0.4-0.8M, and aluminum trichloride concentration is 0.2-0.6M, and time of repose is 1
More than it；
Horseradish peroxidase described in second step is 10mg/ml with the concentration of glucoseoxidase, described
Glucose and the preferred 1:1 of aniline mol ratio, described solution ph preferably 4.5；Polymerization reaction time is 1-2
My god.
Baking temperature described in 3rd step is at 60 DEG C, and drying time is more than 12h.
The principle of the present invention is: polymerization system can carry out in the presence of external electric field preorientation, and then use compound
Enzyme slow release initiation method realizes the electric field orientation to polymerization process, is finally capable of the conjunction of high crystalline polyaniline
Become.
The invention have the advantage that the polyaniline that the present invention obtains has excellent electrochemical properties, at super capacitor
The field such as device, electrochemical sensor has good using value, and compared to tradition polyaniline, thus method obtains
Product electrochemical stability and storing charge are all greatly improved with the ability of release electric charge.
Accompanying drawing explanation
Fig. 1 is that (a is 500nm for the stereoscan photograph of highly crystalline polyaniline in the embodiment of the present invention 3；B is
1000nm)。
Fig. 2 is the XRD figure (quoted from Synthetic Metals, 2007,269-275) of the most common polyaniline.
Fig. 3 is the XRD figure of polyaniline in embodiment of the present invention 1-7 and comparative example example.
Fig. 4 is by embodiment of the present invention Isosorbide-5-Nitrae, 6 and the super capacitor prepared of the polyaniline of comparative example example synthesis
The ratio capacitance of device is with the changing trend diagram of cycle-index.
Detailed description of the invention
Embodiment 1
0.2g aniline (2.1mmol) is dissolved in 25ml distilled water (molar concentration: 0.086M), continues to dissolve
0.293-0.878g NaCl (molar concentration 0.20-0.60M), is respectively placed in this mixed solution in the electric field of 10V, quiet
After putting 24hr, disposable addition contains horseradish peroxidase, (two kinds of enzyme concentrations are 10 to glucoseoxidase
And the 5ml aqueous solution initiation reaction of 0.378g glucose (2.1mmol) mg/ml), controlling solution ph is 4.5,
Product water, ethanol and the washing with acetone that will obtain after 24 hours, is vacuum dried 24h at 60 DEG C, finally grinds
Obtain powdery product.The electrical conductivity of final products is 0.3-0.6S/cm.
Embodiment 2
0.2g aniline (2.1mmol) is dissolved in 25ml distilled water (molar concentration: 0.086M), continues to dissolve
0.293-0.878g NaCl (molar concentration 0.20-0.60M), is respectively placed in this mixed solution in the electric field of 100V,
After standing 24hr, disposable addition contains horseradish peroxidase, (two kinds of enzyme concentrations are 10 to glucoseoxidase
And the 5ml aqueous solution initiation reaction of 0.378g glucose (2.1mmol) mg/ml), controlling solution ph is 4.5,
Product water, ethanol and the washing with acetone that will obtain after 24 hours, is vacuum dried 24h at 60 DEG C, finally grinds
Obtain powdery product.The electrical conductivity of final products is 0.2-0.4S/cm.
Embodiment 3:
0.2g aniline (2.1mmol) is dissolved in 25ml distilled water (molar concentration: 0.086M), continues to dissolve
0.585g NaCl (molar concentration 0.40M), is placed in this mixed solution in the electric field of 20V, after standing 24hr once
Property add containing horseradish peroxidase, glucoseoxidase (two kinds of enzyme concentrations are 10mg/ml) and 0.378g
The 5ml aqueous solution initiation reaction of glucose (2.1mmol), controlling solution ph is will to obtain after 4.5,24 hours
Product use water, ethanol and washing with acetone, at 60 DEG C be vacuum dried 24h, finally grind obtain powdery product.
The electrical conductivity of final products is 1.0S/cm.
Comparison example:
0.2g aniline (2.1mmol) is dissolved in 25ml distilled water (molar concentration: 0.086M), continues to dissolve
0.585g NaCl (molar concentration 0.40M), after standing 24hr in the case of being not added with electric field, disposable addition is containing peppery
Root catalase, glucoseoxidase (two kinds of enzyme concentrations are 10mg/ml) and 0.378g glucose (2.1mmol)
5ml aqueous solution initiation reaction, product water, ethanol and the washing with acetone that will obtain after 24 hours, at 60 DEG C
Vacuum drying 24h, finally grinds and obtains powdery product.The electrical conductivity of final products is 0.2S/cm.
Embodiment 4
0.2g aniline (2.1mmol) is dissolved in 25ml distilled water (molar concentration: 0.086M), continues to dissolve
1.20-2.40g MgSO4(molar concentration 0.40-0.80M), is respectively placed in this mixed solution in the electric field of 10V, quiet
After putting 24hr, disposable addition contains horseradish peroxidase, (two kinds of enzyme concentrations are 10 to glucoseoxidase
And the 5ml aqueous solution initiation reaction of 0.378g glucose (2.1mmol) mg/ml), controlling solution ph is 4.5,
Product water, ethanol and the washing with acetone that will obtain after 24 hours, is vacuum dried 24h at 60 DEG C, finally grinds
Obtain powdery product.The electrical conductivity of final products is 0.4-0.7S/cm.
Embodiment 5
0.2g aniline (2.1mmol) is dissolved in 25ml distilled water (molar concentration: 0.086M), continues to dissolve
1.20-2.40g MgSO4(molar concentration 0.40-0.80M), is respectively placed in this mixed solution in the electric field of 100V,
After standing 24hr, disposable addition contains horseradish peroxidase, (two kinds of enzyme concentrations are 10 to glucoseoxidase
And the 5ml aqueous solution initiation reaction of 0.378g glucose (2.1mmol) mg/ml), controlling solution ph is 4.5,
Product water, ethanol and the washing with acetone that will obtain after 24 hours, is vacuum dried 24h at 60 DEG C, finally grinds
Obtain powdery product.The electrical conductivity of final products is 0.05-0.2S/cm.
Embodiment 6
0.2g aniline (2.1mmol) is dissolved in 25ml distilled water (molar concentration: 0.086M), continues to dissolve
0.668-2.00g AlCl3(molar concentration 0.20-0.60M), is respectively placed in this mixed solution in the electric field of 10V, quiet
After putting 24hr, disposable addition contains horseradish peroxidase, (two kinds of enzyme concentrations are 10 to glucoseoxidase
And the 5ml aqueous solution initiation reaction of 0.378g glucose (2.1mmol) mg/ml), controlling solution ph is 4.5,
Product water, ethanol and the washing with acetone that will obtain after 24 hours, is vacuum dried 24h at 60 DEG C, finally grinds
Obtain powdery product.The electrical conductivity of final products is 0.4-0.6S/cm.
Embodiment 7
0.2g aniline is dissolved in molar concentration (0.086M) in 25ml distilled water, continues to dissolve 0.668-2.00g
AlCl3(molar concentration 0.20-0.60M), is respectively placed in this mixed solution in the electric field of 100V, after standing 24hr
Disposable add containing horseradish peroxidase, glucoseoxidase (two kinds of enzyme concentrations are 10mg/ml) and
The 5ml aqueous solution initiation reaction of 0.378g glucose (2.1mmol), after control solution ph is 4.5,24 hours
Product water, ethanol and the washing with acetone that will obtain, is vacuum dried 24h at 60 DEG C, finally grinds and obtain powder
Shape product.The electrical conductivity of final products is 0.12-0.25S/cm.
The polyaniline with nanofibrous structures has unique advantage in terms of the preparation of electrochemical sensor, by implementing
The electromicroscopic photograph of the product that example 3 obtains is as it is shown in figure 1, product is mainly based on nanofiber as seen from the figure, wherein
The general 40-50nm of fibre diameter, distribution of sizes ratio is more uniform.
The polyaniline obtained at present is amorphous body, and the upper 20-30 ° of interval of its XRD figure (see Fig. 3) has 1 or 2
Wide Bao Feng, if only 1 Kuan Bao peak proves without any structural order, wherein 2 Kuan Bao peaks result from respectively
Polyaniline chain is along the lack of alignment of parallel direction Yu vertical direction.As shown in Figure 2, the polyaniline that prepared by this patent exists
30 ° have other conventional unexistent height of polyaniline system and spikes of moderate strength with 34 °, show made polymer
There is the most orderly state of aggregation, only high crystalline polymer just to occur XRD Radix Rumicis district (more than 10 °)
Sharp-pointed narrow peak, narrow peak number mesh is the most, and the crystallinity of peak intensity the biggest explanation associated products is the highest.Curve 1 in Fig. 3,
2 correspond respectively to embodiment 2,1；Curve 3,4 corresponds respectively to embodiment 5,4；Curve 5,6 correspond respectively to
Embodiment 7,6；Curve 7 is corresponding to embodiment 3, and curve 8 is without the comparison example in electric field system.From Fig. 3
In visible, the crystallinity of the polyaniline obtained in comparative example be far below said method gained, under the electric field can illustrate
Promote the synthesis of high crystalline polyaniline.The ultracapacitor that in embodiment 1,4 and 6, polyaniline prepares passes through
Measuring its ratio capacitance values after 1000 circulations, accordingly result is shown in Fig. 4, closes as seen from Figure 4 in the presence of AlCl3
After 1000 circulations, it is other system same test conditions than electric capacity to the ultracapacitor prepared by polyaniline become
Under more than one times, illustrate that it has good chemical property, compared to tradition polyaniline, thus method obtain
Product electrochemical stability and storing charge are all greatly improved with the ability of release electric charge, are expected to become good
Ultracapacitor candidate material.
Claims (9)
1. a high crystalline polyaniline, it is characterised in that described high crystalline polyaniline is at the Radix Rumicis of XRD
District is i.e. > 10 ° time occur that spike, described high crystalline polyaniline are prepared by following steps:
The first step, aniline is dissolved in inorganic salt solution, is placed in the electric field of 10-100V standing, inorganic
Salt one in sodium chloride, magnesium sulfate or aluminum chloride；
Second step, compound enzyme and glucose are joined initiated polymerization in above-mentioned solution, control solution
PH value is at 4-5, and compound enzyme is horseradish peroxidase and glucoseoxidase；
Water, ethanol and washing with acetone, vacuum drying are used in 3rd step, reaction after terminating, finally grind and obtain
Powdery product.
High crystalline polyaniline the most according to claim 1, it is characterised in that described in the first step
Aniline molar concentration is 0.086M, and described sodium chloride concentration is 0.2-0.6M, described magnesium sulfate concentration
For 0.4-0.8M, described aluminum trichloride concentration is 0.2-0.6M, and described time of repose is more than 1 day.
High crystalline polyaniline the most according to claim 1, it is characterised in that described sodium chloride is dense
Degree is 0.4M.
High crystalline polyaniline the most according to claim 1, it is characterised in that described in second step
Horseradish peroxidase is 10mg/ml, described glucose and aniline with the concentration of glucoseoxidase
Mol ratio is 1:1, and described solution ph is 4.5, and described polymerization reaction time is 1-2 days.
High crystalline polyaniline the most according to claim 1, it is characterised in that described in the 3rd step
Baking temperature is at 60 DEG C, and drying time is more than 12h.
6. the preparation method of a high crystalline polyaniline, it is characterised in that described high crystalline polyaniline leads to
Cross following steps to prepare:
A, being dissolved in inorganic salt solution by aniline, be placed in the electric field of 10-100V standing, inorganic salt is selected from
One in sodium chloride, magnesium sulfate or aluminum chloride；
B, compound enzyme and glucose are joined initiated polymerization in above-mentioned solution, control solution ph
At 4-5, compound enzyme is horseradish peroxidase and glucoseoxidase；
Water, ethanol and washing with acetone, vacuum drying are used in c, reaction after terminating, finally grind and obtain powder
Product.
The preparation method of high crystalline polyaniline the most according to claim 6, it is characterised in that step
Aniline molar concentration described in a is 0.086M, and described sodium chloride concentration is 0.2-0.6M, described
Magnesium sulfate concentration is 0.4-0.8M, and described aluminum trichloride concentration is 0.2-0.6M, and time of repose is 1 day
Above.
The preparation method of high crystalline polyaniline the most according to claim 6, it is characterised in that described
Sodium chloride concentration be 0.4M.
The preparation method of high crystalline polyaniline the most according to claim 6, it is characterised in that step
Horseradish peroxidase described in b is 10mg/ml, described Portugal with the concentration of glucoseoxidase
Grape sugar is 1:1 with aniline mol ratio, and described solution ph is 4.5, and described polymerization reaction time is
1-2 days；Baking temperature described in step c is at 60 DEG C, and drying time is more than 12h.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6018018A (en) * | 1997-08-21 | 2000-01-25 | University Of Massachusetts Lowell | Enzymatic template polymerization |
| CN1730510A (en) * | 2005-09-16 | 2006-02-08 | 西北师范大学 | Water-soluble high temperature-resistant polyaniline conducting material and its preparation method |
| CN1814652A (en) * | 2006-03-02 | 2006-08-09 | 扬州大学 | Polyaniline with electrochemical activity under high-pH value and preparing method |
| CN101942090A (en) * | 2010-09-10 | 2011-01-12 | 太原理工大学 | Preparation method of nano-fiber poly-aniline |
-
2012
- 2012-11-30 CN CN201210506429.9A patent/CN103848987B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6018018A (en) * | 1997-08-21 | 2000-01-25 | University Of Massachusetts Lowell | Enzymatic template polymerization |
| CN1730510A (en) * | 2005-09-16 | 2006-02-08 | 西北师范大学 | Water-soluble high temperature-resistant polyaniline conducting material and its preparation method |
| CN1814652A (en) * | 2006-03-02 | 2006-08-09 | 扬州大学 | Polyaniline with electrochemical activity under high-pH value and preparing method |
| CN101942090A (en) * | 2010-09-10 | 2011-01-12 | 太原理工大学 | Preparation method of nano-fiber poly-aniline |
Non-Patent Citations (1)
| Title |
|---|
| 在外加电场下合成聚苯胺及其衍生物;商凡;《中国优秀硕士学位论文全文数据库 工程科技I辑》;20120715(第7期);第2章第2.2.2 实验方法部分，2.3.5XRD分析部分 * |
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